Method for manufacturing pixel definition layer

Abstract

To prolong the reliability and life of a display, as well as making the color of the display vivid by realizing a colored pattern with high optical density on an electrode substrate.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; and performing post heat processing on the composition. According to the composition and the method of manufacturing the pixel definition layer pattern, the optical density in the panel after the post heat processing is in the range of 0.80 to 1.5 / μm and the visibility and the contrast can be improved.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a pixel defining 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 the light incident from the outside and reflected from the panel. However, applying the polarizing film to a flexible device has a disadvantage in 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 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 due to low reflectivity.

[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] Such a pattern has better visibility as the optical density (OD) is higher to block the light transmitted from the outside or reflected from the bottom. The organic light-emitting display made of the pixels formed in this way can achieve clearer colors. However, there is a need for research to effectively reduce the reflectance around 550 nm, which has the most influence on visibility.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention is for providing a photosensitive resin composition capable of reducing the reflectance near the 550 nm wavelength, which has the most influence on visibility, and improving visibility.

[0010] Also, the present invention is for providing a light-shielding layer manufactured using the photosensitive resin composition and a display device including the light-shielding layer.

Means for Solving the Problems

[0011] The method for manufacturing a pixel definition layer according to the present invention includes steps of applying and coating a photosensitive composition; pre-baking; exposing; developing; and post-heat treatment; after the post-heat treatment step, the optical density (OD) is 0.8 to 1.5 / μm or less, preferably 0.83 to 1.4 / μm or less, more preferably 0.9 to 1.3 / μm or less; and the reflectance is more than 0.01% and less than 6.5%, preferably more than 0.01% and 6.3% or less.

[0012] It is more preferable that the oven temperature in the post-heat treatment stage is 250 to 270 °C.

[0013] It is more preferable that the post-heat treatment stage is 60 to 120 minutes.

[0014] The photosensitive composition preferably contains a colorant.

[0015] The colorant is preferably contained in an amount of 17 to 35% by weight based on the total amount of the photosensitive composition.

[0016] The colorant preferably contains one or more of an inorganic dye, an organic dye, an inorganic pigment, and an organic pigment.

[0017] The colorant is preferably pretreated using a dispersant; or a water-soluble inorganic salt and a wetting agent.

[0018] The photosensitive composition preferably contains a patterning resin containing an acrylic binder resin, a caldo binder resin, or a combination thereof.

[0019] The weight average molecular weight of the acrylic binder resin is preferably 3,000 g / mol to 150,000 g / mol.

[0020] The caldo binder resin preferably contains the repeating structure of Chemical Formula 1 below.

[0021]

Chemical Formula

[0022] In Chemical Formula 1 above,

[0023] 1) R 1 and R 2 are each independently hydrogen; deuterium; halogen; an aryl group of C6 to C 30 ; a C2 to C containing at least one heteroatom 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,

[0024] 2) R 1 and R 2 can form a ring with adjacent groups,

[0025] 3) m or n is independently an integer from 0 to 4,

[0026] 4) A1 and A2 are independently the following Chemical Formula 2 or Chemical Formula 3,

[0027]

Chem.

[0028]

Chem.

[0029] In the said Chemical Formula 2 and Chemical Formula 3,

[0030] 4-1) * indicates the connecting site,

[0031] 4-2) R 3 ~R 6 are independently 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,

[0032] 4-3) R 3 ~R 6 can form a ring with adjacent groups,

[0033] 4-4) Y 1 and Y 2 are independently of each other represented by the following Chemical Formula 6 or Chemical Formula 7,

[0034]

Chemical formula

[0035]

Chemical formula

[0036] In the above Chemical Formula 6 and Chemical Formula 7,

[0037] 4-4-1) * indicates the bonding position,

[0038] 4-4-2) R 9 is hydrogen or methyl,

[0039] 4-4-3) R 10 ~R 13 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 20an alkoxy group; C6-C 30 an aryloxy group; a fluorenyl group: a carbonyl group; an ether group; or a C1-C 20 alkoxycarbonyl group, and

