Method for manufacturing pixel definition layer
Patent Information
- Application Number
- JP2024137870
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-08-19
- Filing Date
- 2024-08-19
- Publication Date
- 2025-03-03
AI Technical Summary
【0075】 〔発明の効果〕 本発明は、2つのパターニング工程を1つに統合して段差を形成する着色パターンを電極基板上に実現して、色相が鮮明なだけでなく、ディスプレイの信頼性及び寿命を高めるためのものである。すなわち、露光及び現像工程後、画素分離層とメタルマスク支持層とを一度に形成して、工程時間短縮及び追加の現像工程及び後熱処理工程によるパネルの損傷を最小化し、画素収縮(pixel shrinkage)を防止して輝度減少と寿命減少を最小化するものである。
Smart Images

Figure 2025028783000001_ABST
Abstract
Description
Detailed Description of the Invention
[0001] [Technical field] The present invention relates to a method for fabricating a pixel defining layer of a light emitting display device using a photosensitive composition.
[0002] [Background technology] The most widely used flat panel displays include liquid crystal display devices (LCDs), organic light emitting display devices (OLEDs), etc. Among them, OLEDs have advantages such as low power consumption, fast response speed, high color reproduction rate, high brightness, and wide viewing angle.
[0003] In the case of the organic light emitting display device, a polarizing film is used to block external light that is reflected from the panel. However, the polarizing film has a drawback in that it is not suitable for application to a flexible device due to a lack of bending properties.
[0004] As a method for solving the above problems, a method of forming an inorganic film for blocking light on the upper substrate in addition to the color filter and black matrix has been proposed, but the method has a limit in obtaining a desired level of anti-reflection effect and does not specifically propose a method for replacing the polarizing film.
[0005] Meanwhile, the colored pattern is red, green, and blue color filters, and is used not only in liquid crystal displays but also in organic light-emitting displays.
[0006] In manufacturing the colored pattern, various kinds of organic pigments as well as carbon black and inorganic pigments are used as colorants, and the pigment dispersion in which these are dispersed is mixed with other compositions to form a pattern. In this case, before the organic light-emitting layer is deposited, a photolithography process is added to support a metal mask for deposition, and then the deposition process is carried out.
[0007] An organic light-emitting display made with pixels formed in this way can achieve clearer colors, but since another supporting layer is formed on the colored pattern, the process time increases, and the addition of coating, exposure, development, and heat curing processes damages the panel, which can cause problems such as outgassing, pixel shrinkage, dark spots, and electrode oxidation, reducing the lifespan and brightness of the organic light-emitting display.
[0008] Summary of the Invention [Problem to be solved by the invention] In an attempt to solve the problems of the prior art, one embodiment of the present invention integrates the processes for making two layers into one process to reduce damage to the panel, thereby realizing a colored pattern on an electrode substrate with a short process time, thereby not only achieving vivid colors but also improving the reliability and lifespan of the display.
[0009] In other words, if the transmittance of some sections of a negative-type photomask that transmits light and hardens is reduced to vary the amount of irradiation, after development, the degree of hardening differs depending on the amount of irradiation, forming steps in the pattern, thereby realizing two layers in one process.
[0010] Yet another embodiment is to provide an organic light emitting display device including a pixel defining layer manufactured by the method.
[0011] Yet another embodiment is to provide an electronic device including the organic light emitting display device.
[0012] [Means for solving the problem] The method for manufacturing a pixel definition layer according to the present invention includes steps of applying and coating a photosensitive composition; pre-baking; exposing; developing; and post-heat treatment. In the exposure step, it is preferable to form one or more layers by dividing the photomask transmittance into three ranges, namely, 0% (non-exposed area), 15 to 60% (half-tone), and 100% (full-tone).
[0013] More preferably, the transmittance of the photomask is 0% (unexposed area), 20 to 50% (half-tone), and 100% (full-tone).
[0014] It is more preferable that the exposure and development steps are carried out at the same time.
[0015] 20 mJ / cm 2 ~400mJ / cm 2 It is preferable to irradiate the film with actinic rays of 1000 nm or more.
[0016] In the exposure step, 90 to 300 mJ / cm 2 It is more preferable to irradiate the film with actinic rays of 1000 nm or more.
[0017] The hot plate temperature in the pre-baking step is preferably 80°C to 150°C.
[0018] More preferably, the hot plate temperature in the pre-baking step is 90°C to 120°C.
[0019] The pre-baking step is preferably performed for 60 to 180 seconds.
[0020] More preferably, the pre-baking step is performed for 100 to 150 seconds.
[0021] After the development step, the thickness of the half-tone is preferably 1.25 to 2.20 μm.
[0022] More preferably, after the developing step, the thickness of the half-tone is 1.40 to 2.00 μm.
[0023] After the development step, the full-tone film preferably has a thickness of 3.20 to 3.42 μm.
[0024] More preferably, after the developing step, the full-tone has a thickness of 3.25 to 3.35 μm.
[0025] The photosensitive composition preferably contains a colorant.
[0026] The colorant preferably includes one or more of an inorganic dye, an organic dye, an inorganic pigment, and an organic pigment.
[0027] The colorant is preferably contained in an amount of 1 to 40% by weight based on the total amount of the photosensitive composition.
[0028] The colorant is preferably pretreated with a dispersing agent; or a water-soluble inorganic salt and a wetting agent.
[0029] The average particle size of the colorant is preferably 20 nm to 110 nm.
[0030] The photosensitive composition preferably includes a patterning resin that includes an acrylic binder resin, a cardo binder resin, or a combination thereof.
[0031] The weight average molecular weight of the acrylic binder resin is preferably 3,000 g / mol to 150,000 g / mol.
[0032] The cardo-based binder resin preferably contains a repeating structure of the following formula 1:
[0033] [ka]
[0034] In the above Chemical Formula 1,
[0035] 1) R 1 and R 2 are each independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group: C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0036] 2) R 1 and R 2 can form a ring with adjacent groups,
[0037] 3) m and n are each independently an integer of 0 to 4;
[0038] 4) A 1 and A 2 are each independently represented by the following formula 2 or 3:
[0039] [ka]
[0040] [ka]
[0041] In the above Chemical Formula 2 and Chemical Formula 3,
[0042] 4-1) * indicates the linkage site,
[0043] 4-2) R 3 ~R 6 are independently hydrogen; deuterium; halogen; C 6 ~C 30aryl groups of the formula: 2 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group: C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0044] 4-3) R 3 ~R 6 can form a ring with adjacent groups,
[0045] 4-4) Y 1 and Y 2 are each independently represented by the following formula 6 or 7:
[0046] [ka]
[0047] [ka]
[0048] In the above Chemical Formula 6 and Chemical Formula 7,
[0049] 4-4-1) * indicates the bond position,
[0050] 4-4-2)R 9 is hydrogen or methyl,
[0051] 4-4-3)R 10 ~R 13 are independently hydrogen; deuterium; halogen; C6 ~C 30 aryl groups; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 30 Heterocyclic group; C 6 ~C30 aliphatic ring and aromatic ring fused ring group; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0052] 4-4-4)L 1 ~L 3 are each independently a single bond; a fluorenylene group; C 2 ~C 30 Arylene;C 2 ~C 30 Heterocycle of;C 1 ~C 30 Alkoxylenes;C 2 ~C 30 Alkyleneoxy;C 6 ~C 30 Aryloxy group; C 2 ~C 30 is a polyethyleneoxy group of the formula
[0053] 4-4-5) q and r are each independently an integer of 0 to 3; provided that q+r=3;
[0054] 5) In the polymer chain of the resin containing the repeating unit represented by chemical formula 1, 1 and A 2 The ratio is 9:1 to 1:9.
