Pixel defining layer preparation method

Abstract

The invention relates to a preparation method of a pixel defining layer, which comprises the steps of primary coating, pre-baking, exposure, development and post-baking treatment processes to form more than one layer, and coloring patterns are realized on an electrode substrate, so that the process time is shortened, the color becomes bright, the reliability of a display is improved, and the service life of the display is prolonged. Specifically, the transmittance of UV actinic rays of a photomask is adjusted to 0% (non-exposure portion), 20 to 50% (Half-tone), and 100% (Full-tone), two layers are formed by one exposure, PDL and CS two-layer processes of an organic light emitting diode panel are integrated into one, and a layer of an exposed pattern is formed, thereby shortening the process time. Moreover, the half-tone thickness is set to be 1.25 to 2.20 [mu] m, the full-tone thickness is set to be 3.20 to 3.42 [mu] m, and when the surface roughness value is maintained to be 1.49 to 2.5 nm, the adhesion of the vapor deposition hole transport layer can be improved. Moreover, the content of the organic pigment is adjusted, the mechanical strength (plastic hardness and modulus) is improved, patterns are formed within the exposure range of 10 mJ / cm < 2 > to 1000 mJ / cm < 2 >, and the display performance is improved.

Description

[0001] Join by reference

[0002] This application claims priority from Korean Patent Application Nos. 10-2023-0135638 and 10-2023-0148328, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The invention relates to a method for preparing a pixel defining layer of a light-emitting display device by utilizing a photosensitive composition. Background Art

[0004] Flat panel display devices widely use liquid crystal display devices (LCD: Liquid crystal display device), organic light emitting display devices (OLED: Organic light emitting display device), etc. Among them, organic light emitting display devices have the advantages of low power consumption, fast response speed, high color reproduction rate, high brightness, wide viewing angle, etc.

[0005] The purpose of using the polarizing film in the organic light emitting display device is to shield the light reflected from the panel after incident external light. However, the disadvantage is that due to the lack of bending properties, the polarizing film is not suitable for use in flexible devices.

[0006] In order to solve the above problems, it has been suggested to use color filters and black matrices and to form a light-shielding inorganic film on the upper substrate. However, this method has limitations in obtaining the desired level of anti-reflection effect, and no specific method for replacing the polarizing film is provided.

[0007] In addition, the colored patterns are used as red, green, and blue color filters not only in liquid crystal displays but also in organic light-emitting displays.

[0008] When manufacturing the colored pattern, not only a variety of organic pigments but also carbon black and inorganic pigments are used as colorants. The equally dispersed pigment dispersion is mixed with other compositions to form a pattern. Before vapor-depositing the organic light-emitting layer, in order to support the metal mask for vapor deposition, a photolithography process is added and then the vapor deposition process is carried out.

[0009] When the pixel thus formed is used to prepare an organic light-emitting display, a clearer color can be achieved. However, the HTL layer is evaporated on the entire area of ​​the organic light-emitting display as a hole transport layer, so the surface roughness (Roughness) of the coloring pattern that divides the pixel is important. When the surface roughness of the coloring pattern is low, peeling occurs between the HTL material in the evaporation process, or, after the pattern is formed, it is peeled off due to external impact, so the probability of bad pixel generation is high. In addition, another supporting layer is formed on the coloring pattern, resulting in an increase in the process time (Tack time) and an increase in the coating, exposure, development, and thermal curing processes, causing panel damage, pixel shrinkage (pixel shrinkage), dark spots (darkspot), electrode oxidation and other problems, thereby shortening the life of the organic light-emitting display and reducing the brightness.

[0010]

Prior technical literature

[0011] [Patent Literature]

[0012] (Patent Document 1) China Authorized Patent No. 107155328 Summary of the invention

[0013] Issues to be solved

[0014] In order to solve the above-mentioned drawbacks of traditional technology, an implementation example of the present invention realizes a colored pattern with a constant surface roughness (Roughness) on an electrode substrate, which will not peel off after the hole transport layer (HTL) is evaporated, thereby improving the reliability of the display and extending its life.

[0015] That is, when the roughness value of the colored pattern after exposure is 1.48 nm or less, it may cause the hole transport layer to peel off and cause pixel failure. Therefore, the purpose is to minimize the surface roughness progression based on the exposure light amount during exposure.

[0016] In addition, the mechanical strength varies depending on the content of the pigment used in preparing the pixel defining layer. When the pigment content is low, the plastic hardness is low, so cracks may occur due to external impact. On the contrary, when the pigment content is increased to increase the plastic hardness, residues may occur, causing black spots on the panel. Therefore, the purpose is to improve the mechanical strength (plastic hardness, modulus) by adjusting the content of the pigment.

[0017] Yet another implementation example provides an organic light emitting display device including a pixel defining layer prepared by the method.

[0018] Yet another implementation example provides an electronic device including the organic light emitting display device.

[0019] Problem Solution

[0020] The method for preparing a pixel defining layer according to the present invention comprises the steps of: coating and coating a photosensitive composition; pre-baking; exposing; developing; and, preferably, the exposure step is performed at 10 mJ / cm 2 Up to 1000mJ / cm 2 The exposure amount is irradiated with actinic rays, and the surface roughness after the exposure step is 1.0 nm to 3.0 nm. More than one layer is prepared by a single exposure and development process.

[0021] Preferably, in the process of preparing more than one layer through a single exposure and development process, the photomask transmittance is divided into three sections, namely, 0% (non-exposed portion), 20 to 50% (half-tone) and 100% (full-tone).

[0022] Preferably, in the photosensitive composition, the content of the pigment dispersion is 10 to 40% by weight.

[0023] Preferably, based on 100 wt % of the pigment dispersion, the content of the organic black pigment is 3 wt % to 25 wt %.

[0024] Further preferably, the surface roughness is 1.2 nm to 2.9 nm.

[0025] More preferably, the surface roughness is 1.49 nm to 2.5 nm.

[0026] Preferably, the coating formed after the post-baking step has a strength of 300 N / mm 2 Up to 500N / mm 2 Plastic hardness and modulus of 5,000Mpa to 7,000Mpa.

[0027] More preferably, the coating film has a strength of more than 400 N / mm after the post-baking treatment. 2 , 500N / mm 2 The plastic hardness is below 5500Mpa and the modulus is below 6500Mpa.

[0028] Preferably, the coating film formed after the post-baking step is free of residue.

[0029] More preferably, the exposure step irradiates 100 mJ / cm 2 Up to 500mJ / cm 2 Actinic rays.

[0030] More preferably, the exposure step irradiates 70 mJ / cm 2Up to 140mJ / cm 2 Actinic rays.

[0031] Further preferably, the exposure step is performed with an exposure dose of 70 mJ / cm 2 Up to 110mJ / cm 2 Actinic rays.

[0032] Preferably, the hot plate temperature of the pre-baking step is 80°C to 150°C.

[0033] Further preferably, the temperature of the hot plate in the pre-baking step is 90°C to 120°C.

[0034] Preferably, the pre-baking step is performed for 60 seconds to 180 seconds.

[0035] More preferably, the pre-baking step is performed for 100 seconds to 150 seconds.

[0036] Preferably, after the development step, the full-tone thickness is 3.20 to 3.42 μm.

[0037] Further preferably, after the development step, the full-tone thickness is 3.25 to 3.35 μm.

[0038] Preferably, after the development step, the half-tone thickness is 1.25 to 2.20 μm.

[0039] Preferably, after the development step, the half-tone thickness is 1.30 to 2.00 μm.

[0040] Preferably, the photosensitive composition comprises a colorant.

[0041] Preferably, the colorant comprises one or more of an inorganic dye, an organic dye, an inorganic pigment and an organic pigment.

[0042] Preferably, the content of the colorant in the total amount of the photosensitive composition is 1 to 40 wt %.

[0044] Preferably, the colorant is pretreated with a dispersant; or a water-soluble inorganic salt and a wetting agent.

[0045] Preferably, the average particle size of the colorant is 20 nm to 110 nm.

[0046] Preferably, the photosensitive composition comprises a pattern forming resin, and the pattern forming resin comprises an acrylic binder resin, a cardo binder resin or a combination thereof.

[0047] Preferably, the acrylic binder resin has a weight average molecular weight of 3,000 g / mol to 150,000 g / mol.