[0040] 4-4-4)L 1 -L 3 are each independently a single bond; a fluorenylene group; a C2-C 30 alkylene; a C6-C 30 arylene; a C2-C 30 heterocyclic ring; a C1-C 30 alkoxylene; a C2-C 30 alkyleneoxy; a C6-C 30 aryloxy group; a C2-C 30 polyethyleneoxy group, and

[0041] 4-4-5)q and r are each independently an integer from 0 to 3; provided that q + r = 3, and

[0042] 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, and

[0043] 6) X 1 is a single bond; O; CO; SO2; CR’R”; SiR’R”; the following Chemical Formula 4; or Chemical Formula 5, and

[0044] 6-1) R’ and R” are each independently hydrogen; deuterium; halogen; a C6-C 30 aryl group; a C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; 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, and

[0045] (6-2)R’ and R” can form a ring with adjacent groups

[0046] [Chemical formula]

[0047] [Chemical formula]

[0048] In the above Chemical formula 4 and Chemical formula 5,

[0049] 6-3)* indicates the bonding position,

[0050] 6-4)R 7 ~R 8 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,

[0051] 6-5)o and p are independently of each other integers from 0 to 4,

[0052] 7)X 2 is a 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 20an 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 alkoxycarbonyl group,

[0053] (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 C1-C 30 alkyl group or a C6-C 30 aryl group-substituted or unsubstituted silane 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 aryloxy group; a C1-C 30 alkyl group, C2-C 30 alkenyl group; C2-C 30 alkynyl group; C6-C 30 aryl group; a C6-C 30 aryl group substituted with deuterium; a fluorenyl group; a C2-C containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P 30 heterocyclic group; C3-C 30 aliphatic ring group; C7-C 30 arylalkyl group; C8-C 30 arylalkenyl group; and can be further substituted with one or more substituents selected from the group consisting of combinations thereof, and adjacent substituents can form a ring with each other.

[0054] The weight average molecular weight of the cardo resin is preferably 1,000 to 100,000 g / mol.

[0055] The caldo resin is preferably contained in an amount of 1 to 30% by weight based on the total amount of the photosensitive composition.

[0056] The photosensitive composition preferably contains 1 to 40% by weight of a reactive unsaturated compound based on the total amount thereof.

[0057] The photosensitive composition preferably contains 0.01 to 10% by weight of a photoinitiator based on the total amount thereof.

[0058] As another specific example, the present invention preferably provides a pixel definition layer manufactured by the manufacturing method.

[0059] As another specific example, the present invention preferably provides an organic light-emitting display device including the pixel definition layer.

[0060] 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.

Advantages of the Invention

[0061] The present invention realizes a colored pattern with high optical density on an electrode substrate, not only has a clear color, but also is for enhancing display reliability and lifespan. In the case of a polarizing plate used in an OLED display, generally the reflectance is at a level of 0.01% to 6%, but it has physical disadvantages such as being inflexible and heavy. On the other hand, the pixel separation layer according to the present invention enables the realization of a flexible display, and reduces the thickness and weight of the display. Also, it has the advantage of being able to achieve a reflectance of 6.5% or less by blocking and absorbing external reflected light.

Embodiments for Carrying Out the Invention

[0062] Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. When adding reference numerals to the components of each drawing, the same components have the same numerals as much as possible even if they are shown on other drawings.

[0063] In the description of the present invention, if it is determined that a specific description of related known configurations or functions may obscure the gist of the present invention, the detailed description thereof may be omitted. When terms such as "comprising", "having", "consisting of", 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.

[0064] In addition, 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 component from other components, and the essence, order, sequence, number, etc. of the component are not limited by such terms.

[0065] In the description of the positional relationship of components, when it is described that two or more components are "connected", "coupled" or "joined", it should be understood that two or more components may be directly "connected", "coupled" or "joined", but two or more components and other components may also be "interposed" 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.

[0066] 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 a component is said to be "directly above" another part, it should be understood to mean that there is no other part in between.

[0067] In the description of the temporal flow relationship related to components, operation methods, manufacturing methods, etc., for example, when the temporal front-back relationship or flow front-back relationship is described such as "after ~", "subsequent to ~", "next to ~", "before ~", etc., it includes cases where it is not continuous unless "immediately" or "directly" is used.