[0055] 6) X 1is a single bond; O; CO; SO2; CR'R"; SiR'R"; Chemical formula 4 below; or Chemical formula 5,
[0056] 6-1) R' and R" are each independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups, C containing at least one heteroatom of O, N, S, Si and P; 2 ~C 30 Heterocyclic groups; C6-C30 fused aliphatic and aromatic ring groups; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group: C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0057] (6-2) R' and R" can form a ring together with adjacent groups,
[0058] [ka]
[0059] [ka]
[0060] In the above Chemical Formula 4 and Chemical Formula 5,
[0061] 6-3) * indicates the bond position,
[0062] 6-4) R 7 ~R 8 are independently hydrogen; deuterium; halogen; C 6 ~C 30aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0063] 6-5) o and p are each independently an integer of 0 to 4;
[0064] 7) X 2 is C 6 ~C 30 aryl groups, C containing at least one heteroatom of O, N, S, Si and P; 2 ~C 30 Heterocyclic groups of C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring, C 1 ~C 20 Alkyl groups of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0065] 8) The R', R", and X 2 , L 1 ~L 3 , R 1~R 8 and R 10 ~R 13 are deuterium, halogen, and C, respectively. 1 ~C 30 or C 6 ~C 30 aryl groups, substituted or unsubstituted silane groups;siloxane groups;boron groups;germanium groups;cyano groups;amino groups;nitro groups;C 1 ~C 30 Alkylthio group; C 1 ~C 30 Alkoxy group; C 6 ~C 30 Arylalkoxy groups of C 1 ~C 30 Alkyl groups of C 2 ~C 30 Alkenyl group of C 2 ~C 30 Alkynyl group of C 1 ~C 30 Aryl groups; deuterium-substituted C 6 ~C 30 an aryl group; a fluorenyl group; a C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 2 ~C 30 Heterocyclic group; C 3 ~C 30 an aliphatic ring group; C 7 ~C 30 Aryl alkyl group;C 8 ~C 30 and combinations thereof, wherein adjacent substituents may be joined to form a ring.
[0066] The cardo resin preferably has a weight average molecular weight of 1,000 to 100,000 g / mol.
[0067] The cardo resin is preferably contained in an amount of 1 to 30% by weight based on the total amount of the photosensitive composition.
[0068] The photosensitive composition preferably contains 1 to 40% by weight of the reactive unsaturated compound based on the total amount of the photosensitive composition.
[0069] The photosensitive composition preferably contains a photoinitiator in an amount of 0.01 to 10% by weight based on the total amount of the photosensitive composition.
[0070] In another embodiment, the present invention preferably provides a pixel defining layer manufactured by the above manufacturing method.
[0071] In still another embodiment, the present invention preferably provides an organic light emitting display device including the pixel defining layer.
[0072] The pixel definition layer is preferably formed on a pixel electrode included in an organic light emitting display device.
[0073] In another embodiment, the present invention preferably provides an electronic device including the display device and a controller for driving the display device.
[0074] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram illustrating an organic light emitting display device according to the present invention.
[0075] [Effects of the Invention] The present invention integrates two patterning processes into one to realize a colored pattern that forms a step on an electrode substrate, thereby not only providing vivid colors but also improving the reliability and lifespan of the display. That is, after the exposure and development processes, the pixel separation layer and the metal mask support layer are formed at once, shortening the process time and minimizing damage to the panel due to additional development and post-heat treatment processes, and preventing pixel shrinkage to minimize reduction in brightness and lifespan.
[0076] [Mode for carrying out the invention] Some embodiments of the present invention will be described in detail below with reference to the accompanying drawings. When reference numerals are used to designate components in each drawing, the same reference numerals are used to designate the same components even if they are displayed in different drawings.
[0077] In the description of the present invention, if it is determined that a specific description of related publicly known configurations or functions may make the gist of the present invention unclear, the detailed description may be omitted. When "comprises," "has," "consists of," and the like are used in this specification, other parts may be added as long as "only" is not used. When a component is expressed in the singular, it includes the plural unless otherwise expressly specified.
[0078] In addition, in describing the components of the present invention, terms such as 1st, 2nd, A, B, (a), (b), etc. are used to distinguish the components from other components, and the terms do not limit the nature, order, sequence, number, etc. of the components.
[0079] In describing the positional relationship of components, when two or more components are described as being "coupled," "coupled," or "connected," it should be understood that the two or more components may be directly "coupled," "coupled," or "connected," but that the two or more components may also be "coupled" or "connected" through further "intervening" components, where the other components may be included in one or more of the two or more components that are "coupled," "coupled," or "connected" to each other.
[0080] In addition, when a component such as a layer, film, region, or plate is described as being "on" or "on" another component, this should be understood to include not only the case where the component is "directly on" the other component, but also the case where there is another component in between. Conversely, when a component is described as being "directly on" another part, it should be understood to mean that there is no other part in between.
[0081] In describing a temporal sequence relating to components, methods of operation, methods of production, etc., when the temporal or flow sequence is described using, for example, "after," "following," "next to," or "before," this also includes cases where the sequence is not consecutive, unless "immediately" or "directly" is used.
[0082] On the other hand, when numerical values or corresponding information for components are mentioned, even if there is no separate explicit description, the numerical values or corresponding information can be interpreted as including an error range that may occur due to various factors (e.g., process factors, internal or external impacts, noise, etc.).
[0083] The terms used in this specification and the appended claims are as follows, unless otherwise specified, within the scope of the present invention.
[0084] The term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise stated.
[0085] The term "alkyl" or "alkyl group", as used in this application, unless otherwise specified, means the radical of a saturated aliphatic group having 1 to 60 carbons linked by a single bond, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.
[0086] The term "haloalkyl group" or "haloalkyl group" as used herein means, unless otherwise specified, an alkyl group substituted with a halogen.
[0087] The terms "alkenyl" or "alkynyl" as used herein, unless otherwise specified, include groups having double or triple bonds, straight or branched chain groups, and having from 2 to 60 carbon atoms, but are not limited thereto.
[0088] The term "cycloalkyl" as used in this application, unless otherwise specified, means an alkyl group forming a ring having 3 to 60 carbon atoms, but is not limited thereto.
[0089] The term "alkoxy group" or "alkyloxy group" as used herein means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.
[0090] The terms "alkeneoxyl group," "alkenoxy group," "alkenyloxyl group," or "alkenyloxy group" as used in this application mean an alkenyl group having an oxygen radical attached thereto, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited to this.
[0091] The terms "aryl group" and "arylene group" used in this application each have 6 to 60 carbon atoms, unless otherwise specified, but are not limited thereto. In this application, the aryl group or arylene group includes a single ring, a ring assembly, a fused multiple ring system compound, etc. For example, the aryl group includes a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, and a substituted fluorenyl group, and the arylene group includes a fluorenylene group and a substituted fluorenylene group.
[0092] The term "ring assemblies" as used in this application means two or more ring systems (single ring or joined ring systems) directly linked to each other by single or double bonds, and the number of such direct connections between rings is one less than the total number of ring systems in the compound. Ring assemblies can be identical or different ring systems directly linked to each other by single or double bonds.
[0093] In the present application, the aryl group includes ring assemblies, and therefore includes biphenyl and terphenyl in which a single aromatic ring, a benzene ring, is connected by a single bond. The aryl group also includes compounds in which an aromatic ring system connected to a single aromatic ring is connected by a single bond, and therefore includes compounds in which an aromatic ring system, such as fluorene, is connected to a single aromatic ring, such as a benzene ring.
[0094] The term "fused ring system" used in this application means a fused ring form sharing at least two atoms, including a fused ring form of two or more hydrocarbon ring systems and a fused ring form of at least one heterocyclic ring system containing at least one heteroatom. Such fused ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings, or combinations of these rings. For example, in the case of an aryl group, it may be a naphthalenyl group, a phenanthrenyl group, a fluorenyl group, etc., but is not limited thereto.
[0095] The term "spiro compound" as used in this application has a "spiro union", which means a union in which two rings share only one atom. In this case, the atom shared by the two rings is called a "spiro atom". Depending on the number of spiro atoms in a compound, these compounds are called "monospiro-", "dispiro-", and "trispiro-" compounds, respectively.
