Method for manufacturing pixel definition layer

Abstract

To provide a method for manufacturing a pixel definition layer aiming to realize a coloring pattern with a constant roughness on an electrode substrate and reduce separation of a common layer (HTL) in a post process and also aiming to enhance the reliability and the life of a display, the method further allowing the pattern to have a constant roughness by minimizing flows in the surface by leaving the temperature high in the post heat processing to deal with the situation in which the pattern with a low roughness after the post heat processing can lead to life reduction due to separation of the common layer and pixel defects (pixel off).SOLUTION: A method for manufacturing a pixel definition layer includes steps of: applying and coating a light-sensitive composition; pre-baking the composition; exposing the composition to light; development; and performing post heat processing on the composition. The post heat processing is performed for 30-120 minutes at temperatures of 230-290 degrees in an oven and the surface roughness after the post heat processing is 1.48-3.0 nm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a pixel definition layer of a light-emitting display device using a photosensitive composition.

Background Art

[0002] Flat panel display devices such as liquid crystal display devices (LCDs) and organic light emitting display devices (OLEDs) are widely used. Among these, organic light emitting display devices have advantages such as low power consumption, fast response speed, high color reproducibility, high brightness, and wide viewing angle.

[0003] In the case of the organic light emitting display device, a polarizing film is used to block light that is incident from the outside and reflected from the panel. However, when applying the polarizing film to a flexible device, there is a disadvantage that it is not suitable due to insufficient bending characteristics.

[0004] As a method for solving the above problems, a method of forming an inorganic film for blocking light on an upper substrate in addition to a color filter and a black matrix has been proposed. However, the above method has limitations in obtaining a desired level of antireflection effect and does not specifically present a method for replacing the polarizing film.

[0005] On the other hand, a colored light-shielding layer, particularly a black light-shielding layer, is used in a liquid crystal display device to prevent color interference between red, green, and blue color filters and improve image quality. Recently, the use of the colored light-shielding layer has also been studied in an organic light emitting display for the same purpose and to improve image visibility with a low reflectance.

[0006] When manufacturing the colored pattern, not only various types of organic pigments but also carbon black and inorganic pigments are used as colorants, and a pigment dispersion liquid in which these are dispersed is mixed with other compositions to form a pattern.

[0007] An organic light-emitting material will be vapor-deposited on the pattern formed in this way. Since the HTL layer, which is a common layer, is vapor-deposited over the entire area of the organic light-emitting display, the adhesion to the coloring pattern that divides the pixels is very important. Therefore, if the surface roughness of the coloring pattern is low, the adhesion to the HTL material is low, so peeling may occur in the subsequent vapor-deposition process, or it may be peeled off by an external impact after panel formation, resulting in a high probability of defective pixels.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] In order to solve the problems of the prior art, one embodiment of the present invention realizes a coloring pattern having a surface roughness (Roughness) of a certain value on an electrode substrate so that there is no peeling phenomenon after vapor-deposition of the common layer (HTL), thereby enhancing display reliability and lifespan.

[0010] That is, when the roughness value of the coloring pattern after post-heat treatment is low, it may cause pixel defects (pixel off) due to common layer peeling. Therefore, the purpose is to minimize the surface flow by leaving it at a high temperature during post-heat treatment.

[0011] Another embodiment is for providing an organic light-emitting display device including the pixel definition layer manufactured by the above method.

[0012] Another embodiment is for providing an electronic device including the organic light-emitting display device.

Means for Solving the Problems

[0013] The method for manufacturing a pixel definition layer according to the present invention is a method for manufacturing a pixel definition layer including steps of applying and coating a photosensitive composition; pre-baking; exposing; developing; and post-heat treatment; wherein the post-heat treatment step is performed at an oven temperature of 230 to 290°C for 30 to 120 minutes, and it is preferable that the surface roughness has a value of 1.48 nm to 3.0 nm after the post-heat treatment step.

[0014] More preferably, the oven temperature in the post-heat treatment step is 230 to 270°C.

[0015] More preferably, the post-heat treatment step is 60 to 120 minutes.

[0016] More preferably, the surface roughness after the post-heat treatment is 1.48 nm to 2.7 nm.

[0017] Preferably, the photosensitive composition contains a colorant.

[0018] Preferably, the colorant contains one or more of an inorganic dye, an organic dye, an inorganic pigment, and an organic pigment.

[0019] Preferably, the colorant is contained in an amount of 1 to 40% by weight based on the total amount of the photosensitive composition.

[0020] Preferably, the colorant is pretreated using a dispersant; or a water-soluble inorganic salt and a wetting agent.

[0021] Preferably, the average particle size of the colorant is 20 nm to 110 nm.

[0022] Preferably, the photosensitive composition contains a patterning resin including an acrylic binder resin, a cardo binder resin, or a combination thereof.

[0023] The weight average molecular weight of the acrylic binder resin is preferably 3,000 g / mol to 150,000 g / mol.

[0024] The curd binder resin preferably contains a repeating structure of the following Chemical Formula 1.

[0025]

Chemical formula

[0026] In Chemical Formula 1,

[0027] 1) R 1 and R 2 are each independently hydrogen; deuterium; halogen; an aryl group having 6 to 30 carbon atoms; a heterocyclic group having 2 to 30 carbon atoms and containing at least one heteroatom selected from O, N, S, Si, and P; a fused ring group of an aliphatic ring and an aromatic ring having 6 to 30 carbon atoms; an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms: an aryloxy group having 6 to 30 carbon atoms; a fluorenyl group: a carbonyl group; an ether group; or an alkoxycarbonyl group having 1 to 20 carbon atoms,

[0028] 2) R 1 and R 2 can form a ring with adjacent groups,

[0029] 3) m or n is each independently an integer from 0 to 4,

[0030] 4) A1 and A2 are each independently the following Chemical Formula 2 or Chemical Formula 3,

[0031]

Chemical formula

[0032]

Chem.

[0033] In the above Chemical Formula 2 and Chemical Formula 3,

[0034] 4-1)* indicates the connecting site,

[0035] 4-2) R 3 ~R 6 are independently of each other hydrogen; deuterium; halogen; a C6~C 30 aryl group; a C2~C heterocyclic group containing at least one heteroatom of O, N, S, Si, and P; a C6~C 30 fused ring group of an aliphatic ring and an aromatic ring; a C1~C 30 alkyl group; a C2~C 20 alkenyl group; a C2~C 20 alkynyl group; a C1~C 20 alkoxy group; a C6~C 20 aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1~C 30 alkoxycarbonyl group, 20 and

[0036] 4-3) R 3 ~R 6 can form a ring with adjacent groups,

[0037] 4-4) Y 1 and Y 2 are independently of each other the following Chemical Formula 6 or Chemical Formula 7,

[0038]

Chem.