[0048] Preferably, the cardo-based binder resin includes a repeating structure represented by the following chemical formula 1:

[0049] <Chemical Formula 1>

[0050]

[0051] In the chemical formula 1,

[0052] 1) R1 and R2 are independently: hydrogen; deuterium; halogen; C6~C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0053] 2) R1 and R2 can form a ring between adjacent groups,

[0054] 3) m or n is independently an integer from 0 to 4,

[0055] 4) A1 and A2 are independently of each other represented by the following chemical formula 2 or chemical formula 3,

[0056] <Chemical Formula 2>

[0057]

[0058] <Chemical formula 3>

[0059]

[0060] In the chemical formula 2 and the chemical formula 3,

[0061] 4-1)* indicates the connected parts,

[0062] 4-2) R3 to R6 are independently hydrogen; deuterium; halogen; C6 to C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0063] 4-3) R3 to R6 can form a ring between adjacent groups,

[0064] 4-4) Y1 and Y2 are independently the following chemical formula: Chemical Formula 6 or Chemical Formula 7,

[0065] <Chemical Formula 6>

[0066]

[0067] <Chemical Formula 7>

[0068]

[0069] In the chemical formula 6 and the chemical formula 7,

[0070] 4-4-1)* indicates the bonding position,

[0071] 4-4-2) R9 is hydrogen or methyl ester;

[0072] 4-4-3)R 10 ~R 13Independently of each other: hydrogen; deuterium; halogen; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 The alkoxycarbonyl group

[0073] 4-4-4) L1 to L3 are independently: a single bond; a fluorenyl group; C2 to C 30 Alkylene; C6~C 30 Arylene; C2~C 30 Heterocyclic ring; C1~C 30 Alkoxylene; C2~C 30 Alkyleneoxy; C6~C 30 aryloxy group; C2~C 30 The polyethyleneoxy group,

[0074] 4-4-5) q and r are independently integers from 0 to 3; however, q+r=3,

[0075] 5) The resin includes a repeating unit represented by Chemical Formula 1, wherein within the polymer chain, the ratio of A1 to A2 is 9:1 to 1:9,

[0076] 6) X1 is a single bond; O; CO; SO2; CR'R"; SiR'R"; the following chemical formula 4; or chemical formula 5,

[0077] 6-1) R' and R" are independently: hydrogen; deuterium; halogen; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 The alkoxycarbonyl group

[0078] 6-2) R' and R" can form a ring between adjacent groups,

[0079] <Chemical Formula 4>

[0080]

[0081] <Chemical Formula 5>

[0082]

[0083] In the chemical formula 4 and the chemical formula 5,

[0084] 6-3)* indicates the bonding position,

[0085] 6-4) R7 to R8 are independently hydrogen; deuterium; halogen; C6 to C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0086] 6-5) o and p are independently integers from 0 to 4,

[0087] 7) X2 is C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0088] 8) R', R", X2, L1-L3, R1-R8 and R 10 ~R 13 may be further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30 aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof, and adjacent substituents may form a ring.

[0089] Preferably, the cardo-based resin has a weight average molecular weight of 1,000 to 100,000 g / mol.

[0090] Preferably, the content of the cardo-based resin in the total amount of the photosensitive composition is 1 to 30 weight %.

[0091] Preferably, as described above, the photosensitive composition comprises: the reactive unsaturated compound in an amount of 1 to 40 wt % in the total amount thereof.

[0092] Preferably, the photosensitive composition comprises: a photoinitiator in an amount of 0.01 to 10 wt % based on the total amount of the photosensitive composition.

[0093] In yet another specific example, preferably, the present invention provides a pixel defining layer prepared by the preparation method.

[0094] In yet another specific example, preferably, the present invention provides an organic light emitting display device including the pixel defining layer.

[0095] In yet another specific example, preferably, the present invention provides an electronic device, which includes the display device and a control unit for driving the display device.

[0096] Effects of the Invention

[0097] The present invention integrates two patterning processes into a single process on an electrode substrate to form a layer, so as to reduce panel damage, thereby making the color brighter and significantly improving the reliability and life of the display.

[0098] The purpose of the present invention is to realize a coloring pattern with a constant roughness value after exposure on an electrode substrate, thereby reducing the peeling of the hole transport layer (HTL) in the subsequent process, and also improving the reliability and life of the display. That is, when the roughness of the pattern after exposure is less than 1.48nm, it will become a cause of the peeling of the hole transport layer and the pixel failure (pixel off) causing the shortening of the life. Therefore, it is intended to include the colorant of the present invention, adjust the light amount during the exposure process, minimize the flow of the surface, and have a roughness of 1.49nm to 2.5nm.

[0099] In addition, the mechanical strength will vary depending on the content of the pigment used when preparing the pixel definition layer. When the pigment content is low, the plastic hardness is low, so cracks may occur due to external impact. On the contrary, when the pigment content is increased to increase the plastic hardness, residues may occur, causing black spots on the panel. Therefore, the mechanical strength (plastic hardness, modulus) can be significantly improved by adjusting the pigment content. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] Figure 1 The cross-sectional schematic diagram of the pixel defining layer described in the embodiment and the comparative example was taken by a scanning electron microscope. DETAILED DESCRIPTION

[0101] Hereinafter, some embodiments of the present invention will be described in detail with reference to the schematic diagrams. When components of each drawing are denoted by reference symbols, the same components are given the same symbols as much as possible even if they are shown in other drawings.

[0102] In the process of describing the present invention, if it is considered that the detailed description of the relevant known structure or function will confuse the main points of the present invention, the detailed description thereof may be omitted. When the present invention adopts "including", "having", "comprising", etc., other parts may be added unless "to only" is used. When the constituent elements are expressed in the singular, unless otherwise clearly stated, the case of expressing them in the plural is included.

[0103] Furthermore, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only used to distinguish the components from other components, and the nature, order, sequence or number of the components are not limited by these terms.

[0104] In the process of describing the positional relationship of constituent elements, when it is mentioned that two or more constituent elements are "connected", "combined" or "accessed", it should be understood that the two or more constituent elements can be directly "connected", "combined" or "accessed", but can also be further "carried with" the two or more constituent elements and other constituent elements to achieve "connection", "combination" or "access". Among them, the other constituent elements can include one or more of the two or more constituent elements that are "connected", "combined" or "accessed" to each other.

[0105] Furthermore, when a component such as a layer, film, region, or plate is located “on” or “over” another component, it should be understood that it includes not only the case where it is located “directly above” another component, but also the case where there is another component in between. Conversely, when a component is located “directly above” another part, it should be understood that there is no other part in between.

[0106] When describing the time flow relationship related to constituent elements, working methods, or manufacturing methods, for example, when describing the time sequence relationship or process sequence relationship such as "after", "next to", "then", "before", etc., since "immediately" or "directly" is not used, discontinuous situations can be further included.

[0107] In addition, when referring to the numerical value of a constituent element or the information corresponding thereto, even if not clearly stated separately, it should be interpreted that the numerical value or the information corresponding thereto includes: the error range caused by various factors (for example, engineering factors, internal or external impact, noise, etc.).

[0108] Unless otherwise described, the terms used in this specification and the appended claims are as follows within the scope that does not depart from the spirit of the present invention.

[0109] Unless otherwise described, the term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0110] Unless otherwise described, the term "alkyl" or "alkyl group" used in this application contains 1 to 60 carbon atoms connected by single bonds, and refers to a free radical of a saturated aliphatic functional group represented by a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, and a cycloalkyl-substituted alkyl group.

[0111] Unless otherwise described, the term "haloalkyl group" or "halogenalkyl group" used in the present application refers to an alkyl group substituted with halogen.

[0112] Unless otherwise described, the term "alkenyl" or "alkynyl" used in the present application respectively has a double bond or a triple bond, contains a straight chain or a side chain, and has 2 to 60 carbon atoms, but is not limited thereto.

[0113] Unless otherwise described, the term "cycloalkyl" used in the present application means a cyclic alkane having 3 to 60 carbon atoms, but is not limited thereto.

[0114] The term "alkoxy group" or "alkyloxy group" used in the present application refers to an alkyl group to which an oxygen radical is bonded, and unless otherwise specified, has 1 to 60 carbon atoms, but is not limited thereto.