[0096] The terms "fluorenyl group", "fluorenylene group", and "fluorenetriyl group" used in this application mean, unless otherwise specified, a monovalent, divalent, or trivalent functional group in which R, R', R" and R'" are all hydrogen in the following structure, respectively, and "substituted fluorenyl group", "substituted fluorenylene group", or "substituted fluorenetriyl group" means that at least one of the substituents R, R', R" and R'" is a substituent other than hydrogen, and includes the case where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In this specification, regardless of the valence such as monovalent, divalent, or trivalent, fluorenyl group, fluorenylene group, and fluorenetriyl group can all be named fluorene group.
[0097] [ka]
[0098] Furthermore, the R, R', R" and R'" are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene, or phenanthrene, and the heterocyclic group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, benzofuranquinazoline, or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group may be a monovalent functional group or a divalent functional group of 9,9-dimethylfluorene, 9,9-diphenylfluorene, and 9,9'-spirobi[9H-fluorene], respectively.
[0099] The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl groups" or "heteroarylene groups" but also non-aromatic rings, and means, but is not limited to, a ring having 2 to 60 carbon atoms and containing one or more heteroatoms, unless otherwise specified. The term "heteroatom" as used herein means N, O, S, P, or Si, unless otherwise specified, and heterocyclic group means a single ring, ring assembly, fused multiple ring system, spiro compound, etc., containing a heteroatom.
[0100] For example, a "heterocyclic group" can have SO instead of the carbon that forms the ring, as in the compound below. 2 , P=O and other heteroatomic groups may also be included.
[0101] [ka]
[0102] The term "ring" as used in this application includes single and multiple rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.
[0103] The term "polycyclic" as used in this application includes ring assemblies such as biphenyls, terphenyls, fused multiple ring systems, and spiro compounds, and includes aromatic as well as non-aromatic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom.
[0104] The term "aliphatic cyclic group" used in the present application means a cyclic hydrocarbon other than aromatic hydrocarbon, including a single ring, a ring assembly, a fused multiple ring system, a spiro compound, etc., and means a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto. For example, a fusion of an aromatic ring, benzene, and a non-aromatic ring, cyclohexane, also falls under the category of an aliphatic ring.
[0105] Also, when the prefixes are named consecutively, it means that the substituents are listed in the order in which they are written, for example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where the arylcarbonyl group is a carbonyl group substituted with an aryl group.
[0106] In addition, unless otherwise specified, in the term "substituted or unsubstituted" used in this application, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~C 30 Alkyl groups of C 1 ~C 30 Alkoxy groups, C 1 ~C 30 Alkylamine group, C 1 ~C 30 Alkylthiophene group, C 6 ~C 30 Arylthiophene group, C 2 ~C 30 Alkenyl group, C 2 ~C 30 Alkynyl groups, C 3 ~C 30 Cycloalkyl groups of C 6 ~C 30 Aryl groups, deuterium-substituted C 6 ~C 30 Aryl groups of C 8 ~C 30 arylalkenyl groups, silane groups, boron groups, germanium groups, and C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; 2 ~C 30 The term "substituted" means that the heterocyclic group is substituted with one or more substituents selected from the group consisting of the following heterocyclic groups, but is not limited to these substituents.
[0107] In this application, the "functional group name" corresponding to an aryl group, an arylene group, a heterocyclic group, etc., which are exemplified as examples of each symbol and its substituent, can be described as the "functional group name reflecting the valence" or as the "parent compound name." For example, in the case of "phenanthrene," which is a type of aryl group, the name of the group can be described by dividing the valence, such as "phenanthryl (group)" for a monovalent "group" and "phenanthrylene (group)" for a divalent group, or it can be described as the parent compound name "phenanthrene" regardless of the valence.
[0108] Similarly, pyrimidine can be described as "pyrimidine" regardless of the valence, or as the "name of the group" of the relevant valence, such as pyrimidinyl (group) in the case of a monovalent group, pyrimidinylene (group) in the case of a divalent group, etc. Thus, when the type of substituent is described in the name of a parent compound in this application, it can mean an n-valent "group" formed by eliminating hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.
[0109] In addition, in this specification, when describing the names of compounds and substituents, numbers and letters indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine may be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene as dimethylfluorene, etc. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline may be described as benzoquinoxaline.
[0110] In addition, unless otherwise expressly stated, the chemical formulas used in the present application are applied in the same manner as the substituent definitions according to the index definitions of the following chemical formulas.
[0111] [ka]
[0112] where a is an integer of 0, the substituent R 1In other words, when a is 0, it means that all the carbons forming the benzene ring are bonded to hydrogen, and in this case, the hydrogen bonded to the carbon may be omitted and the chemical formula or compound may be written. Also, when a is an integer of 1, one substituent R 1 is bonded to any one of the carbons forming a benzene ring. When a is an integer of 2 or 3, it can be bonded as shown below. When a is an integer of 4 to 6, it can be bonded to a carbon of the benzene ring in a similar manner. When a is an integer of 2 or more, R 1 may be the same as or different from each other.
[0113] [ka]
[0114] Unless otherwise stated in this application, by forming a ring it is meant that adjacent groups are joined together to form a single ring or joined rings, and the single rings and joined rings formed include hydrocarbon rings as well as heterocycles containing at least one heteroatom, and include aromatic and non-aromatic rings.
[0115] In addition, unless otherwise specified in this specification, when describing a fused ring, the number in "number-fused ring" indicates the number of fused rings. For example, a form in which three rings are fused to each other, such as anthracene, phenanthrene, benzoquinazoline, etc., can be represented as a 3-fused ring.
[0116] In contrast, the term "bridged bicyclic compound" as used herein, unless otherwise specified, refers to a compound in which two rings share three or more atoms to form a ring, where the shared atoms include carbon or heteroatoms.
[0117] In this application, the organic electronic element may refer to a component(s) between a positive electrode and a negative electrode, or may refer to an organic light-emitting diode or an organic light-emitting display device including a positive electrode, a negative electrode, and a component(s) located therebetween.
[0118] In some cases, the display device in this application may refer to an organic electric element, an organic light-emitting diode, and a panel including the same, or an electronic device including a panel and a circuit. Here, for example, the electronic device may include lighting devices, solar cells, portable or mobile terminals (e.g., smartphones, tablets, PDAs, electronic dictionaries, PMPs, etc.), navigation terminals, game consoles, various TVs, various computer monitors, etc., and may be any type of device that includes the above-mentioned component(s) without being limited thereto.
[0119] Hereinafter, the implementation of the present invention will be described in detail, but it should be understood that the present invention is not limited to the above embodiment, and is defined only by the scope of the claims that follow.
[0120] A composition including a colorant according to an embodiment of the present invention is used to manufacture a red pattern, a green pattern, a blue pattern, or a black matrix, a pixel defining layer (PDL).
[0121] The black pixel defining layer (PDL) according to an embodiment of the present invention may further include an organic black pigment or black dye as an additional colorant other than the colorant contained in the colorant. For example, an organic pigment may be used alone or an organic pigment may be mixed with a color pigment, and in this case, since a color pigment with insufficient light blocking properties is mixed, there is an advantage that the strength of the film (layer) or adhesion to the substrate does not decrease even if the amount of the colorant increases relatively. The negative pixel defining layer (Negative PDL) according to an embodiment of the present invention may include a black pigment or black dye as an additional colorant instead of the colorant contained in the colorant.
[0122] Each component will be specifically described below.
[0123] 1. The manufacturing process of the negative pixel defining layer is as follows:
[0124] (1) Application and coating stage
[0125] The photosensitive composition is a low-viscosity liquid sample, and a spin coater or slit coater is used to coat the substrate at a consistent thickness after application. The faster the spin coater rotates, the less the thickness is, but the greater the reduction in the deviation in flatness over the surface area. For coating large substrates, a slit coater is more preferable than a spin coater. After coating, the surface becomes fluid due to the remaining solvent, which can cause poor flatness. To overcome this, a vacuum chamber dryer (VCD) is used to remove part of the solvent, reducing the fluidity on the surface.