[0039]

Chem.

[0040] In the above Chemical Formula 6 and Chemical Formula 7,

[0041] 4-4-1)* indicates the bonding position,

[0042] 4-4-2)R 9 is hydrogen or methyl,

[0043] 4-4-3)R 10 ~R 13 are independently of each other hydrogen; deuterium; halogen; C6~C 30 aryl group; C2~C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6~C 30 fused ring group of aliphatic ring and aromatic ring; C1~C 20 alkyl group; C2~C 20 alkenyl group; C2~C 20 alkynyl group; C1~C 20 alkoxy group; C6~C 30 aryloxy group; fluorenyl group: carbonyl group; ether group; or C1~C 20 alkoxycarbonyl group,

[0044] 4-4-4)L 1 ~L 3 are independently of each other a single bond; fluorenylene group; C2~C 30 alkylene; C6~C 30 arylene; C2~C 30 heterocycle; C1~C 30 alkoxylene; C2~C 30 alkyleneoxy; C6~C 30 aryloxy group; C2~C 30 polyethyleneoxy group,

[0045] 4-4-5)q and r are independently of each other an integer of 0 to 3; provided that q + r = 3,

[0046] 5) The ratio of A1 and A2 in the polymer chain of the resin containing the repeating unit represented by Chemical Formula 1 is 9:1 to 1:9,

[0047] 6) X 1 is a single bond; O; CO; SO2; CR’R”; SiR’R”; the following Chemical Formula 4; or Chemical Formula 5,

[0048] 6-1) R’ and R” are each independently hydrogen; deuterium; halogen; a C6-C 30 aryl group; a C2-C 30 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; a C6-C 30 fused ring group of an aliphatic ring and an aromatic ring; a C1-C 20 alkyl group; a C2-C 20 alkenyl group; a C2-C 20 alkynyl group; a C1-C 20 alkoxy group; a C6-C 30 aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1-C 20 alkoxycarbonyl group,

[0049] (6-2) R’ and R” can form a ring with adjacent groups,

[0050]

Chemical formula

[0051]

Chemical formula

[0052] In the above Chemical Formula 4 and Chemical Formula 5,

[0053] 6-3)* indicates the bonding position,

[0054] 6-4) R 7 ~R 8 are each independently hydrogen; deuterium; halogen; a C6-C 30 aryl group; a C2-C 30 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; a C6-C 30The fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 The alkyl group of C2-C 20 The alkenyl group of C2-C 20 The alkynyl group of C2-C 20 The alkoxy group of C6-C 30 The aryloxy group; the fluorenyl group: the carbonyl group; the ether group; or the alkoxycarbonyl group of C1-C 20 is the alkoxycarbonyl group of C1-C

[0055] 6-5) o and p are each independently an integer of 0 to 4,

[0056] 7) X 2 is an aryl group of C6-C 30 a heterocyclic group containing at least one heteroatom of O, N, S, Si and P and having C2-C 30 a fused ring group of an aliphatic ring and an aromatic ring of C6-C 30 an alkyl group of C1-C 20 an alkenyl group of C2-C 20 an alkynyl group of C2-C 20 an alkoxy group of C1-C 20 an aryloxy group of C6-C 30 the fluorenyl group: the carbonyl group; the ether group; or the alkoxycarbonyl group of C1-C 20 is the alkoxycarbonyl group of C1-C

[0057] (8) The R', R", X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 are each deuterium; halogen; an alkyl group of C1-C 30 or a silane group substituted or unsubstituted with an aryl group of C6-C 30 a siloxane group; a boron group; a germanium group; a cyano group; an amino group; a nitro group; an alkylthio group of C1-C 30 an alkoxy group of C1-C 30 an arylalkoxy group of C6-C 30 an alkyl group of C1-C 30 an alkyl group of C2-C 30an alkenyl group; C2-C 30 an alkynyl group; C6-C 30 an aryl group; C6-C substituted with deuterium 30 an aryl group; a fluorenyl group; a C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P 30 a heterocyclic group; C3-C 30 an aliphatic cyclic group; C7-C 30 an arylalkyl group; C8-C 30 an arylalkenyl group; and may be further substituted with one or more substituents selected from the group consisting of combinations thereof, and adjacent substituents may form a ring with each other.

[0058] The weight average molecular weight of the cardo resin is preferably 1,000 to 100,000 g / mol.

[0059] The cardo resin is preferably contained in an amount of 1 to 30% by weight based on the total amount of the photosensitive composition.

[0060] The photosensitive composition preferably contains 1 to 40% by weight of a reactive unsaturated compound based on the total amount thereof.

[0061] The photosensitive composition preferably contains 0.01 to 10% by weight of a photoinitiator based on the total amount thereof.

[0062] As another specific example, the present invention preferably provides a pixel definition layer manufactured by the above manufacturing method.

[0063] As another specific example, the present invention preferably provides an organic light emitting display device including the pixel definition layer.

[0064] As another specific example, the present invention preferably provides an electronic device including the display device and a control unit for driving the display device.

Effects of the Invention

[0065] The present invention is for realizing a colored pattern having a certain roughness value on an electrode substrate to reduce peeling in the post-treatment process of the common layer (HTL), and to improve display reliability and lifespan. That is, when the roughness of the pattern after post-heat treatment is low, it may cause common layer peeling and lifespan reduction due to pixel off. Therefore, according to the present invention, a certain roughness can be provided by leaving it at a high temperature during post-heat treatment to minimize the surface flow.

Embodiments for Carrying Out the Invention

[0066] Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. When reference numerals are added to the components of each drawing, the same components should have the same numerals as much as possible even if they are shown on other drawings.

[0067] In the description of the present invention, if it is determined that a specific description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof may be omitted. When terms such as "including", "having", "comprising", etc. mentioned in this specification are used, other parts may be added as long as "only" is not used. When a component is expressed in the singular, it includes a plurality unless there is a special explicit description.

[0068] Also, in the description of the components of the present invention, terms such as first, second, A, B, (a), (b), etc. can be used. Such terms are for distinguishing the components from other components, and the essence, order, sequence, number, etc. of the components are not limited by such terms.

[0069] In the description of the positional relationships of components, when it is described that two or more components are "connected", "coupled", or "joined", it should be understood that the two or more components may be directly "connected", "coupled", or "joined", but two or more components and other components may also be "intervened" and then "connected" or "joined". Here, the other components may be included in one or more of the two or more components that are "connected", "coupled", or "joined" to each other.