[0115] The term "alkenoxyl group", "alkenoxygroup", "alkenyloxyl group" or "alkenyloxy group" used herein means an alkenyl group to which an oxygen radical is bonded, and unless otherwise specified, has 2 to 60 carbon atoms, but is not limited thereto.

[0116] Unless otherwise described, the terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbons, respectively, but are not limited thereto. In the present application, aryl group or arylene group include monocyclic type, cyclopolymer, fused polycyclic compounds, etc. For example, the aryl group may include phenyl group, the monovalent functional group of biphenyl, the monovalent functional group of naphthalene, fluorenyl group and substituted fluorenyl group. Arylene group may include fluorenyl group and substituted fluorenyl group.

[0117] The term "ring assemblies" used in the present application is composed of two or more ring systems (single ring or fused ring systems) directly connected by a single bond or a double bond, indicating that the number of directly connected rings is less than the total number of ring systems contained in the compound by 1. The ring assemblies can be directly connected by the same or different ring systems through a single bond or a double bond.

[0118] In the present application, the aryl group includes a cyclopolymer, and thus, the aryl group includes biphenyl and terphenyl connected by a single bond to a benzene ring as a monocyclic aromatic. In addition, the aryl group also includes a compound in which an aromatic ring system combined with an aromatic monocyclic ring is connected by a single bond, and thus, for example, a compound in which an aromatic ring system combined with a benzene ring as an aromatic monocyclic ring, i.e., fluorene, is connected by a single bond.

[0119] The term "fused polycyclic ring system" used in this application refers to a fused ring that shares at least two atoms, including: a fused form of two or more hydrocarbon ring systems and a fused form of at least one heterocyclic ring system containing at least one heteroatom. The fused polycyclic ring system can be an aromatic ring, an aromatic heterocyclic ring, an aliphatic ring, or a combination of such rings. For example, an aryl group can be a naphthyl group, a phenanthrenyl group, a fluorenyl group, etc., but it is not limited thereto.

[0120] The term "spiro compound" used in the present application has a 'spiro union', which means that two rings share only one atom to form a connection. In this case, the atom shared by the two rings is called a 'spiro atom', and according to the number of spiro atoms contained in one compound, it is called a 'monospiro-', 'dispiro-', 'trispiro-' compound, respectively.

[0121] Unless otherwise described, the terms "fluorenyl group", "fluorenylene group" and "fluorene-triyl group" used in this application respectively represent monovalent, divalent or trivalent functional groups in which R, R', R" and R'" are all hydrogen in the following structures, and "substituted fluorenyl group", "substituted fluorenyl group" or "substituted fluorene-triyl group" means that at least one of the substituents R, R', R", R'" is a substituent other than hydrogen, including the case where R and R' are bonded to each other and form a spiro compound together with the carbon to which they are bonded. In this specification, the fluorenyl group, fluorenylene group and fluorene-triyl group may be named as fluorenyl group without considering the equivalent number of monovalent, divalent and trivalent.

[0122]

[0123] Furthermore, the R, R', R" and R'" may be independently selected from: 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 heterocyclyl group having 2 to 30 carbon atoms. For example, the aryl group may be phenyl, biphenyl, naphthalene, anthracene or phenanthrene, and the heterocyclyl group may be pyrrole, furan, thiophene, pyrazole, imidazole, triazole, pyridine, pyrimidone, pyridazine, pyrazine, triazine, indole, benzofuran, or the like. furan), quinazoline or quinoxaline

[0124] 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.

[0125] The term "heterocyclyl group" used in this application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group", but also non-aromatic rings. Unless otherwise described, they respectively represent rings containing one or more heteroatoms and having a carbon number of 2 to 60, but are not limited thereto. Unless otherwise described, the term "heteroatom" used in this application represents N, O, S, P or Si, and heterocyclyl group represents a monocyclic type, cyclopolymer, fused polycyclic system, spiro compound, etc. containing heteroatoms.

[0126] For example, a "heterocyclyl group" may also replace a cyclic carbon, including the following compounds, and compounds containing heteroatom terminal groups such as SO2 and P=O.

[0127]

[0128] The term "ring" used in the present application includes monocyclic and polycyclic rings, and of course, hydrocarbon rings include heterocyclic rings, the heterocyclic rings contain at least one heteroatom, and include aromatic and non-aromatic rings.

[0129] The term "polycyclic" as used in this application includes ring assemblies such as biphenyl and terphenyl and fused polycyclic systems and spiro compounds, including not only aromatic but also non-aromatic rings. Of course, hydrocarbon rings include heterocyclic rings that contain at least one heteroatom.

[0130] The term "aliphatic cyclo group" used in this application refers to cyclic hydrocarbons other than aromatic hydrocarbons, including monocyclic types, cyclopolymers, fused polycyclic systems, spiro compounds, etc., and unless otherwise specified, refers to a ring with a carbon number of 3 to 60, but is not limited thereto. For example, when fused aromatic cyclobenzene and non-aromatic cyclohexane are also equivalent to aliphatic rings.

[0131] Furthermore, when prefixes are used consecutively, it means that the substituents are arranged in the order of the description. For example, aryl alkoxy group means an alkoxy group substituted with an aryl group, alkoxy carbonyl group means a carbonyl group substituted with an alkoxy group, and aryl carbonyl alkenyl group means an alkenyl group substituted with an arylcarbonyl group, wherein aryl carbonyl group is a carbonyl group substituted with an aryl group.

[0132] Furthermore, unless otherwise specified, in the term "substituted or unsubstituted" used in the present application, "substituted" means substituted with one or more substituents selected from the group consisting of deuterium, halogen, amino group, nitrile group, nitro group, C1-C 30 Alkyl group, C1~C 30 Alkoxy group, C1~C 30 Alkyl amine group, C1~C 30 alkyl thiophene group, C6~C 30 arylthiophene group, C2~C 30 Alkenyl group, C2~C 30 Alkinyl group, C3~C 30 Cycloalkyl group, C6~C 30 aryl group, C6~C 30 Aryl group, C8~C 30 aryl alkenyl group, silane group, boron group, germanium group and C2~C 30 The heterocyclic group, the C2~C 20 The heterocyclic group includes at least one heteroatom selected from the group consisting of O, N, S, Si and P. And, it is not limited by the substituents thereof.

[0133] In the present application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclyl group, etc. described in each label and its substituent examples can be recorded as 'functional group name reflecting valence' or as 'name of the parent compound'. For example, 'phenanthrene' as an aryl group' can be classified and recorded as the name of the 'group' according to the valence, such as recording the monovalent 'group' as 'phenanthryl (group)' and recording the divalent 'group' as 'phenanthryl (group)', etc. However, it can also be recorded as the name of the parent compound 'phenanthrene' without considering the valence.

[0134] Similarly, pyrimidone can be recorded as 'pyrimidone' regardless of the valence, or recorded as pyrimidinyl (base) when it is monovalent, and can be recorded as the 'name of the base' of the corresponding valence when it is divalent, such as pyrimidinylene (base), etc. Therefore, in the present application, when the type of substituent is recorded as the name of the parent compound, it can represent: an n-valent 'base' formed by the desorption of hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0135] In addition, in this specification, when recording the name of a compound or a substituent, the numerals or alphabets indicating the position may be omitted. For example, pyrido[4,3-d]pyrimidone may be recorded as pyrido pyrimidone, benzofuran[2,3-d]pyrimidone may be recorded as benzofuran pyrimidone, 9,9-dimethyl-9H-fluorene may be recorded as dimethylfluorene, etc. Therefore, benzo[g]quinoxaline or benzo[f]quinoxaline may be recorded as benzoquinoxaline.

[0136] Furthermore, unless otherwise expressly stated, the chemical formulae used in this application are also subject to the definitions of substituents according to the index definitions of the following chemical formulae.

[0137]

[0138] Wherein, when a is an integer of 0, it indicates that the substituent R 1 When a is 0, the carbon atoms forming the benzene ring are all bonded with hydrogen atoms. In this case, the symbol of the hydrogen atoms bonded with carbon atoms can be omitted and the chemical formula or compound can be recorded. 1 When a is an integer of 2 or 3, the bonding can be as follows. When a is an integer of 4 to 6, it can also be bonded to the carbon of the benzene ring by a similar method. When a is an integer of 2 or more, R 1 Can be the same or different.