[0068] On the one hand, when a numerical value for a component or its corresponding information is mentioned, even without a separate explicit description, the numerical value or its corresponding information can be interpreted as including an error range that may be generated by various factors (e.g., process factors, internal or external shocks, noise, etc.).

[0069] In the present specification and the appended claims, unless otherwise mentioned, the terms used are as follows within the scope not departing from the idea of the present invention.

[0070] The term "halo" or "halogen" used in the present application includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) unless otherwise explained.

[0071] The term "alkyl" or "alkyl group" used in the present application has 1 to 60 carbons linked by a single bond, and means a radical of a saturated aliphatic functional group including a linear alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycloalkyl group, a cycloalkyl-substituted alkyl group, etc., unless otherwise explained.

[0072] The term "haloalkyl group" or "halogenalkyl group" used in the present application means an alkyl group substituted with a halogen unless otherwise explained.

[0073] The term "alkenyl" or "alkynyl" used in the present application each has a double bond or a triple bond, includes a linear or side-chain group, and has 2 to 60 carbon atoms, but is not limited thereto, unless otherwise explained.

[0074] The term "cycloalkyl" used in the present application means an alkyl forming a ring having 3 to 60 carbon atoms, but is not limited thereto, unless otherwise explained.

[0075] As used herein, 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 unless otherwise specified, but is not limited thereto.

[0076] As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" mean an alkenyl group to which an oxygen radical is attached, and have 2 to 60 carbon atoms unless otherwise specified, but are not limited thereto.

[0077] As used herein, the terms "aryl group" and "arylene group" have 6 to 60 carbon atoms each unless otherwise specified, but are not limited thereto. In the present application, the aryl group or arylene group includes a single cyclic, 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.

[0078] As used herein, the term "ring assemblies" means that two or more ring systems (single ring or fused ring systems) are directly connected to each other by a single bond or a double bond, and the number of such direct connections between the rings is one less than the total number of ring systems contained in the compound. Ring assemblies can have the same or different ring systems directly connected to each other by a single bond or a double bond.

[0079] Since the aryl group in the present application includes ring assemblies, the aryl group includes biphenyl and terphenyl in which a benzene ring, which is a single aromatic ring, is connected by a single bond. Also, since the aryl group includes a compound in which an aromatic ring system joined to an aromatic single ring is connected 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 connected by a single bond.

[0080] As used herein, the term "fused plurality of ring systems" means a fused ring form sharing at least two atoms, including forms where ring systems of two or more hydrocarbons are fused and forms where at least one heterocyclic ring system containing at least one heteroatom is fused. Such a fused plurality of 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.

[0081] As used herein, the term "spiro compound" has a "spiro union", and a spiro union means a linkage 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.

[0082] As used herein, the terms "fluorenyl group", "fluorenylene group", and "fluorenetriyl group" respectively mean a monovalent, divalent, or trivalent functional group in which R, R', R", and R'" are all hydrogen in the following structures, unless otherwise specified. 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 as fluorenyl group.

[0083]

Chemical formula

[0084] Further, 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.

[0085] 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 assembly, a plurality of joined ring systems, spiro compounds, etc. containing heteroatoms.

[0086] For example, the "heterocyclic group" may include compounds containing heteroatomic groups such as SO2, P=O, etc. instead of carbon forming the ring, as in the following compounds.

[0087]

Chemical formula

[0088] 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.

[0089] As used herein, the term "polycyclic" includes ring assemblies such as biphenyl and terphenyl, fused multiple ring systems, and spiro compounds, and includes both aromatic and non-aromatic compounds, including hydrocarbon rings as well as heterocycles containing at least one heteroatom.

[0090] As used herein, the term "alicyclic group" means a cyclic hydrocarbon excluding aromatic hydrocarbons, and includes 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, which is an aromatic ring, is fused with cyclohexane, which is a non-aromatic ring, it also falls within the category of alicyclic rings.

[0091] Also, when prefixes are named consecutively, it means that 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.