[0070] In addition, when components such as layers, films, regions, plates, etc. are said to be "on" or "above" other components, this should be understood to include not only the case where they are "directly above" the other components, but also the case where there are other components in between. Conversely, when it is said that a certain component is "directly above" another part, it should be understood to mean that there is no other part in between.

[0071] In the description of the temporal flow relationships related to components, operating methods, manufacturing methods, etc., for example, when temporal front - back relationships or flow front - back relationships such as "after ~", "subsequent to ~", "next to ~", "before ~", etc. are described, it includes cases where they are not continuous unless "immediately" or "directly" is used.

[0072] On the other hand, when a numerical value or its corresponding information for a component is mentioned, even without a separate explicit description, the numerical value or its corresponding information can be interpreted as including the error range that may be caused by various factors (e.g., process factors, internal or external impacts, noise, etc.).

[0073] The terms used in this specification and the appended claims are as follows, unless otherwise mentioned, within the scope of not departing from the idea of the present invention.

[0074] The term "halo" or "halogen" used in this application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) unless otherwise explained.

[0075] As used in this application, the term "alkyl" or "alkyl group" means a radical of a saturated aliphatic functional group having 1 to 60 carbons connected by a single bond, including linear alkyl groups, branched alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, cycloalkyl-substituted alkyl groups, etc., unless otherwise specified.

[0076] As used in this application, the term "haloalkyl group" or "halogenated alkyl group" means an alkyl group substituted with halogen, unless otherwise specified.

[0077] As used in this application, the terms "alkenyl" or "alkynyl" each have a double bond or a triple bond respectively, include linear or side-chain groups, and have 2 to 60 carbon atoms, but are not limited thereto, unless otherwise specified.

[0078] As used in this application, the term "cycloalkyl" means alkyl that forms a ring having 3 to 60 carbon atoms, but is not limited thereto, unless otherwise specified.

[0079] As used in this application, the term "alkoxy group" or "alkyloxy group" means an alkyl group to which an oxygen radical is bonded, and has 1 to 60 carbon atoms, but is not limited thereto, unless otherwise specified.

[0080] As used in this application, the terms "alkeneoxyl group", "alkeneoxy group", "alkenyloxyl group", or "alkenyloxy group" mean an alkenyl group to which an oxygen radical is attached, and have 2 to 60 carbon atoms, but are not limited thereto, unless otherwise specified.

[0081] As used herein, the terms "aryl group" and "arylene group" each have from 6 to 60 carbon atoms, unless otherwise specified, but are not limited thereto. As used herein, an aryl group or an arylene group includes a monocyclic, ring assembly, a plurality of fused ring systems, etc. For example, the aryl group includes a phenyl group, a monovalent moiety of biphenyl, a monovalent moiety of naphthalene, a fluorenyl group, a substituted fluorenyl group, and the arylene group includes a fluorenylene group, a substituted fluorenylene group.

[0082] As used herein, the term "ring assemblies" means that two or more ring systems (a single ring or a fused ring system) are directly linked to each other by a single bond or a double bond, and the number of such direct linkages between the rings is one less than the total number of ring systems contained in the compound. Ring assemblies can be directly linked to each other by single bonds or double bonds of the same or different ring systems.

[0083] Since the aryl group includes ring assemblies as used herein, the aryl group includes biphenyl and terphenyl in which a benzene ring, which is a single aromatic ring, is linked by a single bond. Further, since the aryl group also includes a compound in which an aromatic ring system joined to an aromatic single ring is linked by a single bond, for example, it also includes a compound in which fluorene, which is an aromatic ring system joined to a benzene ring, which is an aromatic single ring, is linked by a single bond.

[0084] As used herein, the term "a plurality of fused ring systems" means a fused ring form sharing at least two atoms, and includes a form in which two or more hydrocarbon ring systems are fused and a form in which at least one heterocyclic ring system containing at least one heteroatom is fused. Such a plurality of fused ring systems may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination 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.

[0085] The term "spiro compound" as used in this application has a "spiro union", and the spiro union means a union formed by two rings sharing only one atom. At this time, the atom shared by the two rings is called a "spiro atom", and depending on the number of spiro atoms in a compound, these are respectively called "monospiro-", "dispiro-", "trispiro-" compounds.

[0086] The terms "fluorenyl group", "fluorenylene group", and "fluorenetriyl group" as used in this application, unless otherwise specified, respectively mean monovalent, divalent, or trivalent functional groups in the following structures where R, R', R", and R'"" are all hydrogen, and a "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, including 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, trivalent, etc., the fluorenyl group, fluorenylene group, and fluorenetriyl group can all be named fluorenyl group.

[0087]

Chemical formula

[0088] Also, each of R, R’, R” and R’” is 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, benzofuran, quinazoline or quinoxaline. For example, the substituted fluorenyl group and fluorenylene group may be monovalent or divalent functional groups of 9,9-dimethylfluorene, 9,9-diphenylfluorene and 9,9’-spirobi[9H-fluorene], respectively.

[0089] As used in this application, the term "heterocyclic group" includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group", but also non-aromatic rings, and means a ring having 2 to 60 carbon atoms containing one or more heteroatoms each, unless otherwise specified, but is not limited thereto. As used in this application, the term "heteroatom" means N, O, S, P or Si unless otherwise specified, and the heterocyclic group means a single cyclic ring, a ring aggregate, a plurality of joined ring systems, a spiro compound, etc. containing a heteroatom.

[0090] For example, the "heterocyclic group" may also include compounds containing heteroatomic groups such as SO2 and P=O as shown in the following compounds instead of carbon forming the ring.

[0091]

Chemical formula

[0092] As used in this application, the term "ring" includes single rings and polycyclic rings, including hydrocarbon rings as well as heterocyclic rings containing at least one heteroatom, and including aromatic and non-aromatic rings.

[0093] As used herein, the term "polycyclic" includes ring assemblies such as biphenyl and terphenyl, fused multiple ring systems, and spiro compounds, including both aromatic and non-aromatic ones, including hydrocarbon rings as well as heterocyclic rings containing at least one heteroatom.

[0094] As used herein, the term "alicyclic group" means a cyclic hydrocarbon excluding aromatic hydrocarbons, including single cyclic, ring assemblies, fused multiple ring systems, spiro compounds, etc., and means a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto. For example, when benzene, an aromatic ring, is fused with cyclohexane, a non-aromatic ring, it also falls within the category of alicyclic rings.

[0095] Also, when prefixes are named consecutively, it means that the substituents are listed in the order described. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group; in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxy group; and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group, where the arylcarbonyl group is a carbonyl group substituted with an aryl group.