[0139]

[0140] In the present application, unless otherwise described, forming a ring means that adjacent groups are bonded to each other to form a monocyclic ring or a fused polycyclic ring. The monocyclic ring and the fused polycyclic ring formed include not only hydrocarbon rings but also heterocyclic rings. The heterocyclic ring contains at least one heteroatom and may include aromatic and non-aromatic rings.

[0141] In addition, in this specification, unless otherwise described, when a condensed ring is represented, in the term "number-condensed ring", the number represents the number of condensed rings. For example, a condensed form of three rings can be represented as a 3-condensed ring, such as anthracene, phenanthrene, benzo quinozoline, etc.

[0142] In addition, unless otherwise described, the term "bridged bicyclic compound" used in the present application refers to a compound in which two rings share three or more atoms to form a ring. In this case, the shared atoms may include carbon or heteroatoms.

[0143] In the present application, an organic electrical element refers to a component(s) between an anode and a cathode, or refers to an organic light emitting diode including anode and cathode and a component(s) therebetween.

[0144] Furthermore, depending on the circumstances, the display device of the present application refers to an organic electrical element, an organic light emitting diode and a panel including the same, or an electronic device including a panel and a circuit. For example, the electronic device includes all lighting devices, solar cells, portable or mobile terminals (for example, smart phones, tablet computers, PDAs, electronic dictionaries, PMPs, etc.), navigation terminals, game consoles, various TVs, various computer displays, etc., but is not limited thereto, and any form of device is acceptable as long as it includes the aforementioned (several) components.

[0145] Hereinafter, an implementation example of the present invention will be described in detail, but this is for illustrative purposes only and the present invention is not limited thereto. The present invention is only defined by the scope of the following claims.

[0146] According to an implementation example of the present invention, a composition including a colorant may be used to prepare a red pattern, a green pattern, a blue pattern or a black matrix, and a pixel definition layer (PDL).

[0147] According to an implementation example of the present invention, the black pixel defining layer (PDL) may further include an additional colorant in addition to the colorant contained in the colorant, that is, an organic black pigment or a black dye. For example, the organic pigment can be used alone or mixed with the organic pigment and the coloring pigment. The advantage at this time is that, due to the mixed coloring pigment with insufficient light-shielding property, even if the amount of the colorant is relatively increased, the strength of the film (layer) or the adhesion of the substrate will not decrease. According to an implementation example of the present invention, the negative pixel defining layer (Negative PDL (Pixel define layer)) may include an additional colorant, that is, a black pigment or a black dye, to replace the colorant contained in the colorant.

[0148] Hereinafter, each component is described in detail.

[0149] 1. The preparation process of the negative pixel defining layer is as follows.

[0150] (1) Coating and coating steps

[0151] The photosensitive composition is a low-viscosity liquid reagent. In order to form a coating with a certain thickness after coating on a substrate, a spin coater or a slit coater is used. The advantage of a spin coater is that the higher the number of rotations, the thinner the thickness, but the flatness deviation in the area is reduced. In order to form a coating on a large-area substrate, a slit coater is preferably used compared to a spin coater, but its disadvantage is that after the coating is formed, the surface exhibits fluidity due to the residual solvent, resulting in a decrease in flatness. In order to overcome this drawback, VCD (vacuum chamber dry) is used to locally remove the solvent to reduce the fluidity of the surface.

[0152] (2) Pre-baking step

[0153] This process uses a hot plate or oven to heat the substrate of the coating at a certain temperature and time to partially remove the solvent contained in the coating film. If the surface or deep part of the coating film is not dry, it will cause photomask contamination when the next process is exposed. When irradiated with ultraviolet light, the exposed part is not well cured. If it is not cured, it will cause the development process to not form and remove the pattern.

[0154] (3) Exposure Step

[0155] When the pre-baking process is completed, the process uses a photomask with a pattern to irradiate actinic rays (ultraviolet rays) to cure the formed film. The types of lamps that generate actinic rays include LED lamps or metal (mercury) lamps, and the wavelengths include g-line (436nm), h-line (405nm), i-line (365nm), and Deep UV (<260nm), which can be used separately or in combination.

[0156] (4) Development step

[0157] When the exposure step irradiates actinic rays, the photomask is divided into an exposed part and a non-exposed part. In the case of a positive type, the exposed part is dissolved by a developer, while the non-exposed part resists the developer and leaves a pattern. In the case of a negative type, the exposed part is cured and resistant to the developer, while the non-exposed part is developed. The black pixel defining layer (Black PDL) prepared using a composition containing the colorant of the present invention is a negative type, which can be divided into an exposed part (cured) and a non-exposed part (developed) to form a pattern.

[0158] (5) Post-exposure step

[0159] After the development process is completed, the process step is to irradiate the patterned substrate with actinic rays (ultraviolet rays) again to further solidify the formed film. The types of lamps that generate actinic rays include LED lamps or metal (mercury) lamps, and the wavelengths include g-line (436nm), h-line (405nm), i-line (365nm), and Deep UV (<260nm), which can be used alone or in combination.

[0160] (6) Post-baking step

[0161] The process heats the developed substrate at a high temperature of 210°C or above to remove residual solvent and fume. If the process does not completely remove the solvent and fume, degassing during the process after post-baking will affect the components, thereby causing black spots or affecting pixel shrinkage.

[0162] 2. The composition for forming the negative pixel defining layer including the colorant is as follows.

[0163] (1) Pattern forming resin

[0164] According to an embodiment of the present invention, the pattern forming resin may include an acrylic binder resin, a cardo binder resin or a combination thereof.

[0165] 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 including one or more acrylic repeating units.

[0166] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof. The content of the first ethylenically unsaturated monomer in the total amount of the acrylic binder resin may be 5 wt % to 50 wt %, for example, 10 wt % to 40 wt %.

[0167] The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, etc.; an unsaturated carboxylic acid ester compound such as methyl (meta)acrylate, ethyl (meta)acrylate, butyl (meta)acrylate, 2-hydroxyethyl (meta)acrylate, 2-hydroxybutyl (meta)acrylate, benzyl (meta)acrylate, cyclohexyl (meta)acrylate, benzene (meta)acrylate, etc.; an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl (meta)acrylate, 2-dimethylaminoethyl (meta)acrylate, etc.; a carboxylic acid vinyl ester compound such as vinyl acetate; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meta)acrylate, a vinyl cyanide compound such as (meta)acrylonitrile, an unsaturated amide compound such as (meta)acrylamide, etc., and the like may be used alone or in combination of two or more.

[0168] Specific examples of the acrylic binder resin include: (meta) acrylic acid / benzyl methacrylate copolymer, (meta) acrylic acid / benzyl methacrylate / styrene copolymer, (meta) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meta) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but it is not limited to this. They can also 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.

[0169] The cardo-based resin includes a repeating structure represented by the following Chemical Formula 1.

[0170] <Chemical Formula 1>

[0171]

[0172] In the chemical formula 1,

[0173] 1) R1 and R2 are independently: hydrogen; deuterium; halogen; C6~C 30an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0174] 2) R1 and R2 can form a ring between adjacent groups,

[0175] 3) m or n is independently an integer from 0 to 4,

[0176] 4) A1 and A2 are independently of each other represented by the following chemical formula 2 or chemical formula 3,

[0177] <Chemical Formula 2>

[0178]

[0179] <Chemical formula 3>

[0180]

[0181] In the chemical formula 2 and the chemical formula 3,

[0182] 4-1)* indicates the connected parts,

[0183] 4-2) R3 to R6 are independently hydrogen; deuterium; halogen; C6 to C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0184] 4-3) R3 to R6 can form a ring between adjacent groups,

[0185] 4-4) Y1 and Y2 are independently represented by the following chemical formula 6 or chemical formula 7,

[0186] <Chemical Formula 6>

[0187]

[0188] <Chemical Formula 7>

[0189]

[0190] In the chemical formula 6 and the chemical formula 7,

[0191] 4-4-1)* indicates the bonding position,

[0192] 4-4-2) R9 is hydrogen or methyl ester;

[0193] 4-4-3)R 10 ~R 13 Independently of each other: hydrogen; deuterium; halogen; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 The alkoxycarbonyl group

[0194] 4-4-4) L1 to L3 are independently: a single bond; a fluorenyl group; C2 to C 30 Alkylene; C6~C 30 Arylene; C2~C 30 Heterocyclic ring; C1~C 30 Alkoxylene; C2~C 30 Alkyleneoxy; C6~C 30 aryloxy group; C2~C 30 The polyethyleneoxy group,