[0092] 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 It means being substituted with one or more substituents selected from the group consisting of a heterocyclic group, and is not limited to these substituents.

[0093] In this application, for the “functional group name” corresponding to an aryl group, an arylene group, a heterocyclic group, etc. exemplified as examples of each symbol and its substituents, it is also possible to describe the “name of the functional group reflecting the valence number”, but it is also possible to describe it 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)”, the divalent group can be described as “phenanthrylene (group)” by distinguishing the valence number, etc., but it can also be described as “phenanthrene” which is the name of the parent compound regardless of the valence number.

[0094] Similarly, in the case of pyrimidine, it can be described as “pyrimidine” regardless of the valence number, or in the case of monovalence, it can be described as pyrimidinyl (group), and in the case of divalence, it can be described as pyrimidinylene (group) etc. as the “name of the group” of the corresponding valence number. Therefore, when describing the type of substituent by the name of the parent compound in this application, it can mean an n-valent “group” formed by the elimination of a hydrogen atom bonded to a carbon atom and / or a heteroatom of the parent compound.

[0095] Also, in this specification, when describing a compound name or a substituent name, numbers, alphabets, etc. indicating positions 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.

[0096] Also, unless otherwise explicitly stated, the chemical formulas used in this application are applied in the same way as the substituent definitions according to the exponent definitions of the following chemical formulas.

[0097] [Chem.]

[0098] 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 representation 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.

[0099] [Chem.]

[0100] 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.

[0101] Also, unless otherwise stated in this specification, when representing 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.

[0102] 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 atoms shared include carbon or heteroatoms.

[0103] In this application, an 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.

[0104] 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 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 that includes the above-mentioned component(s) may be used.

[0105] 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. The present invention is only defined by the scope of the claims described later.

[0106] 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, a black matrix, or a pixel definition layer (PDL).

[0107] 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 in combination with a colored pigment. At this time, in order to mix a colored 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.

[0108] Hereinafter, each component will be specifically described.

[0109] 1. The manufacturing process of the negative pixel definition layer is as follows.

[0110] (1) Coating and coating stage

[0111] 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 surface becomes fluid due to the remaining solvent, which has the disadvantage of deteriorating flatness. In order to overcome this, a part of the solvent is removed using a VCD (vacuum chamber dry) to reduce the fluidity on the surface.

[0112] (2) Pre-bake stage

[0113] 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 deep part 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 part during ultraviolet light irradiation, and due to non-curing, the pattern will be removed without being formed in the development step.

[0114] (3) Exposure step

[0115] When 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 respectively or in combination.

[0116] (4) Development step

[0117] In the exposure step, when irradiating with actinic rays, it is divided into an exposed part and a non-exposed part by a photomask. In the case of a positive type, the exposed part becomes soluble in the developer, and the non-exposed part withstands the developer and the pattern remains. In the case of a negative type, the exposed part cures and has resistance to the developer, and the non-exposed part 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 part (cured) and a non-exposed part (developed) to form a pattern.

[0118] (5) Post-heat treatment step

[0119] This is a step of heating the developed substrate at a high temperature of 210 °C or higher to remove the remaining solvent and moisture. If the solvent and moisture are not completely removed in the corresponding step, the remaining solvent and moisture after post-heat treatment will affect the element, thereby affecting the life of the element such as dark spots or pixel shrinkage.

[0120] In the present invention, the oven temperature in the post-heat treatment step is preferably 250 to 270 °C. Further, the post-heat treatment step is preferably 60 to 120 minutes.

[0121] 2. The composition for forming a negative pixel defining layer containing a colorant is as follows.

[0122] (1) Patterning resin

[0123] The patterning resin according to an embodiment of the present invention contains a caldo-based binder resin.

[0124] 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.

[0125] 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.

[0126] 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 combination of two or more.

[0127] 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.

[0128] The cardo resin contains a repeating structure as shown in Chemical Formula 1 below.