[0096] Also, unless otherwise explicitly stated, in the term "substituted or unsubstituted" as used herein, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1 - C 30 alkyl group, C1 - C 30 alkoxy group, C1 - C 30 alkylamine group, C1 - C 30 alkylthiophene group, C6 - C 30 arylthiophene group, C2 - C 30 alkenyl group, C2 - C 30 alkynyl group, C3 - C 30 cycloalkyl group, C6 - C 30 aryl group, C6 - C substituted with deuterium 30 aryl group, C8 - C 30an arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P 30 is meant to be substituted with one or more substituents selected from the group consisting of the heteroaryl groups, etc., and is not limited to these substituents.

[0097] In the present application, for the aryl group, arylene group, heteroaryl group, etc. exemplified as examples of each symbol and its substituents, the "name of the functional group" corresponding to them can be described as the "name of the functional group reflecting the valence", but can also be described as the "name of the parent compound". For example, in the case of "phenanthrene" which is a kind of aryl group, the monovalent "group" can be described as "phenanthryl (group)", and the divalent group can be described as "phenanthrylene (group)" by classifying the valence, etc., but it can also be described as "phenanthrene" which is the name of the parent compound regardless of the valence.

[0098] Similarly, in the case of pyrimidine, it can be described as "pyrimidine" regardless of the valence, or as the "name of the group" of the corresponding valence such as pyrimidinyl (group) in the monovalent case and pyrimidinylene (group) in the divalent case. Therefore, when the type of substituent is described by the name of the parent compound in the present application, it can mean an n-valent "group" formed by the elimination of the hydrogen atom bonded to the carbon atom and / or heteroatom of the parent compound.

[0099] Also, in this specification, when describing the compound name and substituent name, the numbers, alphabets, etc. indicating the position may be omitted. For example, pyrido[4,3-d]pyrimidine can be described as pyridopyrimidine, benzofuro[2,3-d]pyrimidine can be described as benzofuropyrimidine, 9,9-dimethyl-9H-fluorene can be described as dimethylfluorene, etc. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

[0100] Unless otherwise explicitly stated, the chemical formulas used in this application are applied in the same manner as the substituent definitions based on the exponent definitions of the following chemical formulas.

[0101] [Chemical Formula]

[0102] Here, when a is an integer of 0, it means that the substituent R 1 does not exist. That is, when a is 0, it means that all hydrogens are bonded to the carbons forming the benzene ring. At this time, the display of the hydrogens bonded to the carbons may be omitted, and the chemical formula or compound may be described. Also, when a is an integer of 1, one substituent R 1 is bonded to any one of the carbons forming the benzene ring. When a is an integer of 2 or 3, for example, it can be bonded as follows. When a is an integer of 4 to 6, it is also bonded to the carbons 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.

[0103] [Chemical Formula]

[0104] Unless otherwise stated in this application, forming a ring means that adjacent groups are bonded to each other to form a single ring or a plurality of joined rings. The single ring and the plurality of joined rings formed include hydrocarbon rings as well as heterocyclic rings containing at least one heteroatom, and include aromatic and non-aromatic rings.

[0105] Also, unless otherwise stated in this specification, when indicating a fused ring, in "number - fused ring", the number indicates the number of rings to be fused. For example, a form in which three rings are fused to each other, such as anthracene, phenanthrene, benzobenzoxazoline, etc., can be denoted as 3 - fused ring.

[0106] On the one hand, unless otherwise specified, the term "bridged bicyclic compound" used in this application refers to a compound in which two rings share three or more atoms to form a ring. At this time, the shared atoms include carbon or heteroatoms.

[0107] In this application, the organic electronic device can mean the component(s) between the positive electrode and the negative electrode, or can also mean an organic light-emitting diode including the positive electrode, the negative electrode, and the component(s) located therebetween.

[0108] Also, in some cases, the display device in this application can mean an organic electronic device, an organic light-emitting diode, and a panel including the same, or can also mean an electronic device including a panel and a circuit. Here, for example, the electronic device may include all of a lighting device, a solar cell, a portable or mobile terminal (e.g., smartphone, tablet, PDA, electronic dictionary, PMP, etc.), a navigation terminal, a game machine, various TVs, various computer monitors, etc., and without being limited thereto, any form of device as long as it includes the component(s) may be used.

[0109] Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims described later.

[0110] A composition containing 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 and a pixel definition layer (PDL).

[0111] According to an embodiment of the present invention, the black pixel definition layer (PDL) may further include an organic black pigment or a black dye as an additional colorant other than the colorant contained in the aforementioned colorant. For example, the organic pigment can be used alone or mixed with a coloring pigment. At this time, in order to mix a coloring pigment with insufficient light-shielding property, even if the amount of the colorant relatively increases, there is an advantage that the strength of the film (layer) or the adhesion to the substrate does not decrease. According to an embodiment of the present invention, the negative pixel definition layer (Negative PDL (Pixel define layer)) may include a black pigment or a black dye as an additional colorant instead of the colorant contained in the aforementioned colorant.

[0112] Hereinafter, each component will be specifically described.

[0113] 1. The manufacturing process of the negative pixel definition layer is as follows.

[0114] (1) Coating and coating stage

[0115] The photosensitive composition is a low-viscosity liquid sample. After being applied to a substrate, a spin coater or a slit coater is used to coat it with a certain thickness. The spin coater has the advantage that the higher the rotation speed, the thinner the thickness, but the flatness deviation in terms of area decreases. For coating a large-area substrate, a slit coater is preferred over a spin coater. After coating, the remaining solvent makes the surface fluid, which has the disadvantage of deteriorating flatness. To overcome this, a part of the solvent is removed using VCD (vacuum chamber dry) to reduce the fluidity on the surface.

[0116] (2) Pre-bake stage

[0117] This is a step of heating the coated substrate on a hot plate or in an oven at a constant temperature for a certain time to remove a part of the solvent contained in the coating film. If the surface or the depth of the coating film does not dry, contamination of the photomask will occur during exposure in the next step, and curing will not be successfully performed in the exposed area during ultraviolet light irradiation. As a result, due to non-curing, the pattern will not be formed in the development step and will be removed.

[0118] (3) Exposure step

[0119] After the pre-baking step is completed, this is a step of curing the film formed by irradiating actinic rays (ultraviolet rays) using a photomask with a formed pattern. The types of lamps that generate actinic rays include LED lamps or metal (mercury) lamps, and the wavelengths are g-line (436 nm), h-line (405 nm), i-line (365 nm), Deep UV (<260 nm), and they can be used individually or in combination.

[0120] (4) Development step

[0121] In the exposure step, when irradiating actinic rays, it is divided into an exposed area and a non-exposed area by a photomask. In the case of a positive type, the exposed area becomes soluble in the developer, and the non-exposed area withstands the developer and the pattern remains. In the case of a negative type, the exposed area is cured and has resistance to the developer, and the non-exposed area is developed. The black pixel definition layer (Black PDL) manufactured with the composition containing the colorant of the present invention is of the negative type, and is divided into an exposed area (cured) and a non-exposed area (developed) to form a pattern.