[0195] 4-4-5) q and r are independently integers from 0 to 3; however, q+r=3,

[0196] 5) The resin includes a repeating unit represented by Chemical Formula 1, wherein within the polymer chain, the ratio of A1 to A2 is 9:1 to 1:9,

[0197] 6) X1 is a single bond; O; CO; SO2; CR'R"; SiR'R"; the following chemical formula 4; or chemical formula 5,

[0198] 6-1) R' and R" are independently: hydrogen; deuterium; halogen; C6~C 30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 The alkoxycarbonyl group

[0199] 6-2) R' and R" can form a ring between adjacent groups,

[0200] <Chemical Formula 4>

[0201]

[0202] <Chemical Formula 5>

[0203]

[0204] In the chemical formula 4 and the chemical formula 5,

[0205] 6-3)* indicates the bonding position,

[0206] 6-4) R7 to R8 are independently hydrogen; deuterium; halogen; C6 to C 30 an aryl group; a C2-C 30 Heterocyclyl group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0207] 6-5) o and p are independently integers from 0 to 4,

[0208] 7) X2 is C6~C30 an aryl group; a C2-C 30 heterocyclic group; C6~C 30 A fused ring group of an aliphatic ring and an aromatic ring (cyclo group); C1~C 20 Alkyl group; C2~C 20 alkenyl group; C2~C 20 Alkinyl group; C1~C 20 Alkoxy group; C6~C 30 aryloxy group; fluorenyl group; carbonyl group; ether group; or C1~C 20 Alkoxy carbonyl group,

[0209] 8) R', R", X2, L1-L3, R1-R8 and R 10 ~R 13 may be further substituted with one or more substituents selected from the group consisting of the following components: deuterium; halogen; substituted or unsubstituted C1-C 30 Alkyl group or C6~C 30 aryl group, silane group, siloxane group, boron group, germanium group, cyano group, amino group, nitro group, C1~C 30 Alkylthio group; C1~C 30 Alkoxy group; C6~C 30 Aryl alkoxy group; C1~C 30 Alkyl group; C2~C 30 alkenyl group; C2~C 30 Alkinyl group; C6~C 30 aryl group; C6~C 30aryl group; fluorenyl group; C2~C 30 A heterocyclic group comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P; C3~C 30 Aliphatic ring group; C7~C 30 Aryl alkyl group; C8~C 30 and combinations thereof, and adjacent substituents may form a ring.

[0210] The R', R", X2, L1~L3, R1~R8 and R 10 ~R 13 When it is an aryl group, preferably, it can be C6 to C 30 The aryl group may be C6 to C 18 The aryl group may be, for example, phenyl, biphenyl, naphthyl, terphenyl, or the like.

[0211] The R', R", X2, L1~L3, R1~R8 and R 10 ~R 13 When it is a heterocyclic group, preferably, it can be C2 to C 30 The heterocyclic group (heterocyclyl group), further preferably, can be C2~C 18 The heterocyclyl group may be, for example, dibenzo furan, dibenzothiophene, naphtho benzo thiophene, naphtho benzofuran, or the like.

[0212] The R', R", R1 to R8 and R 10 ~R 13 When it is a fluorenyl group, preferably, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl, 9,9'-spirobifluorene, or the like.

[0213] When L1 to L3 are arylene groups, preferably, they can be C6 to C 30 The arylene group may be C6 to C 18 The arylene group may be, for example, phenyl, biphenyl, naphthyl, terphenyl, or the like.

[0214] The R', R", X2, R1 to R8 and R 10 ~R 13 When it is an alkyl group, preferably, it can be C1 to C 10 The alkyl group may be, for example, a methyl group, a t-butyl group, or the like.

[0215] The R', R", X2, R1 to R8 and R 10 ~R 13 When it is an alkoxy group, it is preferably C1 to C 20 The alkoxy group, more preferably, may be C1 to C 10 The alkoxy group may be, for example, methoxy, t-butoxy, or the like.

[0216] The R', R", X2, L1~L3, R1~R8 and R 10 ~R 13 The ring formed by bonding adjacent groups can be C6 to C 60 Aromatic ring group; fluorenyl group; C2~C 60 or C3~C 60 For example, when adjacent groups are bonded to each other to form an aromatic ring, preferably, a C6-C 20 The aromatic ring may preferably form a C6 to C 14 The aromatic ring can form, for example, benzene, naphthalene, phenanthrene, etc.

[0217] For example, the cardo resin can be prepared by mixing two or more of the following components: fluorene-containing compounds such as 9,9-bis(4-oxiranemethoxyphenyl)fluorene; anhydride compounds such as benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; ethanol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol monomethyl ether acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and ammonium or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylammonium, triethylammonium, tributylammonium, and benzyltriethylammonium chloride.

[0218] 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, and more preferably 1,000 to 30,000 g / mol. If the weight average molecular weight of the resin is included in the range, no residue is generated when preparing the light-shielding layer, the pattern forming effect is good, and there is no loss in film thickness during development, and a good pattern can be obtained. In the total amount of the photosensitive resin composition, the content of the resin is 1 to 30% by weight, and more preferably, the content can be 3 to 20% by weight. When the content of the resin is included in the range, excellent sensitivity, developability and adhesion (tightness) can be obtained.

[0219] (2) Reactive unsaturated compounds

[0220] The reactive unsaturated compound is an essential component of the negative pattern and has an ethylene unsaturated double bond. Therefore, when the pattern forming process is exposed, it can initiate sufficient polymerization to form a pattern with excellent heat resistance, light resistance and chemical resistance.

[0221] 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.

[0222] Commercially available products of the reactive unsaturated compound are, for example, the following.

[0223] For example, the difunctional esters of (meth)acrylic acid include: aronyx M-210, M-240, M-6200, etc. from Toa Synthetic Chemical Industry Co., Ltd.; KAYARAD HDDA, HX-220, R-604, etc. from Nippon Chemical Co., Ltd.; V-260, V-312, V-335HP, etc. from Osaka Organic Chemical Industry Co., Ltd.

[0224] For example, the trifunctional esters of (meth) acrylic acid include: aronyx M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc. from Toa Synthetic Chemical Industry Co., Ltd.; KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-

[0225] 120, etc.; V-295, V-300, V-360, etc. from Osaka Organic Chemical Industry Co., Ltd.

[0226] The above products can be used alone or in combination of two or more.

[0227] In order to have a better developability, the reactive unsaturated compound may be used after being treated with an acid anhydride. In the total amount of the photosensitive resin composition, the content of the reactive unsaturated compound may be 1 to 40% by weight, for example, 1 to 20% by weight. When the content of the reactive unsaturated compound is included in the range, sufficient curing is induced when the pattern forming process is exposed, so that the reliability is excellent, the heat resistance, light resistance and chemical resistance of the pattern are excellent, and the clarity and adhesion are also excellent.

[0228] (3) Photoinitiator

[0229] In order to present a negative pattern through a photolithography machine, a photoradical initiator is required. The molar absorption coefficient of the photoinitiator in the 330 to 380 nm region is 10,000 (L / mol·cm) or more, and the temperature at which the photoinitiator loses 5% by weight is below 200°C. The molar absorption coefficient can be calculated by the beer-Lambert Law. In addition, the weight loss was detected by TGA in a nitrogen atmosphere at a rate of 5°C per minute to 300°C.

[0230] The photopolymerization initiator is generally used in a photosensitive resin composition, and for example, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, etc. may be used.

[0231] For example, the acetophenone 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)-butane-1-one, etc.

[0232] For example, the benzophenone 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, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0233] For example, the thioxanthone compounds include thioxanthone, 2-chlorothiazolone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone and the like.

[0234] For example, the benzoic acid ketone-based compounds include benzoic acid ketone, benzoic acid ketone methyl ether, benzoic acid ketone ethyl ether, benzoic acid ketone isopropyl ether, benzoic acid ketone isobutyl ether, benzyl dimethyl ketal, and the like.

[0235] For example, the triazine compounds include: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-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, (Trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphtho-1-ol)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-ol)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl (4'-methoxyphenylvinyl)-6-triazine, etc.

[0236] In addition to compounds, the photoinitiator may 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.