[0126] (2) Pre-bake stage
[0127] This is a process in which the coated substrate is heated at a certain temperature and time on a hot plate or in an oven to remove a portion of the solvent contained in the coating film. If the surface or deep part of the coating film is not dried, contamination of the photomask occurs during exposure in the next process, and the exposed part does not harden well when irradiated with ultraviolet light, and the uncured part is removed without forming a pattern in the development process.
[0128] (3) Exposure stage
[0129] After the pre-bake process is completed, the photomast with the pattern is used to irradiate actinic rays (ultraviolet rays) to harden the film. The types of lamps that generate actinic rays include LED lamps and metal (mercury) lamps, and the wavelengths are g-line (436nm), h-line (405nm), i-line (365nm), and deep UV (<260nm), which can be used individually or in combination.
[0130] (4) Development stage
[0131] In the exposure step, exposed and non-exposed areas are separated by a photomask when irradiated with actinic radiation. In the case of a positive type, the exposed areas are dissolved by a developer, while the non-exposed areas are resistant to the developer, leaving a pattern. In the case of a negative type, the exposed areas are hardened and resistant to the developer, while the non-exposed areas are developed. The black pixel defining layer (Black PDL) manufactured using a composition containing the colorant of the present invention is a negative type, and a pattern is formed by dividing the exposed areas (hardened) and non-exposed areas (developed).
[0132] 2. The composition forming the negative pixel defining layer containing the colorant is as follows:
[0133] (1) Patterning resin
[0134] The patterning resin according to an embodiment of the present invention may include an acrylic binder resin, a cardo binder resin, or a combination thereof.
[0135] The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing one or more acrylic repeating units.
[0136] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxy groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof. The first ethylenically unsaturated monomer may be contained in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight, based on the total amount of the acrylic binder resin.
[0137] Examples of the second ethylenically unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, and vinylbenzyl methyl ether; unsaturated carboxylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and phenyl (meth)acrylate; unsaturated carboxylate aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; carboxylate vinyl ester compounds such as vinyl acetate; and unsaturated carboxylate glycidyl ester compounds such as glycidyl (meth)acrylate; cyanide vinyl compounds such as (meth)acrylonitrile; and unsaturated amide compounds such as (meth)acrylamide. These may be used alone or in combination of two or more.
[0138] Specific examples of the acrylic binder resin include, but are not limited to, (meth)acrylic acid / benzyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene copolymer, (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. These may be used alone or in combination of two or more. The weight average molecular weight of the acrylic binder resin may be 3,000 g / mol to 150,000 g / mol, for example, 5,000 g / mol to 50,000 g / mol, for example, 20,000 g / mol to 30,000 g / mol.
[0139] Cardo resins contain a repeating structure as shown in Formula 1 below.
[0140] [ka]
[0141] In the above Chemical Formula 1,
[0142] 1) R 1 and R 2 are independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0143] 2) adjacent groups of R' and R" can form a ring;
[0144] 3) m and n are each independently an integer of 0 to 4;
[0145] 4) A 1 and A 2 are each independently represented by the following formula 2 or 3:
[0146] [ka]
[0147] [ka]
[0148] In the above Chemical Formula 2 and Chemical Formula 3,
[0149] 4-1) * indicates the linkage site,
[0150] 4-2) R 3 ~R 6 are independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl groups of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0151] 4-3) R 3 ~R 6 can form a ring with adjacent groups,
[0152] 4-4) Y 1 and Y 2 are each independently represented by the following formula 6 or 7:
[0153] [ka]
[0154] [ka]
[0155] In the above Chemical Formula 6 and Chemical Formula 7,
[0156] 4-4-1) * indicates the bond position,
[0157] 4-4-2)R 9 is hydrogen or methyl,
[0158] 4-4-3)R 10 ~R 13 are independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups; C containing at least one hetero group selected from O, N, S, Si, and P; 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl groups of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0159] 4-4-4)L 1 ~L 3 are each independently a single bond; a fluorenylene group; C 2 ~C 30 Alkylene;C 6 ~C 30 Arylene;C 2 ~C 30 Heterocycle of;C 1 ~C 30 Alkoxylenes;C 2 ~C 30 alkyleneoxy; C6-C30 aryloxy; C 2 ~C 20 is a polyethyleneoxy group of the formula
[0160] 4-4-5) q and r are each independently an integer of 0 to 3, provided that q+r=3;
[0161] 5) In the polymer chain of the resin containing the repeating unit represented by chemical formula 1, 1 and A 2 The ratio is 9:1 to 1:9.
[0162] 6) X 1 is a single bond; O; CO; SO2; CR'R"; SiR'R"; the following chemical formula 4; or chemical formula 5,
[0163] 6-1) R' and R" are each independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0164] 6-2) R' and R" can form a ring with adjacent groups,
[0165] [ka]
[0166] [ka]
[0167] In the above Chemical Formulas 4 and 5,
[0168] 6-3) * indicates the bond position,
[0169] 6-4) R 7 ~R 8 are independently hydrogen; deuterium; halogen; C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30 an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0170] 6-5) o and p are each independently an integer of 0 to 4;
[0171] 7) X 2 is C 6 ~C 30 aryl groups of the formula: 2 ~C 30 Heterocyclic group; C 6 ~C 30 A fused ring group of an aliphatic ring and an aromatic ring; C 1 ~C 20 Alkyl group of C 2 ~C 20 Alkenyl group of C 2 ~C 20 Alkynyl group of C 1 ~C 20 Alkoxy group; C 6 ~C 30an aryloxy group; a fluorenyl group; a carbonyl group; an ether group; or C 1 ~C 20 is an alkoxycarbonyl group of the formula
[0172] 8) The R', R", and X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 are deuterium, halogen, and C, respectively. 1 ~C 30 or C 6 ~C 30 aryl groups or unsubstituted silane groups;siloxane groups;boron groups;germanium groups;cyano groups;amino groups;nitro groups;C 1 ~C 30 Alkylthio group; C 1 ~C 30 Alkoxy group; C 6 ~C 30 Arylalkoxy groups of C 1 ~C 30 Alkyl group of C 2 ~C 30 Alkenyl group of C 2 ~C 30 Alkynyl group of C 6 ~C 30 Aryl groups; deuterium-substituted C 6 ~C 30 an aryl group; a fluorenyl group; a C group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; 2 ~C 30 Heterocyclic group; C 3 ~C 30 an aliphatic ring group; C 7 ~C 30 Aryl alkyl group;C 8 ~C 30 and combinations thereof, wherein adjacent substituents may be joined to form a ring.
[0173] The R', R", and X2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 When is an aryl group, preferably, C 6 ~C 30 More preferably, C 6 ~C 18 The aryl groups may be, for example, phenyl, biphenyl, naphthyl, terphenyl, and the like.
[0174] The R', R", and X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 When is a heterocyclic group, it is preferably 2 ~C 30 More preferably, 2 ~C 18 heterocyclic groups such as dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.
[0175] The R′, R″ and R 1 ~R 8 and R 10 ~R 13 When is a fluorenyl group, it may be preferably 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl, 9,9'-spirobifluorene, or the like.
[0176] Said L 1 ~L 3 When is an arylene group, preferably, C 6 ~C 30 More preferably, the arylene group is 6 It may be an arylene group having 1 to 18 carbon atoms, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.
[0177] The R', R", and X 2 , R 1 ~R8 and R 10 ~R 13 When is an alkyl group, it is preferably 1 ~C 10 and may be, for example, methyl, t-butyl, and the like.
[0178] The R', R", and X 2 , R 1 ~R 8 and R 10 ~R 13 When is an alkoxy group, preferably, C 1 ~C 20 More preferably, an alkoxy group of C 1 ~C 10 The alkoxy group may be, for example, methoxy, t-butoxy, and the like.