[0122] (5) Post-heat treatment step

[0123] This is a step of heating the developed substrate at a high temperature of 230 °C or higher to remove the remaining solvent and moisture. If the solvent and moisture are not completely removed in this step, the remaining solvent and moisture after post-heat treatment will affect the device, thereby affecting the life of the device such as dark spots or pixel shrinkage.

[0124] In the present invention, the post-heat treatment step is carried out at an oven temperature of 230 to 290°C, more preferably 230 to 270°C. Further, the post-heat treatment step is carried out for 30 minutes to 120 minutes, more preferably 60 minutes to 120 minutes.

[0125] It is preferable that the surface roughness has a value of 1.48 nm to 3.0 nm, more preferably 1.48 nm to 2.7 nm, after the post-heat treatment step.

[0126] 2. The composition for forming a negative pixel defining layer containing a colorant is as follows.

[0127] (1) Patterning resin

[0128] The patterning resin according to an embodiment of the present invention contains a cardo-based binder resin.

[0129] 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.

[0130] 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.

[0131] The second ethylenically unsaturated monomer includes aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester 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 carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate, vinyl carboxylate compounds such as vinyl acetate, unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; and these can be used alone or in admixture of two or more thereof.

[0132] 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 can 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.

[0133] The cardo resin contains a repeating structure as shown in Chemical Formula 1 below.

[0134] [Chemical Formula]

[0135] In the above Chemical Formula 1,

[0136] 1) R 1 and R 2 are each independently hydrogen; deuterium; halogen; an aryl group of C6-C 30 ; a heterocyclic group of C2-C containing at least one heteroatom of O, N, S, Si and P 30 ; a fused ring group of an aliphatic ring and an aromatic ring of C6-C 30 ; an alkyl group of C1-C 20 ; an alkenyl group of C2-C 20 ; an alkynyl group of C2-C 20 ; an alkoxy group of C1-C 20 ; an aryloxy group of C6-C 30 ; a fluorenyl group; a carbonyl group; an ether group; or an alkoxycarbonyl group of C1-C 20 and

[0137] 2) R’ and R” can form a ring with adjacent groups

[0138] 3) m or n is each independently an integer from 0 to 4

[0139] 4) A1 and A2 are each independently the following Chemical Formula 2 or Chemical Formula 3

[0140]

Chemical Formula

[0141]

Chemical Formula

[0142] In the above Chemical Formula 2 and Chemical Formula 3

[0143] 4-1) * indicates the connection site

[0144] 4-2) R 3 ~R 6 are each independently hydrogen; deuterium; halogen; an aryl group of C6-C30 an aryl group; a C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6-C 30 fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 alkyl group, C2-C 20 alkenyl group; C2-C 20 alkynyl group; C1-C 20 alkoxy group; C6-C 30 aryloxy group; fluorenyl group: carbonyl group; ether group; or C1-C 20 alkoxycarbonyl group, and

[0145] 4-3)R 3 ~R 6 can form a ring with adjacent groups,

[0146] 4-4)Y 1 and Y 2 are independently of each other the following Chemical Formula 6 or Chemical Formula 7,

[0147]

Chemical formula

[0148]

Chemical formula

[0149] In the said Chemical Formula 6 and Chemical Formula 7,

[0150] 4-4-1)* indicates the bonding position,

[0151] 4-4-2)R 9 is hydrogen or methyl,

[0152] 4-4-3)R 10 ~R 13 are independently of each other hydrogen; deuterium; halogen; C6-C 30 aryl group; C2-C containing at least one hetero of O, N, S, Si and P30 heterocyclic group; C6-C 30 fused ring group of aliphatic ring and aromatic ring; C1-C 20 alkyl group; C2-C 20 alkenyl group; C2-C 20 alkynyl group; C1-C 20 alkoxy group; C6-C 30 aryloxy group; fluorenyl group: carbonyl group; ether group; or C1-C 20 alkoxycarbonyl group,

[0153] 4-4-4)L 1 ~L 3 are, independently of each other, a single bond; fluorenylene group; C2-C 30 alkylene; C6-C 30 arylene; C2-C 30 heterocycle; C1-C 30 alkoxylene; C2-C 30 alkyleneoxy; C6-C 30 aryloxy group; C2-C 20 polyethyleneoxy group,

[0154] 4-4-5)q and r are independently of each other integers from 0 to 3, provided that q + r = 3,

[0155] 5) The ratio of A1 to A2 in the polymer chain of the resin containing the repeating unit represented by Chemical Formula 1 is from 9:1 to 1:9,

[0156] 6)X 1 is a single bond; O; CO; SO2; CR’R”; SiR’R”; the following Chemical Formula 4; or Chemical Formula 5,

[0157] 6-1)R’ and R” are independently of each other hydrogen; deuterium; halogen; C6-C 30 aryl group; C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; C6-C 30 fused ring group of aliphatic ring and aromatic ring; C1-C 20 alkyl group; C2-C 20an alkenyl group; C2-C 20 an alkynyl group; C1-C 20 an alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1-C 20 an alkoxycarbonyl group,

[0158] 6-2) R’ and R” can form a ring with adjacent groups,

[0159]

Chemical formula

[0160]

Chemical formula

[0161] In the above Chemical formulas 4 and 5,

[0162] 6-3) * indicates the bonding position,

[0163] 6-4) R 7 ~R 8 are independently of each other hydrogen; deuterium; halogen; C6-C 30 an aryl group; a C2-C containing at least one heteroatom of O, N, S, Si and P 30 a heterocyclic group; C6-C 30 a fused ring group of an aliphatic ring and an aromatic ring; C1-C 20 an alkyl group; C2-C 20 an alkenyl group; C2-C 20 an alkynyl group; C1-C 20 an alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1-C 20 an alkoxycarbonyl group,

[0164] 6-5) o and p are independently of each other integers from 0 to 4,

[0165] 7) X2 is C6 - C 30 aryl group; a C2 - C 30 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; a C6 - C 30 fused ring group of an aliphatic ring and an aromatic ring; a C1 - C 20 alkyl group; a C2 - C 20 alkenyl group; a C2 - C 20 alkynyl group; a C1 - C 20 alkoxy group; a C6 - C 30 aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1 - C 20 alkoxycarbonyl group,

[0166] 8) said R’, R”, X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 are each deuterium; a halogen; a silane group substituted or unsubstituted with a C1 - C 30 alkyl group or a C6 - C 30 aryl group; a siloxane group; a boron group; a germanium group; a cyano group; an amino group; a nitro group; a C1 - C 30 alkylthio group; a C1 - C 30 alkoxy group; a C6 - C 30 aryloxyalkyl group; a C1 - C 30 alkyl group; a C2 - C 30 alkenyl group; a C2 - C 30 alkynyl group; a C6 - C 30 aryl group; a C6 - C 30 aryl group substituted with deuterium; a fluorenyl group; a C2 - C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; a C3 - C 30 aliphatic ring group; a C7 - C 30 arylalkyl group; a C8 - C 30an arylalkenyl group; and can be further substituted with one or more substituents selected from the group consisting of these combinations, and adjacent substituents can form a ring with each other.