[0129]

Chemical formula

[0130] In the above Chemical Formula 1,

[0131] 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

[0132] 2) R’ and R” can form a ring with adjacent groups

[0133] 3) m or n is each independently an integer from 0 to 4

[0134] 4) A1 and A2 are each independently the following Chemical Formula 2 or Chemical Formula 3

[0135]

Chemical Formula

[0136]

Chemical Formula

[0137] In the above Chemical Formula 2 and Chemical Formula 3,

[0138] 4 - 1) * indicates the connection site

[0139] 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

[0140] 4-3)R 3 ~R 6 can form a ring with adjacent groups,

[0141] 4-4)Y 1 and Y 2 are independently of each other represented by the following Chemical Formula 6 or Chemical Formula 7,

[0142]

Chem.

[0143]

Chem.

[0144] In the above Chemical Formula 6 and Chemical Formula 7,

[0145] 4-4-1)* indicates the bonding position,

[0146] 4-4-2)R 9 is hydrogen or methyl,

[0147] 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,

[0148] 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,

[0149] 4-4-5)q and r are independently of each other integers from 0 to 3, provided that q + r = 3,

[0150] 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,

[0151] 6)X 1 is a single bond; O; CO; SO2; CR’R”; SiR’R”; the following Chemical Formula 4; or Chemical Formula 5,

[0152] 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 C1-C 20 is an alkoxycarbonyl group,

[0153] 6-2) R’ and R” can form a ring with adjacent groups,

[0154]

Chemical formula

[0155]

Chemical formula

[0156] In the above Chemical formulas 4 and 5,

[0157] 6-3) * indicates the bonding position,

[0158] 6-4) R 7 ~R 8 are independently of each other hydrogen; deuterium; halogen; C6-C 30 an aryl group; a C2-C heterocyclic group 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 C1-C 20 is an alkoxycarbonyl group,

[0159] 6-5) o and p are independently of each other an integer from 0 to 4,

[0160] 7) X2 is a C6-C 30 aryl group; a C2-C containing at least one heteroatom of O, N, S, Si and P 30 heterocyclic group; a fused ring group of an aliphatic ring and an aromatic ring of C6-C 30 ; 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,

[0161] 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 aryl group substituted with deuterium 30 ; a fluorenyl group; a C2-C heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P 30 ; 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.

[0162] 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.

[0163] 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.

[0164] Said R‘, R”, R 1 ~R 8 and R 10 ~R 13 when being a fluorenyl group, preferably 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9’-spirobifluorene, etc.

[0165] 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.

[0166] The above R’, R”, X 2 , R 1 ~R 8 and R 10 ~R 13 When they are alkyl groups, preferably, they are C1-C 10 alkyl groups, for example, they can be methyl, t-butyl, etc.

[0167] The above R’, R”, X 2 , R 1 ~R 8 and R 10 ~R 13 When they are alkoxyl groups, preferably, they are C1-C 20 alkoxyl groups, more preferably, they are C1-C 10 alkoxyl groups, for example, they can be methoxy, t-butoxy, etc.

[0168] The above R’, R”, X 2 , L 1 ~L 3 , R 1 ~R 8 and R 10 ~R 13 The ring formed by the adjacent groups of the above R’, R”, X 60 , L 60 ~L 60 and R 20 ~R 14 is a C6-C

[0169] 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, and tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, and benzyltriethylammonium chloride.

[0170] 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. When the weight average molecular weight of the resin is within the above range, pattern formation can be successfully performed without residue during the production of the light-shielding layer, there is no loss in 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 adhesion (adhesion strength) can be obtained.

[0171] (2) Reactive unsaturated compound

[0172] 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.

[0173] 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.

[0174] Examples of commercially available products of the reactive unsaturated compound are as follows.

[0175] 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.; V - 260, V - 312, V - 335HP, etc. of Osaka Organic Chemical Industry Co., Ltd.

[0176] 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.; V - 295, V - 300, V - 360, etc. of Osaka Organic Chemical Industry Co., Ltd.

[0177] The above products can be used alone or in combination of two or more.

[0178] 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, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability, heat resistance, light resistance, chemical resistance of the pattern, and also excellent resolution and adhesion.

[0179] (3) Photoinitiator

[0180] In order to realize a negative pattern in 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 330 to 380 nm region 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 heating up to 300 °C at a rate of 5 °C per minute in a nitrogen atmosphere.