[0237] The photoinitiator is a free radical polymerization initiator, and may be a peroxide compound, an azobis compound, or the like.

[0238] For example, the peroxide compounds include: ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide, etc.; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, etc.; hydroperoxides such as 2,4,4,-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, t-butyl hydroperoxide, etc.; diisopropylbenzene peroxide, 2,5-dimethyl-2,5-di(t-butylperoxide) dialkyl peroxides such as butyl peroxy (butyl) hexane, 1,3-bis (t-butoxyisopropyl) benzene, t-butyl peroxy valerate, etc.; alkyl succinates such as 2,4,4-trimethylpentyl peroxy phenoxy acetate, α-peroxy neodecanoate cumyl, t-butyl peroxy benzoic acid, di-t-butyl peroxy trimethyl adipic acid, etc.; percarbonates such as di-3-methoxy butyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, bis-4-t-cyclohexyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, acetyl peroxy cyclohexyl sulfonyl, t-butyl peroxy carbonate, etc.

[0239] For example, the azobis compounds include: 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2,-azobis(methyl isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α'-azobis(isobutyronitrile) and 4,4'-azobis(4-cyanovaleric acid).

[0240] After the photoinitiator absorbs light and transitions to an excited state, it transfers its energy and is used together with a photosensitizer that undergoes a chemical reaction. For example, the photosensitizer includes: triethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0241] The content of the photoinitiator in the total amount of the photosensitive composition may be 0.01 to 10% by weight, for example, 0.1 to 5% by weight. When the content of the photoinitiator is within the above range, sufficient curing is induced when the pattern forming process is exposed, so that the reliability is excellent, the heat resistance, light resistance and chemical resistance of the pattern are excellent, and the clarity and adhesion are also excellent. In addition, the reduction of transmittance caused by the unreacted initiator can be prevented.

[0242] (4) Colorant

[0243] Both organic pigments and inorganic pigments and dyes can be used as the colorant.

[0244] The colorant may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

[0245] For example, the red pigment includes: 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.

[0246] For example, the green pigment includes: halogen-substituted copper phthalocyanine pigments, such as CI green pigment 36, CI green pigment 7, and the like.

[0247] For example, the blue pigment includes 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.

[0248] For example, the yellow pigment includes isoindoline pigments such as CI yellow pigment 139, quinophthalone pigments such as CI yellow pigment 138, nickel composite pigments such as CI yellow pigment 150, and the like.

[0249] For example, the black pigment includes organic black pigments such as lactam black, aniline black, perylene black, and Irgaphor Black S 100 CF (from BASF), or inorganic black pigments such as titanium black and carbon black.

[0250] Furthermore, according to an implementation example, the colorant in the photosensitive resin composition may include a pigment, a dye, or a combination thereof. For example, the dye may include a phthalocyanine compound.

[0251] The above components can be used alone or in combination of two or more as the pigment and dye, but are not limited thereto.

[0252] The black pigment in the above components can be used to effectively shield the light from the light shielding layer. When the black pigment is used, it can also be used together with a color-correcting agent such as anthraquinone pigments, perylene pigments, phthalocyanine pigments, and azo pigments.

[0253] In order to disperse the pigment in the photosensitive resin composition, a dispersant may be included to form a pigment dispersion. Specifically, the pigment may be used after surface pretreatment with a dispersant, or, when preparing the photosensitive resin composition, a dispersant may be added together with the pigment before use.

[0254] The dispersant may be a nonionic dispersant, anionic dispersant, cationic dispersant, etc. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, oxyalkylene polyol ester additives, alcohol alkylene oxide additives, sulfonic acid esters, sulfonic acid salts, carboxylates, carboxylates, oxyalkylene alkylamide additives, alkyl amines, etc., which may be used alone or in combination of two or more.

[0255] The dispersant products on sale include, for example, 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. produced by BYK;

[0256] EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemical Company; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc. from Zeneka Company; or PB711, PB821, etc. from Ajinomoto Company.

[0257] The content of the dispersant in the total amount of the photosensitive resin composition may be 0.1 wt % to 15 wt %. When the content of the dispersant is within the above range, the composition has excellent dispersibility, and accordingly, when preparing a light shielding layer, the stability, developability and patternability are excellent.

[0258] The pigment can also be pre-treated with a water-soluble inorganic salt and a wetting agent before use. When the pigment is used after the pre-treatment, the average particle size of the pigment can be refined.

[0259] The pretreatment is achieved by kneading the pigment together with a water-soluble inorganic salt and a wetting agent; and then filtering and washing the pigment obtained in the kneading step.

[0260] The kneading may be performed at a temperature of 40° C. to 100° C., and the filtering and washing may be performed by washing the inorganic salt with water or the like and filtering.

[0261] For example, the water-soluble inorganic salts include sodium chloride, potassium chloride, etc., but are not limited thereto.

[0262] The wetting agent uniformly mixes the pigment and the water-soluble inorganic salt, thereby playing the role of a medium that makes the pigment easy to crush. For example, the wetting agent includes: 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, and the like. These can be used alone or in combination of two or more.

[0263] The pigment subjected to 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, not only heat resistance and light resistance are excellent, but also a fine pattern can be effectively formed.

[0264] The content of the pigment in the total amount of the photosensitive resin composition may be 1% to 40% by weight, more specifically, 2% to 30% by weight. When the pigment is included within the above range, the color reproduction rate is excellent, and the curability and adhesion of the pattern are also excellent.

[0265] (5) Solvent

[0266] The solvent is compatible with the cardo-based resin, the reactive unsaturated compound, the pigment, the cardo-based compound, and the initiator, and a non-reactive substance may be used.

[0267] For example, the solvent includes: alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethyl acetate glycol ethers such as methoxyethyl acetate, ethoxyethyl acetate, and diethoxyethyl acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol Propylene glycol alkyl ether acetates such as 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-di-n-amyl ketone, 2-heptanone; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, methyl oxyacetate, butyl oxyacetate; methoxy Alkoxyacetic acid alkyl esters such as methyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3-oxopropionic acid alkyl esters such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, etc. 2-alkoxypropionic acid alkyl esters such as ethyl 2-ethoxypropionate, 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 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 hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate; keto acid esters such as ethyl pyruvate, etc.

[0268] In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol phenyl acetate can be used.

[0269] Taking into account the compatibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether (ethylene glycolmonoethyl ether); ethylene glycol acetate alkoxy ethers such as ethoxyethyl acetate; ethers such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

[0270] In the total amount of the photosensitive resin composition, the solvent may be included as a balance, specifically, the content may be 40 to 90% by weight. When the content of the solvent is included in the range, the photosensitive resin composition may have an appropriate viscosity, thereby achieving excellent processability when preparing a pattern layer.

[0271] (6) Other additives

[0272] In order to prevent the occurrence of marks or spots, improve the leveling performance and prevent the generation of residues due to undevelopment when applying the photosensitive composition, the composition may further include additives such as malonic acid; 3-amino-1,2-propanediol; a silane coupling agent containing a vinyl or (meth)acryloxy group; a leveling agent; a fluorine-based surfactant; a silicon-based surfactant; and a free radical polymerization initiator.

[0273] For example, in order to improve adhesion to a substrate, 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.

[0274] For example, the silane coupling agent includes trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltrioxysilane, γ-glycidyloxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc., which can be used alone or in combination of two or more.

[0275] The weight part of the silane coupling agent may be 0.01 parts by weight to 10 parts by weight in 100 parts by weight of the photosensitive resin composition. When the weight part of the silane coupling agent is within the above range, the adhesion and storage properties are excellent.

[0276] Furthermore, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant, as required. The surfactant has the effects of improving coating properties and preventing defects.

[0277] Furthermore, the photosensitive resin composition may further include a surfactant as required.

[0278] For example, there are fluorine-based surfactants and silicon-based surfactants, which have the effects of improving coating properties and preventing the occurrence of flaws.

[0279] The fluorine-based surfactant can be the following fluorine-based surfactants available on the market: etc.; Mecha Pack F of Dainippon Ink & Chemicals Co., Ltd. Same model F Same model F Same model F etc.; Lard from Sumitomo 3M Co. Same style Same style Same style etc.; Saffron from Asahi Glass Co., Ltd. Same style Same style Same style Same style etc.; Toray Silicon Corporation Same style Same style wait.