[0179] The R', R", and X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 The ring formed by bonding adjacent groups of is C 6 ~C 60 an aromatic ring group; a fluorenyl group; a C group containing at least one heteroatom selected from O, N, S, Si and P; 2 ~C 60 or C 3 ~C 60 For example, when adjacent groups are bonded to each other to form an aromatic ring, preferably, 6 ~C 20 More preferably, the aromatic ring of 6 ~C 14 can form aromatic rings such as benzene, naphthalene, phenanthrene, etc.
[0180] The cardo resin may be prepared by mixing two or more of the following: a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; an anhydride compound such as benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride; a glycol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; a phosphorus compound such as triphenylphosphine; and an amine or ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, and benzyltriethylammonium chloride.
[0181] The weight average molecular weight of the cardo resin may be 1,000 to 100,000 g / mol, preferably 1,000 to 50,000 g / mol, and more preferably 1,000 to 30,000 g / mol. When the weight average molecular weight of the resin is within the above range, the pattern formation is performed well without residue during the production of the light-shielding layer, and a good pattern can be obtained without loss of film thickness during development. The resin may be included in an amount of 1 to 30 wt %, more preferably 3 to 20 wt %, based on the total amount of the photosensitive resin composition. When the resin is included within the above range, excellent sensitivity, developability, and adhesion (adhesion) can be obtained.
[0182] (2) Reactive unsaturated compounds
[0183] The reactive unsaturated compound, which is essential for a negative pattern, has an ethylenically unsaturated double bond, and thereby undergoes sufficient polymerization upon exposure in the pattern formation process, thereby enabling the formation of a pattern having excellent heat resistance, light resistance and chemical resistance.
[0184] Specific examples of the reactive unsaturated compound include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, and tripentaerythritol octaacrylate.
[0185] Examples of commercially available products of the reactive unsaturated compounds are as follows:
[0186] Examples of the bifunctional ester of (meth)acrylic acid include Aronix M-210, M-240, M-6200, etc., manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA, HX-220, R-604, etc., manufactured by Nippon Kayaku Co., Ltd.; and V-260, V-312, V-335HP, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd.
[0187] Examples of the trifunctional esters of (meth)acrylic acid include ARONIX M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc., available from Toagosei Chemical Industry Co., Ltd.; KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc., available from Nippon Kayaku Co., Ltd.; and V-295, V-300, V-360, etc., available from Osaka Organic Chemical Industry Co., Ltd.
[0188] The above products can be used alone or in combination of two or more.
[0189] The reactive unsaturated compound may be treated with an acid anhydride to provide better developability. The reactive unsaturated compound may be contained in an amount of 1 to 40% by weight, for example, 1 to 20% by weight, based on the total amount of the photosensitive resin composition. When the reactive unsaturated compound is contained within the above range, curing occurs sufficiently upon exposure in the pattern formation process, resulting in excellent reliability, and the pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion.
[0190] (3) Photoinitiator
[0191] To realize a negative pattern in photolithography, a photoradical initiator must be used. The photoinitiator has a molar absorption coefficient of 10,000 (L / mol cm) or more in the 330-380 nm region, and a 5% weight loss occurs at 200°C or less. Here, the molar absorption coefficient can be calculated by the Beer-Lambert Law. The weight loss was measured by heating up to 300°C at a rate of 5°C per minute in a nitrogen atmosphere using a TGA.
[0192] The photopolymerization initiator is an initiator commonly used in photosensitive resin compositions, and examples of the photopolymerization initiator that can be used include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, and triazine-based compounds.
[0193] Examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-(morpholinophenyl)-butan-1-one, and the like.
[0194] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.
[0195] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
[0196] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
[0197] Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl) )-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth1-yl)4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like.
[0198] In addition to the above compounds, the photoinitiator may be a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a non-imidazole-based compound, or the like.
[0199] The photoinitiator may be a radical polymerization initiator such as a peroxide-based compound or an azobis-based compound.
[0200] Examples of the peroxide-based compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl) hydroperoxide, and the like. peroxyhexane, 1,3-bis(t-butyloxyisopropyl)benzene, t-butylperoxyvaleric acid n-butyl ester and other dialkyl peroxides; 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate and other alkyl peresters; di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis-4-t-butylcyclohexylperoxydicarbonate, diisopropylperoxydicarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate and other percarbonates.
[0201] Examples of the azobis compounds include 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α'-azobis(isobutylnitrile), and 4,4'-azobis(4-cyanovaleric acid).
[0202] The photoinitiator may be used together with a photosensitizer that absorbs light, becomes excited, and then transfers the energy to initiate a chemical reaction. Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc.
[0203] The photoinitiator may be included in an amount of 0.01 to 10 wt %, for example, 0.1 to 5 wt %, based on the total amount of the photosensitive composition. When the photoinitiator is included within this range, curing occurs sufficiently upon exposure in the pattern formation process, so that excellent reliability can be obtained, and the pattern has excellent heat resistance, light resistance, and chemical resistance, excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiator can be prevented.
[0204] (4) Colorant
[0205] As the colorant, organic pigments, inorganic pigments, and dyes can all be used.
[0206] As the colorant, red pigments, green pigments, blue pigments, yellow pigments, black pigments, etc. can be used.
[0207] Examples of the red pigment include CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, and the like.
[0208] Examples of the green pigment include halogen-substituted copper phthalocyanine pigments such as CI Green Pigment 36 and CI Green Pigment 7.
[0209] Examples of the blue pigment include copper phthalocyanine pigments such as CI Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3, CI Blue Pigment 15:4, CI Blue Pigment 15:5, and CI Blue Pigment 16.
[0210] Examples of the yellow pigment include isoindoline pigments such as CI Yellow Pigment 139, quinophthalone pigments such as CI Yellow Pigment 138, nickel complex pigments such as CI Yellow Pigment 150, and the like.
[0211] Examples of the black pigment include lactam black, aniline black, perylene black, titanium black, and carbon black.
[0212] In addition, the colorant in the photosensitive resin composition according to the embodiment may include a pigment, a dye, or a combination thereof. For example, the dye may include a phthalocyanine-based compound.
[0213] The pigments and dyes may be used alone or in combination, and are not limited to these examples.
[0214] Among these, the black pigment can be used to efficiently block light in the light-shielding layer. When the black pigment is used, it can be used together with a color correction agent such as anthraquinone pigments, perylene pigments, phthalocyanine pigments, and azo pigments.
[0215] A dispersant may be used together with the pigment in order to disperse the pigment in the photosensitive resin composition. Specifically, the pigment may be surface-treated with a dispersant before use, or the dispersant may be added together with the pigment during the preparation of the photosensitive resin composition.
[0216] The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. Specific examples of the dispersant include polyalkylene glycol and its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc., which may be used alone or in combination of two or more.
[0217] Examples of commercially available dispersant products include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc., from BYK; Examples of such products include EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, and EFKA-450 from Cal; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, and Solsperse 28000 from Zeneka; and PB711 and PB821 from Ajinomoto.
[0218] The dispersant may be contained in an amount of 0.1% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the dispersibility of the composition is excellent, and therefore the stability, developability, and patternability during the production of the light-shielding layer are excellent.
[0219] The pigment may be pretreated with a water-soluble inorganic salt and a wetting agent before use. When the pigment is pretreated, the average particle size of the pigment may be reduced.
[0220] The pretreatment includes kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained from the kneading step.
[0221] The kneading is carried out at a temperature of 40° C. to 100° C., and the filtering and washing are carried out by washing the inorganic salt with water or the like and then filtering.
[0222] Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride.
[0223] The wetting agent serves as a medium for uniformly mixing the pigment and the water-soluble inorganic salt to facilitate pulverization of the pigment. Examples of the wetting agent include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.; alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin polyethylene glycol, and these can be used alone or in combination of two or more.
[0224] The pigment having undergone the kneading step may have an average particle size of 20 nm to 110 nm. When the average particle size of the pigment is within the above range, it is possible to effectively form a fine pattern while having excellent heat resistance and light resistance.