[0167] Said R’, R”, X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 When being an aryl group, preferably, an aryl group of C6~C 30 , more preferably an aryl group of C6~C 18 , and can be, for example, phenyl, biphenyl, naphthyl, terphenyl, etc.

[0168] Said R’, R”, X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 When being a heterocyclic group, preferably, a heterocyclic group of C2~C 30 , more preferably a heterocyclic group of C2~C 18 , and can be, for example, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, etc.

[0169] Said R‘, R”, R 1 ~R 8 and R 10 ~R 13 When being a fluorenyl group, preferably, it can be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9’-spirobifluorene, etc.

[0170] Said L 1 ~L 3 When being an arylene group, preferably, an arylene group of C6~C 30 , more preferably an arylene group of C6~C 18 , and can be, for example, phenyl, biphenyl, naphthyl, terphenyl, etc.

[0171] Said R', R", X 2 , R 1 ~R 8 and R 10 ~R 13 When being an alkyl group, preferably, it is an alkyl group having C1 to C 10 and can be, for example, methyl, t-butyl and the like.

[0172] Said R', R", X 2 , R 1 ~R 8 and R 10 ~R 13 When being an alkoxyl group, preferably, it is an alkoxyl group having C1 to C 20 , more preferably, it is an alkoxyl group having C1 to C 10 and can be, for example, methoxy, t-butoxy and the like.

[0173] Said R', R", X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 The ring formed by bonding adjacent groups of said R', R", X 60 , R 60 ~R 60 is an aromatic ring group having C6 to C 20 , a fluorenyl group, a heterocyclic group having at least one heteroatom of O, N, S, Si and P and having C2 to C 14 or an aliphatic ring group having C3 to C

[0174] The cardo resin can be produced by mixing two or more of, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; anhydride compounds such as benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol, polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate, N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, benzyltriethylammonium chloride.

[0175] The weight average molecular weight of the cardo resin is 1,000 to 100,000 g / mol, preferably 1,000 to 50,000 g / mol, more preferably 1,000 to 30,000 g / mol. When the weight average molecular weight of the resin is within the above range, pattern formation can be successfully carried out without residue during the production of the light-shielding layer, there is no loss of film thickness during development, and a good pattern can be obtained. The resin may be contained in an amount of 1 to 30% by weight, more preferably 3 to 20% by weight, based on the total amount of the photosensitive resin composition. When the resin is contained within the above range, excellent sensitivity, developability, and adhesiveness (adhesion) can be obtained.

[0176] (2) Reactive unsaturated compound

[0177] The reactive unsaturated compound that is essential for the negative pattern must have an ethylenically unsaturated double bond, so that sufficient polymerization occurs during exposure in the pattern formation process to form a pattern with excellent heat resistance, light resistance, and chemical resistance.

[0178] 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, tripentaerythritol octaacrylate, and the like.

[0179] Examples of commercially available products of the reactive unsaturated compound are as follows.

[0180] Examples of the bifunctional esters of the (meth)acrylic acid include Aronix M - 210, M - 240, M - 6200, etc. of Toagosei Co., Ltd.; KAYARAD HDDA, HX - 220, R - 604, etc. of Nippon Kayaku Co., Ltd.; and V - 260, V - 312, V - 335HP, etc. of Osaka Organic Chemical Industry Co., Ltd.

[0181] Examples of the trifunctional esters of the (meth)acrylic acid include Aronix M - 309, M - 400, M - 405, M - 450, M - 7100, M - 8030, M - 8060, etc. of Toagosei Co., Ltd.; KAYARAD TMPTA, DPCA - 20, DPCA - 60, DPCA - 120, etc. of Nippon Kayaku Co., Ltd.; and V - 295, V - 300, V - 360, etc. of Osaka Organic Chemical Industry Co., Ltd.

[0182] These products can be used alone or in combination of two or more.

[0183] The reactive unsaturated compound can also be treated with an acid anhydride and used to impart 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 during exposure in the pattern forming process, and it has excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, and also excellent resolution and adhesion.

[0184] (3) Photoinitiator

[0185] In order to realize a negative pattern by photolithography, a photo radical initiator must be used. The photoinitiator has a molar absorption coefficient of 10,000 (L / mol·cm) or more in the wavelength range of 330 to 380 nm and is a photoinitiator in which a 5% weight loss occurs at 200 °C or lower. Here, the molar absorption coefficient can be calculated by the beer-Lambert Law. Also, the weight loss was measured using TGA while raising the temperature to 300 °C at a rate of 5 °C per minute in a nitrogen atmosphere.

[0186] The photopolymerization initiator is an initiator generally used in the photosensitive resin composition. For example, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, etc. can be used.

[0187] Examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-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.

[0188] Examples of the benzophenone-based compound 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, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0189] Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methyloxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0190] Examples of the benzoin-based compound include benzoin, methyl benzoin ether, ethyl benzoin ether, isopropyl benzoin ether, isobutyl benzoin ether, benzyldimethyl ketal, and the like.

[0191] Examples of the triazine 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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl) 4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4’-methoxystyryl)-6-triazine, and the like.

[0192] In addition to the above compounds, the photoinitiator can also be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a non-imidazole compound, and the like.

[0193] As the radical polymerization initiator, the photoinitiator can use a peroxide compound, an azobis compound, and the like.

[0194] Examples of the peroxide compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butyloxyisopropyl)benzene, t-butyl peroxy valerate n-butyl ester; alkyl peresters such as 2,4,4-trimethylpentyl peroxyphenoxyacetate, α-cumyl peroxyneodecanoate, t-butyl peroxybenzoate, di-t-butyl peroxytriethyl adipate; percarbonates such as di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis-4-t-butylcyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyallyl carbonate, and the like.

[0195] Examples of the azo compound 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).