[0280] The silicon-based surfactant can be the following silicon-based surfactants available on the market: 3030, 3034, 3886, etc.; 303, 308, 3236, etc. from AFCONA; BYK-379, BYK-3550, BYK-3751, BYK-3754, etc. from BYK.

[0281] In 100 parts by weight of the photosensitive resin composition, the weight of the surfactant can be 0.001 parts by weight to 5 parts by weight. When the weight of the surfactant is within the range, the coating uniformity can be ensured, no streaking occurs, and the wettability of the glass substrate is excellent. In addition, the photosensitive resin composition can be added with a certain amount of antioxidants, stabilizers and other additives within the range that does not damage the physical properties.

[0282] In another implementation example, the photosensitive resin composition can be used to perform patterning on a pixel separation portion of an organic light emitting element electrode.

[0283] Hereinafter, the synthesis examples and examples of the present invention will be described in detail, but the synthesis examples and examples of the present invention are not limited thereto.

[0284] (Preparation of black photosensitive composition)

[0285] Synthesis Example 1: (Chemical formula 8 represents the preparation of 9,9-Bis[4-(glycidyloxy)phenyl]fluorene)

[0286] 20 g of 9,9'-bisphenolfluorene (Sigma Aldrich), 8.67 g of glycidyl chloride (Sigma Aldrich), 30 g of anhydrous potassium carbonate and 100 ml of dimethylformamide were poured into a 300 ml three-necked round-bottom flask equipped with a distillation tube, heated to 80°C, and reacted for 4 hours. Then, the temperature was lowered to 25°C, and the reaction liquid was filtered. Then, the filtrate was stirred and dropped into 1000 ml of water. The precipitated powder was filtered, washed with water, reduced pressure at 40°C and dried to obtain 25 g of 9,9-bis(4-(glycidyloxy)phenyl]fluorene represented by the following compound 8. The purity of the powder was obtained by HPLC analysis, and the purity was 98%.

[0287] <Chemical Formula 8>

[0288]

[0289] Synthesis Example 2: Preparation of Cardo-based binder resin

[0290] 25 g (54 mmol) of compound 1 obtained in Synthesis Example 1, 8 g of acrylic acid (Oi Kakin Co., Ltd.), 0.2 g of benzyl triethylammonium chloride (Oi Kakin Co., Ltd.), 0.2 g of hydroquinone (Oi Kakin Co., Ltd.) and 52 g of propylene glycol methyl ether acetate (Sigma Aldrich Co., Ltd.) were poured into a 300 ml 3-neck round bottom flask equipped with a distillation tube, and stirred at 110° C. for 6 hours. After the reaction was completed, 8 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas Co., Ltd.) and 1.8 g of tetrahydrophthalic acid (Sigma Aldrich Co., Ltd.) were further poured, and then stirred at 110° C. for 6 hours. After the reaction was completed, the reaction solution was recovered and analyzed, and as a result, a cardo-based binder resin having a molecular weight of 4,580 and a solid powder content of 45% was obtained.

[0291] Preparation Example 1: Preparation of Pigment Dispersion

[0292] Using a paint shaker (Asada), Irgaphor Black S 100 CF (black pigment) was added to the

[0293] / BASF) 15 g, Disperbyk 163 8.5 g (BYK) and SR-3613 6.5 g (SMS), propylene glycol methyl ether acetate 70 g, and zirconia beads 100 g with a diameter of 0.5 mm (Toray) were dispersed for 10 hours to obtain a dispersion.

[0294] Ⅰ. Surface roughness, hole transport layer evaporation and adhesion evaluation

[0295] In order to evaluate the surface roughness of the pixel defining layer prepared according to the present invention, the evaporation and adhesion of the hole transport layer, the components in Table 1 below were used to prepare a photosensitive composition liquid.

[0296] Specifically, an initiator is dissolved in a solvent, and then stirred at room temperature, wherein a binder resin and a polymerizable compound are added, and stirred at room temperature. Then, a colorant and other additives are added to the obtained reactant, and stirred at room temperature. Then, the resultant is filtered three times to remove impurities, and a photosensitive resin composition is prepared.

[0297]

Table 1

[0298] Component ratio (%) Pigment dispersion (Preparation Example 1) 23 Cardo binder (Synthesis Example 2) 15 Miraemer M600 (Mihara Chemical Co., Ltd.) 12.5 PBG-304(Trony) 0.5 Propylene glycol methyl ether acetate 49

[0299] The method for preparing a negative pixel definition layer (negative PDL) using the photosensitive composition is as follows.

[0300] (1) Coating and coating steps

[0301] On a cleaned and metal-evaporated 10cm*10cm substrate, a photosensitive composition is coated with a constant thickness using a spin coater, and then a portion of the solvent is removed using a vacuum chamber dry (VCD) to form a coating film. The thickness of the coating of the photosensitive composition after VCD is 3.5 microns to 3.3 microns.

[0302] (2) Pre-baking step

[0303] On a hot plate, heat at 80°C to 150°C, preferably at 90°C to 120°C for 50 seconds to 200 seconds to remove the solvent contained in the obtained coating film. Preferably, heat for 60 seconds to 180 seconds. More preferably, heat for 100 seconds to 150 seconds. This process removes a certain amount of solvent so that when the next process (exposure) step is implemented, the mask contamination of the pixel morphology is reduced and a clean pattern is prepared.

[0304] (3) Exposure Step

[0305] On the coating film obtained above, a mask in the form of pixels is interspersed to form the desired pattern and a certain thickness. Then, 190nm to 600nm actinic rays are irradiated by an exposure machine. Preferably, a metal or LED light source with ghi-line can be irradiated to form a pattern. The exposure amount for pattern formation is 10 to 2000mJ / cm 2 The photoresist material of the negative type has a transmittance of three sections, namely, 0% (non-exposed part), 20 to 50% (half-tone), and 100% (full-tone), to form a pattern.

[0306] (4) Development step

[0307] After the exposure step, the image pattern is formed by dipping the image with a 2.38 wt% developer of TMAH (tetramethylhydroxyammonium) at 23±2°C for a certain time (minutes), and then washing with deionized water (DI water) to dissolve and remove the unexposed part, leaving only the exposed part. The thickness of the coating is 1.30 to 1.95 μm when half-tone is used, and 3.20 to 3.40 μm when full-tone is used.

[0308] (5) Surface roughness testing

[0309] On a glass substrate, a composition containing a colorant is used for coating, exposure, development and post-baking to form a negative pixel definition layer, and an evaluation substrate including the negative pixel definition layer is obtained and used as a sample for roughness detection. Atomic force microscopy (AFM, parksystems / XE-

[0310] 100) The physical properties of the evaluation substrate were tested in non-contact mode with a scan rate of 0.3 (Hz), a set point of 11.26 nm, and an area of ​​2 μm long x 2 μm wide.

[0311] (6) Hole transport layer evaporation and adhesion evaluation

[0312] The coloring pattern is formed by the preparation process, and then, a coloring machine is used to evaporate the hole transport layer (HTL) with a thickness of 120 to 140 nm. 100 cut surfaces are formed on the evaporated test piece by cross-cutting, and then the NICHIBAN peeling tape (CT-24) is pasted on the cut surface without bubbles. When the tape is peeled off, the UTM (QM 100S) equipment produced by Coretech Korea is used, fixed on a 90° fixture, and then a certain force is applied at a speed of 300 mm / min for peeling. The number of tears on the cut surface after peeling was detected compared to before the peeling test, and the adhesion was confirmed.

[0313]

Table 2

[0314]

[0315]

[0316] After irradiating the exposure energy in various ways, the substrates obtained under the same development conditions were used to compare the surface roughness and the adhesion with the hole transport layer (HTL). 2 When irradiated with high intensity, the surface roughness was 4.898nm, which was confirmed to be high. This shows that the adhesion with the hole transport layer is good, but when the hole transport layer is evaporated, the surface roughness is high and uneven, which will produce pinholes, which will reduce the reliability of the subsequent process. This result has a negative impact on the life of the display.

[0317] In contrast, the exposure dose of Examples 1 to 19 was 10 mJ / cm 2 Up to 1000mJ / cm 2In the example 1, the surface roughness value is extremely low when compared with the comparative examples 2 and 3, and the adhesion is also good. According to this result, based on the good adhesion between the hole transport layer, pixel defects can be minimized, the reliability of the display can be improved, and the life can be extended.