[0225] The pigment may be contained in an amount of 1 to 40% by weight, more specifically 2 to 30% by weight, based on the total amount of the photosensitive resin composition. When the pigment is contained within the above range, the color reproduction rate is excellent, and the curing property and adhesion of the pattern are excellent.
[0226] (5) Solvent
[0227] The solvent used is a material that is compatible with, but does not react with, the cardo resin, the reactive unsaturated compound, the pigment, the cardo compound, and the initiator.
[0228] Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethyl glycol monomethyl ester, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Ketones such as methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; and ketone acid esters such as ethyl pyruvate.
[0229] Also usable are high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.
[0230] Among the above solvents, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate may be used.
[0231] The solvent may be contained as the remainder based on the total amount of the photosensitive resin composition, specifically, 40 to 90% by weight. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus has excellent processability during the production of the pattern layer.
[0232] (6) Other additives
[0233] The photosensitive composition may further contain additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl group or a (meth)acryloxy group; a leveling agent; a fluorine-based surfactant; a silicon-based surfactant; and a radical polymerization initiator in order to prevent stains and spots during application, improve leveling performance, and prevent the generation of residues due to undeveloped state.
[0234] For example, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion to a substrate.
[0235] Examples of the silane coupling agent include trimethoxysilylbenzoic acid, gamma methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma isocyanatepropyltriethoxysilane, gamma glycidoxypropyltrimethoxysilane, and beta epoxycyclohexylethyltrimethoxysilane. These may be used alone or in combination of two or more.
[0236] The silane coupling agent may be contained in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the composition has excellent adhesion, storage stability, and the like.
[0237] In addition, the photosensitive resin composition may further contain a surfactant, for example, a fluorine-based surfactant or a silicon-based surfactant, in order to improve coating properties and prevent the generation of defects, if necessary.
[0238] The fluorine-based surfactant is BM Fluorosurfactants commercially available under the names of BM-1000 (registered trademark), BM-1100 (registered trademark) and the like from Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark) and the like from Dainippon Ink and Chemicals Co., Ltd.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark) and the like from Sumitomo 3M Co., Ltd.; Surflon S-112 (registered trademark), S-113 (registered trademark), S-131, S-141, S-145 and the like from Asahi Glass Co., Ltd.; SH-28PA (registered trademark), S-190 (registered trademark), S-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark) and the like from Dray Silicon Co., Ltd. may also be used.
[0239] As the silicone surfactant, silicone surfactants commercially available under the names EFKA (registered trademark) 3030, EFKA (registered trademark) 3034, EFKA (registered trademark) 3886, etc. from BASF; 3030, 3085, 3236, etc. from AFCONA; and BYK-379, BYK-3550, BYK-3751, BYK-3754, etc. may be used.
[0240] The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within this range, coating uniformity is ensured, spots are not generated, and wetting to glass substrates is excellent. In addition, the photosensitive resin composition may contain other additives such as antioxidants and stabilizers in a certain amount within a range that does not impair physical properties.
[0241] In another embodiment, a patterned pixel defining layer may be formed on a pixel separating portion of an organic light emitting device electrode using the above-mentioned photosensitive resin composition.
[0242] The organic light-emitting display device will now be described with reference to FIG. 1. The organic light-emitting display device according to an embodiment of the present invention may include a substrate 1, a TFT layer 2 on the substrate, a planar layer 3 on the TFT layer, an organic light-emitting element layer 6 on the planar layer, a sealing layer 7 arranged on the organic light-emitting element layer, a touch panel 8 arranged on the sealing layer, a color filter 9 arranged on the touch panel, an OCA layer 11 arranged on the color filter, and a cover glass layer 12 arranged on the OCA layer 11.
[0243] A pixel defining layer 5 according to the present invention is preferably formed on said pixel electrodes 4 .
[0244] The pixel definition layer 5 is preferably formed of one or more layers depending on the photomask transmittance (0% (non-exposed area), 15 to 60% (half-tone), and 100% (full-tone)), more preferably the photomask transmittance is 0% (non-exposed area), 20 to 50% (half-tone), and 100% (full-tone), and more preferably formed of a double layer consisting of half-tone on full-tone.
[0245] Depending on the transmittance of the photomask, the thickness of the half-tone is suitably 30% to 80% of the thickness of the full-tone, and more preferably 35% to 70%. If the thickness of the half-tone is less than 30% of the thickness of the full-tone, the pixel size increases and the brightness increases, but the durability of the manufactured pixel definition layer may decrease. If the thickness of the half-tone is more than 80% of the thickness of the full-tone, the brightness and lifespan of the device are reduced, making it inefficient.
[0246] The substrate 1 may be a flexible substrate. The substrate may be made of a plastic material having excellent heat resistance and durability, such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphtalate (PEN), polycarbonate (PC), polyarylate (PAR), polyetherimide (PEI), and polyethersulphone (PES).
[0247] However, the present invention is not limited thereto, and various flexible materials such as metal foil and thin glass may be used. Alternatively, the substrate may be a rigid substrate, in which case the substrate may be SiO 2 It may also be made of a glass material containing the above as a main component.
[0248] In the case of a bottom emission type where an image is realized in the direction of the substrate, the substrate must be made of a transparent material. However, in the case of a top emission type where an image is realized in the opposite direction of the substrate, the substrate does not necessarily have to be made of a transparent material. In this case, the substrate may be made of a metal. In the case of a metal substrate, the substrate may include one or more selected from the group consisting of carbon, iron, chromium, manganese, nickel, titanium, molybdenum, and stainless steel (SUS), but is not limited thereto.
[0249] A TFT layer 2 may be disposed on the substrate. The term TFT layer referred to in this specification is a common name for a thin film transistor (TFT) array for driving an organic light emitting element, and refers to a driving part for displaying an image. Although only an organic light emitting element and a driving thin film transistor for driving the organic light emitting element are shown in FIG. 1, this is for convenience of explanation, and the present invention is not limited to the illustrated example, and it is obvious to those skilled in the art that a number of thin film transistors, storage capacitors, and various wirings may be further included.
[0250] The TFT layer may be covered and protected by a planarization layer 3. The planarization layer may include an inorganic insulating film and / or an organic insulating film. Examples of inorganic insulating films that can be used for the planarization layer include silicon oxide (SiO 2 ), silicon nitride (SiN x ), silicon oxynitride (SiON), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), tantalum oxide (Ta 2 O 5 ), hafnium oxide (HfO 2 ), zirconium oxide (ZrO 2 ), BST (Barium Strontium Titanate), and PZT (Lead Zirconate-Titanate).
[0251] In addition, examples of organic insulating films that can be used for the planarizing layer 3 may include general-purpose polymers (PMMA, PS), polymer derivatives having a phenol group, acrylic polymers, imide polymers, aryl ether polymers, amide polymers, fluorine polymers, p-xylene polymers, vinyl alcohol polymers, and blends thereof.
[0252] Meanwhile, the planarizing layer may have a composite laminate structure of an inorganic insulating film and an organic insulating film. The planarizing layer may also include the photosensitive composition of the present invention. Details regarding the photosensitive composition of the present invention are the same as those in the above embodiment of the present invention, and therefore will not be described here.
[0253] An organic light emitting device layer may be formed on the planar layer. The organic light emitting device layer may include a pixel electrode 4 formed on the planar layer, a counter electrode 7 disposed opposite the pixel electrode 4, and an organic layer 6 interposed therebetween. When a voltage is applied between the pixel electrode and the counter electrode, the organic layer may emit light. The organic layer may emit red light, green light, blue light, or white light. The organic light emitting display may further include blue, green, and red color filters to express a color image when the organic layer emits white light, or to improve color purity and light efficiency when the organic layer emits red light, green light, or blue light.
[0254] Organic light emitting display devices can be classified into bottom emission types, top emission types, and dual emission types depending on the light emitting direction. In a bottom emission type organic light emitting display device, the pixel electrode is provided as a light transmissive electrode, and the counter electrode is provided as a reflective electrode. In a top emission type organic light emitting display device, the pixel electrode is provided as a reflective electrode, and the counter electrode is provided as a semi-transmissive electrode. In the present invention, a description will be given based on a top emission type in which the organic light emitting element emits light in the direction of the sealing layer.