[0196] The photoinitiator may be used together with a photochromic agent that causes a chemical reaction by absorbing light and then transferring its energy after becoming excited. Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0197] The photoinitiator may be contained in an amount of 0.01 to 10% by weight, for example, 0.1 to 5% by weight based on the total amount of the photosensitive composition. When the photoinitiator is contained within this range, sufficient curing occurs during exposure in the pattern forming process, and excellent reliability can be obtained. The pattern has excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion, and can prevent a decrease in transmittance due to unreacted initiator.

[0198] (4) Colorant

[0199] As the colorant, all of organic pigments, inorganic pigments, and dyes can be used.

[0200] As the colorant, red pigments, green pigments, blue pigments, yellow pigments, black pigments, and the like can be used.

[0201] Examples of the red pigment include C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 270, C.I. Pigment Red 272, C.I. Pigment Red 177, C.I. Pigment Red 89, and the like.

[0202] Examples of the green pigment include copper phthalocyanine pigments substituted with halogens such as C.I. Pigment Green 36 and C.I. Pigment Green 7.

[0203] Examples of the cyan pigment include copper phthalocyanine pigments such as C.I. Pigment Blue 15:6, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:5, and C.I. Pigment Blue 16.

[0204] Examples of the yellow pigment include isoindoline-based pigments such as C.I. Pigment Yellow 139, quinophthalone-based pigments such as C.I. Pigment Yellow 138, nickel complex pigments such as C.I. Pigment Yellow 150, and the like.

[0205] Examples of the black pigment include lactam black, aniline black, perylene black, titanium black, carbon black, and the like.

[0206] Also, 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.

[0207] The pigments and dyes may be used alone or in combination of two or more, and are not limited to these examples.

[0208] Among these, the black pigment can be used to efficiently block light in the light-shielding layer. When using the black pigment, it can also be used together with a color corrector such as an anthraquinone-based pigment, a perylene-based pigment, a phthalocyanine-based pigment, or an azo-based pigment.

[0209] A dispersant can be used together to disperse the pigment in the photosensitive resin composition. Specifically, the pigment can be surface-treated with a dispersant in advance before use, or a dispersant can be added together with the pigment during the production of the photosensitive resin composition for use.

[0210] As the dispersant, nonionic dispersants, anionic dispersants, cationic dispersants, etc. can be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines, etc. These can be used alone or in combination of two or more.

[0211] Examples of commercially available products of the dispersant include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc. of BYK; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemicals; Solsperse5000, Solsperse12000, Solsperse13240, Solsperse13940, Solsperse17000, Solsperse20000, Solsperse24000GR, Solsperse27000, Solsperse28000, etc. of Zeneka; or PB711, PB821, etc. of Ajinomoto.

[0212] The dispersant can be contained in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the composition has excellent dispersibility, and thus excellent stability, developability and patternability during the production of the light-shielding layer.

[0213] The pigment can also be pretreated and used by utilizing a water-soluble inorganic salt and a wetting agent. When the pigment is pretreated and used, the average particle size of the pigment can be refined.

[0214] The pretreatment is carried out through a step of kneading the pigment together with a water-soluble inorganic salt and a wetting agent, and then through a step of filtering and washing the pigment obtained in the kneading step.

[0215] The kneading is carried out at a temperature of 40°C to 100°C, and the filtering and washing are carried out by filtering after washing the inorganic salt with water or the like.

[0216] Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride, potassium chloride, and the like.

[0217] The wetting agent serves as a medium for uniformly mixing the pigment and the water-soluble inorganic salt to facilitate the pulverization of the pigment. Examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether; alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin polyethylene glycol. These can be used alone or in combination of two or more.

[0218] The pigment that has undergone the kneading step can have an average particle size of 100 nm or less. When the average particle size of the pigment is within the above range, a fine pattern can be effectively formed while having excellent heat resistance and light resistance.

[0219] The pigment may be contained in an amount of 1 to 40% by weight, more specifically, 17 to 35% by weight based on the total amount of the photosensitive resin composition. When the pigment is contained within the above range, it has excellent color reproducibility and excellent curability and adhesion of the pattern.

[0220] (5) Solvent

[0221] The solvent used is one having compatibility with the cardo resin, the reactive unsaturated compound, the pigment, the cardo compound, and the initiator, but is a non-reactive substance.

[0222] 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; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-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, methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc., monoxy monocarboxylic acid alkyl esters; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate; ketonic acid esters such as ethyl pyruvate, etc.

[0223] In addition, high-boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, 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, phenyl cellosolve acetate can also be used.

[0224] Among the above solvents, considering 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; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate can be used.

[0225] The solvent can be included as the remaining amount with respect to the total amount of the photosensitive resin composition, specifically, it is included in an amount of 40 to 90% by weight. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus is excellent in processability during the production of the pattern layer.

[0226] (6) Other additives

[0227] In order to prevent stains and spots during coating, improve leveling performance, and prevent the generation of residues due to undevelopment, 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 radical polymerization initiator.

[0228] For example, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc. in order to improve adhesion to a substrate.

[0229] Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0230] The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the above range, it is excellent in adhesion, storage stability, etc.

[0231] Further, the photosensitive resin composition may further contain a surfactant, for example, a fluorine-based surfactant, if necessary, for the effect of improving coating properties and preventing defect generation.

[0232] As the fluorosurfactant, those commercially available under the names such as BM-1000 (registered trademark), BM-1100 (registered trademark) of BM Chemie; Megafac F142D (registered trademark), F172 (registered trademark), F173 (registered trademark), F183 (registered trademark) of Dainippon Ink and Chemicals, Inc.; Fluorad FC-135 (registered trademark), FC-170C (registered trademark), FC-430 (registered trademark), FC-431 (registered trademark) of Sumitomo 3M Limited; Surfynol S-112 (registered trademark), S-113 (registered trademark), S-131, S-141, S-145 of Asahi Glass Co., Ltd.; SH-28PA (registered trademark), -190 (registered trademark), -193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark) of Drey Silicon Co., Ltd. may be used.

[0233] 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 contained within the above range, coating uniformity is ensured, no stains occur, and it is excellent in wettability with respect to the glass substrate. Further, other additives such as an antioxidant and a stabilizer may be added in a certain amount within a range that does not inhibit the physical properties of the photosensitive resin composition.

[0234] Another embodiment can pattern the pixel isolation part of the organic light-emitting element electrode using the aforementioned photosensitive resin composition.

[0235] Hereinafter, synthesis examples and examples according to the present invention will be specifically described, but the synthesis examples and examples of the present invention are not limited thereto.