[0318] Furthermore, the exposure amount of Examples 14 to 19 was 500 mJ / cm 2 Up to 1000mJ / cm 2 According to the results, it can be confirmed that the exposure dose is 500mJ / cm 2 When the exposure dose is 1000 mJ / cm 2 When the surface roughness is above 0.1, the surface roughness value is extremely low, which results in a decrease in the adhesion of the hole transport layer and causes pixel failure.

[0319] Ⅱ. Plastic hardness and modulus (nanometer counter) evaluation

[0320] Second, in order to evaluate the plastic hardness and modulus of the pixel definition layer prepared by the present invention, a photosensitive composition liquid was prepared using the components in Table 3 below.

[0321] Specifically, an initiator is dissolved in a solvent, and then stirred at room temperature, wherein a binder resin and a polymerizable compound are added, and stirred at room temperature. Then, a colorant and other additives are added to the obtained reactant, and stirred at room temperature. Then, the resultant is filtered three times to remove impurities, and a photosensitive resin composition is prepared.

[0322]

Table 3

[0323]

[0324] The method for preparing a negative pixel definition layer (negative PDL) using the photosensitive composition is as follows.

[0325] (1) Coating and coating steps

[0326] On a cleaned and metal-evaporated 10cm*10cm substrate, a photosensitive composition is coated with a constant thickness using a spin coater, and then a portion of the solvent is removed using a vacuum chamber dry (VCD) to form a coating film. The thickness of the coating of the photosensitive composition after VCD is 3.5 microns to 3.3 microns.

[0327] (2) Pre-baking step

[0328] On a hot plate, heat at 80°C to 150°C, preferably at 90°C to 120°C for 50 seconds to 200 seconds to remove the solvent contained in the obtained coating film. Preferably, heat for 60 seconds to 180 seconds. More preferably, heat for 100 seconds to 150 seconds. This process removes a certain amount of solvent so that when the next process (exposure) step is implemented, the mask contamination of the pixel morphology is reduced and a clean pattern is prepared.

[0329] (3) Exposure Step

[0330] On the coating film obtained above, a mask in the form of pixels is interspersed to form the desired pattern and a certain thickness. Then, 190nm to 600nm actinic rays are irradiated by an exposure machine. Preferably, a metal or LED light source with ghi-line can be irradiated to form a pattern. The exposure amount for pattern formation is 20 to 150mJ / cm 2 , preferably 70 mJ / cm 2 Up to 140mJ / cm 2 , further preferably, 80 to 110 mJ / cm 2 The transmittance of the photomask used in the exposure has three sections, namely, 0% (non-exposed part), 20 to 50% (half-tone), and 100% (full-tone), forming a pattern.

[0331] (4) Development step

[0332] After the exposure step is performed, the image is developed at 23±2° C. for a certain time (minutes) using a 2.38 wt % developer solution of TMAH (tetramethylhydroxyammonium) by dipping method, and then rinsed with deionized water (DI water) to dissolve and remove the unexposed part, leaving only the exposed part to form an image pattern.

[0333] After the development step, the thickness of the half-tone is preferably 1.25 μm to 2.20 μm, more preferably 1.40 μm to 2.00 μm, and the thickness of the full-tone is preferably 3.20 μm to 3.42 μm, more preferably 3.25 μm to 3.35 μm after the development step.

[0334] (5) Post-exposure step

[0335] Following the development step, in order to prevent pattern disintegration after post-baking, a photomask is not used, but the entire area is irradiated with a light source having 190nm to 600nm actinic rays, preferably a metal or LED light source having a ghi-line, to increase the strength of the coating. The exposure amount for increasing the intensity is 50 to 1,000mJ / cm 2 .

[0336] (6) Post-baking step

[0337] In order to obtain the image pattern obtained by the post-exposure treatment, post baking is carried out in an oven at 200 to 300° C. for 30 to 120 minutes to completely remove the solvent, solidify the pattern and form a film, and then detect it using a scanning microscope.

[0338] (7) Plastic hardness and modulus (nanometer counter) testing

[0339] In order to detect the plastic hardness and modulus, a composition containing a colorant was coated on the glass surface, exposed, developed and post-baked to form a negative pixel definition layer, and an evaluation substrate including the negative pixel definition layer was obtained. The physical properties of the evaluation substrate were tested under the conditions of test force (0.2mN), loading time (8sec) and creep time (5sec) using a nanometer counter (Fischer HM2000).

[0340]

Table 4

[0341]

[0342] The photosensitive composition coating film prepared by the process steps was tested and compared in terms of plastic hardness and modulus. As shown in Table 4 above, in Examples 20 to 23, when the content of the organic pigment was 10 to 40 wt%, it was confirmed that the plastic hardness and modulus of the photosensitive composition coating film were 300 N / mm 2 Up to 500N / mm 2 In contrast, in Comparative Example 4, due to the low content of the organic pigment, the plastic hardness and modulus are low, and thus cracks may occur due to external impact.

[0343] And, if Figure 1As shown, the pixel patterns of the photosensitive compositions prepared in Examples 20 to 23 and Comparative Examples 4 to 6 were detected using an optical microscope to confirm the degree of residue. It was confirmed that the residue levels of Examples 20 to 23 and Comparative Example 4 were excellent, and when the organic pigment content of Comparative Examples 5 and 6 was 40 wt % or more, it was confirmed that the mechanical and physical properties met the requirements, but residues were present on the periphery or inside the pixel.

[0344] The above description is merely an example of the present invention, and a person skilled in the art in the art to which the present invention belongs can make various modifications without departing from the essential characteristics of the present invention.

[0345] Therefore, the embodiments disclosed in this specification are used to describe the present invention, rather than to limit the present invention, and the idea and scope of the present invention are not limited by such embodiments. The scope of the claims of the present invention should be interpreted according to the following claims, and should be interpreted as including all technologies within the scope equivalent thereto falling within the scope of the claims of the present invention.

Claims

1. A method for preparing a pixel defining layer, characterized in that: The method comprises the steps of: coating and coating a photosensitive composition; pre-baking; exposing; Development, the exposure step at 10mJ / cm 2 Up to 1000mJ / cm 2 The exposure amount is irradiated with actinic rays, and the surface roughness after the exposure step is 1.0 nm to 3.0 nm. More than one layer is prepared by a single exposure and development process.

2. The method for preparing a pixel defining layer according to claim 1, wherein: The transmittance of the photomask is divided into three sections, ie, 0% (non-exposed portion), 20 to 50% (half-tone), and 100% (full-tone), and more than one layer is formed through a single exposure and development process.

3. The method for preparing a pixel defining layer according to claim 1, wherein: It further includes a post-exposure process; and a post-baking process.

4. The method for preparing a pixel defining layer according to claim 3, characterized in that: The coating film formed after the post-baking step has a thermal conductivity of 300 N / mm 2 Up to 500N / mm 2 Plastic hardness and modulus of 5,000Mpa to 7,000Mpa.

5. The method for preparing a pixel defining layer according to claim 3, wherein: The coating film formed after the post-baking step has no residue.

6. The method for preparing a pixel defining layer according to claim 1, characterized in that: In the photosensitive composition, the content of the pigment dispersion is 10 to 40% by weight.

7. The method for preparing a pixel defining layer according to claim 6, wherein: Based on 100 wt % of the pigment dispersion, the content of the organic black pigment is 3 wt % to 25 wt %.

8. The method for preparing a pixel defining layer according to claim 1, characterized in that: After the development step, the full-tone thickness was 3.20 to 3.42 μm.

9. The method for preparing a pixel defining layer according to claim 1, wherein: After the development step, the half-tone thickness is 1.25 to 2.20 μm.

10. The method for preparing a pixel defining layer according to claim 1, characterized in that: The photosensitive composition includes a colorant.

11. The method for preparing a pixel defining layer according to claim 1, characterized in that: The photosensitive composition includes a pattern forming resin, and the pattern forming resin includes an acrylic binder resin, a cardo binder resin, or a combination thereof.

12. A pixel defining layer prepared according to claim 1. 13 . An organic light emitting display device comprising the pixel defining layer according to claim 12 .

14. An electronic device, characterized in that: The invention comprises the display device according to claim 13 and a control unit for driving the display device.

Images