[0255] The pixel electrode may be a reflective electrode. The pixel electrode may include a laminated structure of a reflective layer and a transparent or semi-transparent electrode layer having a high work function. The reflective layer may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or an alloy thereof. The transparent or semi-transparent electrode layer may be made of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium oxide (In 2 O 3The conductive layer may include at least one material selected from transparent conductive oxide materials such as indium oxide (IGO), indium gallium oxide (IGO), and aluminum zinc oxide (AZO).
[0256] The reflectance can be changed by adjusting the thickness of the reflective layer and the electrode layer of the pixel electrode. The thickness of the electrode layer is preferably 50 to 200 Å, more preferably 80 to 150 Å. The thickness of the reflective layer is preferably 500 to 2000 Å, more preferably 800 to 1500 Å.
[0257] The pixel electrodes may be patterned to have an irregular shape corresponding to each pixel.
[0258] The pixel electrode can also function as an anode electrode.
[0259] Meanwhile, a pixel defining film 5 including a predetermined opening that covers the edge of the pixel electrode and exposes the center of the pixel electrode may be disposed on the pixel electrode. An organic layer including an organic light emitting layer that emits light may be disposed on the area defined by the opening. The area where the organic layer is disposed may be defined as a light emitting area.
[0260] Meanwhile, when a light-emitting region is formed within the opening of the pixel defining layer, a protruding region is disposed between the light-emitting regions by the pixel defining layer, and since an organic light-emitting layer is not formed in the protruding region, it can be defined as a non-light-emitting region. The pixel defining layer may include the photosensitive composition of the present invention. Details regarding the photosensitive composition of the present invention are the same as those in the above-mentioned embodiment of the present invention, and therefore will not be described.
[0261] The counter electrode may be a transparent electrode. The counter electrode may be a thin semi-transparent film made of a metal having a small work function, such as Li, Ca, LiF / Ca, LiF / Al, Al, Mg, or Ag. To overcome the high resistance problem of the thin metal semi-transparent film, a transparent conductive film made of a transparent conductive oxide may be laminated on the metal semi-transparent film.
[0262] The counter electrode may be formed over the entire surface of the substrate in the form of a common electrode.
[0263] Such a counter electrode can also function as a cathode electrode.
[0264] The pixel electrode and the counter electrode may have opposite polarities.
[0265] The organic layer includes an organic light-emitting layer that emits light, and the organic light-emitting layer can be made of a low molecular weight organic material or a high molecular weight organic material. When the organic light-emitting layer is a low molecular weight organic layer made of a low molecular weight organic material, a hole transport layer (HTL) and a hole injection layer (HIL) are disposed in the direction of the pixel electrode centered on the organic light-emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) are disposed in the direction of the counter electrode.
[0266] Of course, in addition to the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer, other functional layers may be laminated.
[0267] A sealing layer 7 may be disposed on the organic light emitting device layer to cover the organic light emitting device layer. The organic light emitting device included in the organic light emitting device layer is made of an organic material and may be easily deteriorated by external moisture or oxygen. Therefore, in order to protect the organic light emitting device, the organic light emitting device layer must be sealed. The sealing layer may have a structure in which a plurality of inorganic films and a plurality of organic films are alternately laminated as a means for sealing the organic light emitting device layer.
[0268] In the organic light-emitting display device of this embodiment, it is preferable that the sealing layer is formed of a thin film in which a plurality of inorganic films and a plurality of organic films are alternately stacked, which is not a sealing substrate. By using a thin film as a sealing means, it is possible to easily realize a flexible and thin organic light-emitting display device.
[0269] The sealing layer may include a plurality of inorganic films and a plurality of organic films, and the inorganic films and the organic films may be laminated alternately.
[0270] The inorganic film may be made of a metal oxide, a metal nitride, a metal carbide, or a combination thereof. For example, the inorganic film may be made of aluminum oxide, silicon oxide, or silicon nitride. In another example, the inorganic film may include a laminated structure of a plurality of inorganic insulating layers. The inorganic film may function to prevent external moisture and / or oxygen from penetrating into the organic light emitting device layer.
[0271] The organic film may be a polymer organic compound. For example, the organic film may include any one of epoxy, acrylate, and urethane acrylate. The organic film may function to relieve the internal stress of the inorganic film or to complement defects of the inorganic film to perform planarization.
[0272] The order of lamination of the inorganic and organic layers constituting the sealing layer is not limited, and an organic or inorganic layer may be laminated on the organic light emitting device layer, and the uppermost layer of the sealing layer may also be an organic or inorganic layer.
[0273] A touch panel 8 may be formed on the sealing layer. The touch panel may include a first touch electrode formed on the sealing layer, a second touch electrode disposed opposite the first touch electrode, and an insulating layer interposed therebetween.
[0274] The first and second touch electrodes may be formed in a lattice pattern or a specific pattern. The first touch electrode may be formed on the sealing layer, and an inorganic layer may be further provided between the sealing layer and the first touch electrode.
[0275] The first and second touch electrodes may be formed of ITO or a metal mesh, and are preferably formed of a metal mesh.
[0276] Metal mesh is an electrode manufactured by printing opaque metal (copper, silver, gold, aluminum, etc.) in a lattice pattern with a thickness of 1~7μm, and since it uses a highly conductive metal, it has a very low resistance, a fast touch response speed, is easy to realize a large screen, and has the advantage of being cheaper in cost than ITO film.In addition, metal mesh electrodes have better durability against repeated bending compared to ITO electrodes, making them suitable for use as touch panel electrodes for foldable displays.
[0277] The touch panel is preferably a capacitive touch panel that recognizes the part where the amount of electric current is changed by using the capacitance of the human body when a user touches it, calculates the size, and detects the position.
[0278] It will be apparent to those skilled in the art that the organic light emitting display device of the present invention is not limited to the illustrated example, and may further include a control IC that converts an analog signal transmitted from a touch panel into a digital signal and controls coordinate values necessary for determining the coordinates of a touch area, an optical transparent adhesive, a flexible printed circuit board (FPCB) on which conductive and signal line patterns are formed and which transmits various signals to electronic components, and various other electronic components and wiring.
[0279] A color filter may be formed on the touch panel. The color filter may include color portions 10 located on the upper portion of the touch panel and aligned vertically with light-emitting regions of the organic light-emitting element layer, and color separation portions 11 aligned vertically with the non-light-emitting regions to separate the color portions.
[0280] It will be obvious to those skilled in the art that the position of each layer in the structure of the above-mentioned organic light-emitting display device is not limited, and various functional layers having specific purposes and functions can be additionally disposed between each layer, and the organic light-emitting display device of the present invention is not limited to the above-mentioned structure and drawings.
[0281] Synthesis examples and examples according to the present invention will be specifically described below, but the synthesis examples and examples of the present invention are not limited thereto.
[0282] (Preparation of Black Photosensitive Composition)
[0283] Synthesis Example 1: (Production of 9,9-Bis[4-(glycidyloxy)phenyl]fluorene of Chemical Formula 8)
[0284] 20g of 9,9'-bisphenolfluorene (Sigma Aldrich), 8.67g of glycidyl chloride (Sigma Aldrich), and 30g of anhydrous potassium carbonate were placed in a 300ml three-necked round-bottom flask equipped with 100ml of dimethylformamide and a distillation tube, and the mixture was heated to 80°C and reacted for 4 hours. The temperature was then lowered to 25°C, and the reaction solution was filtered. The filtrate was added dropwise to 1000ml of water with stirring, and the precipitated powder was filtered, washed with water, and dried under reduced pressure at 40°C to obtain 25g of 9,9-Bis[4-(glycidyloxy)phenyl]fluorene of the following chemical formula 8. The purity of the obtained powder was 98% as a result of HPLC analysis.