[0236] (Production of black photosensitive composition)

[0237] Synthesis Example 1: (Production of 9,9-Bis[4-(glycidyloxy)phenyl]fluorene of Chemical Formula 8)

[0238] 20 g of 9,9'-bisphenol fluorene (Sigma Aldrich), 8.67 g of glycidyl chloride (Sigma Aldrich), and 30 g of potassium carbonate anhydrous were placed in a 300 ml three-necked round-bottom flask equipped with a dimethylformamide of 100 ml and a distillation tube. After heating to 80 °C and reacting for 4 hours, the temperature was lowered to 25 °C, and the reaction solution was filtered. After that, the filtrate was added dropwise with stirring to 1000 ml of water. The precipitated powder was filtered, washed with water, and dried under reduced pressure at 40 °C to obtain 25 g of 9,9-Bis[4-(glycidyloxy)phenyl]fluorene of the following Chemical Formula 8. The obtained powder was analyzed by HPLC, and as a result of the purity analysis, it showed a purity of 98%.

[0239]

Chemical formula

[0240] Synthesis Example 2: Production of Cardo-based Binder Resin

[0241] 25 g (54 mmol) of the compound 1 obtained from Synthesis Example 1, 8 g of acrylic acid (Daejung Chemicals & Metals), 0.2 g of benzyltriethylammonium chloride (Daejung Chemicals & Metals), and 0.2 g of hydroquinone (Daejung Chemicals & Metals) were placed in a 300 ml three-necked round-bottom flask equipped with a distillation tube together with 52 g of propylene glycol methyl ether acetate (Sigma Aldrich), and stirred at 110 °C for 6 hours. After completion of the reaction, 8 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 1.8 g of tetrahydrophthalic acid (Sigma Aldrich) were added, and then stirred again at 110 °C for 6 hours. After completion of the reaction, the reaction solution was collected and analyzed. As a result, a cardo-based binder resin with a solid content of 45% and a molecular weight of 4,580 was obtained.

[0242] Production Example 1: Production of Black Pigment Dispersion

[0243] 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) were dispersed with 70 g of propylene glycol methyl ether acetate and 100 g of zirconia beads with a diameter of 0.5 mm (Toray) using a paint shaker (Asada) for 10 hours to obtain a dispersion.

[0244] A photosensitive composition solution was produced with the composition as shown in Table 1 below.

[0245] Specifically, after dissolving the initiator in the solvent and stirring at room temperature, the binder resin and the polymerizable compound were added thereto and stirred at room temperature. Subsequently, a colorant and other additives were put into the obtained reactant and stirred at room temperature. Subsequently, the product was filtered three times to remove impurities, thereby producing a photosensitive resin composition.

[0246]

Table 1

[0247] The method for manufacturing a negative pixel definition layer (negative PDL) using the photosensitive composition is as follows.

[0248] (1) Coating and coating stage

[0249] The photosensitive composition was applied to a 10 cm * 10 cm metal-evaporated substrate that had been cleaned at a specific thickness using a spin coater, and then a part of the solvent was removed using VCD (vacuum chamber dry) to form a coating film. The coating thickness of the photosensitive composition forms a film with a thickness of 2.0 micrometers to 1.7 micrometers after VCD.

[0250] (2) Pre-bake stage

[0251] In order to remove the solvent contained in the obtained coating film, it is heated on a hot plate at 80°C to 120°C for 50 seconds to 200 seconds. By removing a certain amount of solvent in this process, mask contamination in the form of pixels can be reduced during the next process (exposure) stage, and a clean pattern can be created.

[0252] (3) Exposure stage

[0253] After interposing a mask in the form of pixels to obtain the necessary pattern formation and a certain thickness on the obtained coating film, a pattern can be formed by irradiating a light source of a metal or LED lamp having actinic rays of 190 nm to 600 nm, preferably ghi-line, using an exposure machine. The exposure dose irradiated for pattern formation is 20~150 mJ / cm 2 and it is a negative-type photoresist material to be formed.

[0254] (4) Development stage

[0255] Following the exposure stage, after developing by dipping in a 2.38 wt% TMAH (tetramethylammonium hydroxide) developer at 23 ± 2°C for a certain time (minutes), and then washing with ultrapure water (DI water), the unexposed portions are dissolved and removed to leave only the exposed portions to form an image pattern.

[0256] (5) Post-heat treatment stage

[0257] In order to obtain the image pattern obtained by the development, post-baking is performed at 230~290°C for 30 minutes to 120 minutes using an oven to cure the obtained pattern and measure the roughness.

[0258] (6) Surface roughness measurement

[0259] As a sample for roughness measurement, an evaluation substrate including a negative pixel definition layer formed by coating, exposure, development, and post-heat treatment with a composition containing a colorant on a glass surface was obtained. The physical properties of the corresponding evaluation substrate were measured with an atomic force microscope (AFM, Park Systems / XE-100) in non-contact mode at a scan rate of 0.3 (Hz), a set-point of (11.26 nm), and an area of 2 μm × 2 μm.

[0260] (7) Common layer deposition and adhesion evaluation

[0261] After forming a colored pattern by the above manufacturing process, a common layer (HTL) was deposited with a thickness of 120 to 140 nm using a vapor deposition machine. After forming 100 cut surfaces on the deposited specimen using cross-cut, a peeling tape (CT-24) from NICHIBAN was pasted on the cut surface without bubbles. Tape peeling was performed using a UTM (QM 100S) facility manufactured by Coretech Korea Co., Ltd. fixed to a 90° jig and then peeled with a constant force at a speed of 300 mm / min. The adhesion was confirmed by measuring the number of peeled surfaces after peeling compared to before the peeling test.

[0262]

Table 2

[0263] For the substrate obtained in the process after the post-heat treatment stage, the surface roughness and film peeling (adhesion) with the common layer (HTL) were compared. Referring to Comparative Examples 1 to 6 in Table 2 above, it was confirmed that as the post-heat treatment temperature increased and the time increased, the surface roughness was 1.48 nm or less. When the surface roughness decreased to 1.48 nm or less after the post-heat treatment, the adhesion with the common layer (HTL) decreased together with the above adhesion, and the number of peeled layers increased.

[0264] The above description is merely illustrative of the present invention, and those with ordinary knowledge in the technical field to which the present invention pertains can make various modifications without departing from the essential characteristics of the present invention.

[0265] Therefore, the embodiments disclosed in this specification are not for limiting the present invention, but for explaining it, and the idea and scope of the present invention are not limited by such embodiments. The protection scope of the present invention should be interpreted by the claims, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims

【Claim 1】 A method for manufacturing a pixel definition layer, comprising the steps of applying and coating a photosensitive composition; pre-baking; exposing; developing; and post-heat treatment; wherein the post-heat treatment step is performed at an oven temperature of 230 to 290 °C for 30 minutes to 120 minutes, and the surface roughness has a value of 1.48 nm to 3.0 nm after the post-heat treatment step.

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