[0285] [ka]
[0286] Synthesis Example 2: Production of Cardo-based binder resin
[0287] 25g (54mmol) of compound 1 obtained from Synthesis Example 1, 8g of acrylic acid (Daejung Chemicals & Metals), 0.2g of benzyltriethylammonium chloride (Daejung Chemicals & Metals) and 0.2g of hydroquinone (Daejung Chemicals & Metals) were placed in a 300ml three-necked round-bottom flask equipped with a distillation tube together with 52g of propylene glycol methyl ether acetate (Sigma Aldrich), and stirred at 110°C for 6 hours. After the reaction was completed, 8g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 1.8g of tetrahydrophthalic acid (Sigma Aldrich) were added, and the mixture was stirred again at 110°C for 6 hours. After the reaction was completed, the reaction solution was collected and analyzed, and it was found that a cardo-based binder resin with a molecular weight of 4,580 and a solid content of 45% was obtained.
[0288] Production Example 1: Production of black pigment dispersion
[0289] A dispersion was obtained by dispersing 15 g of Irgaphor Black S 100 CF (black pigment / BASF), 8.5 g of Disperbyk 163 (BYK), and 6.5 g of SR-3613 (SMS) together with 70 g of propylene glycol methyl ether acetate using a paint shaker (Asada) and 100 g of zirconia beads (Toray) with a diameter of 0.5 mm for 10 hours.
[0290] A photosensitive liquid composition was prepared according to the composition shown in Table 1 below.
[0291] Specifically, the initiator was dissolved in a solvent and stirred at room temperature, and then the binder resin and the polymerizable compound were added thereto and stirred at room temperature. Then, the colorant and other additives were added to the obtained reaction product and stirred at room temperature. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.
[0292] [Table 1]
[0293] A method for preparing a negative pixel defining layer (NDL) using the photosensitive composition is as follows.
[0294] (1) Application and coating stage
[0295] The photosensitive composition is applied to a cleaned 10cm x 10cm metal-deposited substrate using a spin coater to a certain thickness, and then a coating is formed by removing part of the solvent using VCD (vacuum chamber dry). The coating thickness of the photosensitive composition is 3.3 to 3.5 micrometers after VCD.
[0296] (2) Pre-bake stage
[0297] In order to remove the solvent contained in the obtained coating film, it is heated on a hot plate at 80°C to 150°C, preferably 90°C to 120°C, for 50 seconds to 200 seconds, preferably 60 seconds to 180 seconds, more preferably 100 seconds to 150 seconds. By removing a certain amount of the solvent in this process, it is possible to reduce pixel-shaped mask contamination in the next process (exposure) and create a clean pattern.
[0298] (3) Exposure stage
[0299] In order to obtain a desired pattern and a certain thickness of the obtained coating film, a pixel-shaped mask is interposed, and then the film is irradiated with actinic radiation of 190 nm to 600 nm, preferably a light source of a metal or LED lamp having a ghi-line, using an exposure machine to form a pattern. The exposure dose for forming a pattern is 20 to 400 mJ / cm. 2 , preferably 90 to 300 mJ / cm 2The photomask used for exposure had three transmittance ranges of 0% (non-exposed area), 15-60% (half-tone), and 100% (full-tone) to form a pattern.
[0300] (4) Development stage
[0301] Following the exposure step, the resist is developed by dipping in a 2.38 wt% TMAH (tetramethylammonium hydroxide) developer at 23±2°C for a certain time (minutes), and then washed with ultrapure water (DI water), dissolving and removing the non-exposed areas, leaving only the exposed areas to form an image pattern.
[0302] After the developing step, the thickness of the half-tone is preferably 1.25 μm to 2.20 μm, more preferably 1.40 to 2.00 μm, and the thickness of the full-tone is preferably 3.20 μm to 3.42 μm, more preferably 3.25 to 3.35 μm.
[0303] (5) Pattern and thickness analysis
[0304] To confirm the image pattern and thickness obtained by the development, a scanning electron microscope (JEOL) was used to measure the cross-sectional shape and thickness of the pattern. The top of the pattern with the highest height at the bottom was defined as full-tone, and the center was defined as half-tone, and the height according to the exposure dose was confirmed. The size of the blue pixel was measured based on the length of the major axis. The length of the major axis of the blue pixel is preferably 21.3 μm to 25.0 μm.
[0305] (6) Element reliability evaluation
[0306] Using the photosensitive composition, a pattern was formed on a substrate through steps (1) to (4) and a heat treatment was performed to prepare a test piece, and then an organic material was deposited to evaluate the device reliability and confirm the luminance reliability verification factor. The current value during the evaluation was fixed at 14.2 J.
[0307] [Table 2]
[0308] The exposure dose is 100 mJ / cm 2 After irradiating with an intensity of 1500 nm and developing for 60 seconds, the thicknesses of the half-tone and full-tone were measured and compared. Referring to Examples 1 to 10, when the transmittance of the photomask is 15 to 60%, the thicknesses of the half-tone and full-tone are in the range of 30% to 80%, and the pixel size is in the range of 21.3 μm to 25.0 μm, which indicates a suitable size.
[0309] Referring to Comparative Example 1 in Table 2, it was confirmed that when irradiation was performed with a photomask transmittance of less than 15%, the thickness was reduced to less than 1.25 μm for half-tone and less than 3.20 μm for full-tone. This is because the mask transmittance is low and the photocuring degree of the photosensitive composition is low. Although the pixel size increases and the brightness increases, the durability of the manufactured pixel defining layer may decrease. In addition, in Comparative Example 2, it was confirmed that when the photomask transmittance exceeded 60%, the thickness increased to more than 2.20 μm for half-tone and more than 3.42 μm for full-tone. In this case, the pixel size did not reach 21.3 μm, which is disadvantageous in that the brightness and lifespan are reduced.
[0310] The above description is merely illustrative of the present invention, and various modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention.
[0311] Therefore, the embodiments disclosed in this specification are for illustrative purposes only and are not intended to limit the present invention, and the spirit and scope of the present invention are not limited by such embodiments. The scope of protection of the present invention should be interpreted by the claims, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention. [Brief description of the drawings]
[0312] [Figure 1] 1 is a schematic diagram illustrating an organic light emitting display device according to an embodiment of the present invention;
Claims
1. The method for manufacturing a pixel defining layer includes the steps of applying and coating a photosensitive composition; pre-baking; exposing; and developing, and in the exposure step, the transmittance of a photomask is divided into three ranges, namely, 0% (non-exposed area), 15% to 60% (half-tone), and 100% (full-tone), to form one or more layers.
2. 2. The method of claim 1, wherein the exposing and developing steps are performed at the same time.
3. 2. The method of claim 1, wherein the thickness of the half-tone is 1.25 μm to 2.20 μm after the developing step.
4. 2. The method of claim 1, wherein a full-tone thickness after the developing step is 3.20 μm to 3.42 μm.
5. 2. The method of claim 1, wherein a ratio of a half-tone thickness to a full-tone thickness is 30% or more and 80% or less.
6. 2. The method of claim 1, wherein the pre-baking step is performed at a hot plate temperature of 80.degree. C. to 150.degree. C.
7. 2. The method of claim 1, wherein the pre-baking step is performed for 60 to 180 seconds.
8. The method of claim 1 , wherein the photosensitive composition includes a colorant.
9. 2. The method of claim 1, wherein the photosensitive composition comprises a patterning resin comprising an acrylic binder resin, a cardo binder resin, or a combination thereof.
10. 2. The method of claim 1, wherein the photosensitive composition comprises a reactive unsaturated compound.
11. The method of claim 1 , wherein the photosensitive composition comprises a photoinitiator.
12. A pixel defining layer manufactured according to claim 1.
13. An organic light emitting display comprising a pixel defining layer according to claim 12.
14. The organic light emitting display device of claim 13 , wherein the pixel defining layer is formed on a pixel electrode.
15. 15. An electronic device comprising: the display device of claim 14; and a control unit for driving said display device.
Citation Information
Cited By
Digital printing with transparent blank ink
US12318808B2