[0181] 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.

[0182] 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, etc.

[0183] Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0184] Examples of the thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methyloxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0185] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, and the like.

[0186] 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.

[0187] In addition to the above compounds, the photoinitiator can also use carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, and the like.

[0188] As the radical polymerization initiator, the photoinitiator can use peroxide compounds, azobis compounds, and the like.

[0189] Examples of the peroxide compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, and acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butyloxyisopropyl)benzene, and t-butyl peroxy valeric acid n-butyl ester; alkyl peresters such as 2,4,4-trimethylpentyl peroxyphenoxyacetate, α-cumyl peroxyneodecanoate, t-butyl peroxybenzoate, and 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, and t-butyl peroxyallyl carbonate, and the like.

[0190] Examples of the azo-based 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).

[0191] The photoinitiator may be used together with a photochromic agent that causes a chemical reaction by absorbing light and becoming excited and then transmitting its energy. Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0192] 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 formation 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.

[0193] (4) Colorant

[0194] As the colorant, all of organic pigments, inorganic pigments, and dyes can be used.

[0195] As the colorant, red pigments, green pigments, blue pigments, yellow pigments, black pigments, and the like can be used.

[0196] Examples of the red pigment include C.I. Red Pigment 254, C.I. Red Pigment 255, C.I. Red Pigment 264, C.I. Red Pigment 270, C.I. Red Pigment 272, C.I. Red Pigment 177, C.I. Red Pigment 89, and the like.

[0197] Examples of the green pigment include copper phthalocyanine pigments substituted with halogens such as C.I. Green Pigment 36 and C.I. Green Pigment 7.

[0198] 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.

[0199] 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.

[0200] Examples of the black pigment include lactam black, aniline black, perylene black, titanium black, carbon black, and the like.

[0201] In addition, the colorant in the photosensitive resin composition according to the embodiment may include a pigment, a dye, or a combination thereof. For example, the dye may include a phthalocyanine-based compound.

[0202] The pigments and dyes may be used alone or in combination of two or more, and are not limited to these examples.

[0203] 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, and an azo-based pigment.

[0204] 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.

[0205] 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 admixture of two or more thereof.

[0206] Examples of products of the commercially available dispersants 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.

[0207] The dispersant can be contained in an amount of 0.1% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the composition has excellent dispersibility, and thus excellent stability, developability and patternability during the production of the light-shielding layer.

[0208] 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.

[0209] The pretreatment is carried out through the steps of 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.

[0210] 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.

[0211] Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride, potassium chloride, etc.

[0212] 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.

[0213] 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.

[0214] 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 curing properties and adhesion of the pattern.

[0215] (5) Solvent

[0216] 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.

[0217] 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., monooxy monocarboxylic acid alkyl esters; 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.

[0218] 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.

[0219] Among the above solvents, 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 considering compatibility and reactivity.

[0220] The solvent can be contained as the remaining amount with respect to the total amount of the photosensitive resin composition, specifically, it is contained in an amount of 40 to 90% by weight. When the solvent is contained 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.

[0221] (6) Other additives

[0222] 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 fluorosurfactant; a radical polymerization initiator in order to prevent stains and spots during coating, improve leveling performance, and prevent the generation of residues due to undevelopment.

[0223] 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, etc.

[0224] Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0225] The silane coupling agent may be contained in an amount of 0.01 part by weight to 10 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, it is excellent in adhesion, storage stability, etc.

[0226] In addition, the photosensitive resin composition may further contain a surfactant, for example, a fluorosurfactant, as necessary, for the effect of improving coating properties and preventing the generation of defects.

[0227] As the fluorosurfactant, for example, BM-1000 (registered trademark), BM-1100 (registered trademark), etc. of BM Chemie; Megafac F142D (registered trademark), Megafac F172 (registered trademark), Megafac F173 (registered trademark), Megafac F183 (registered trademark), etc. of Dainippon Ink and Chemicals, Incorporated; Fluorad FC-135 (registered trademark), Fluorad FC-170C (registered trademark), Fluorad FC-430 (registered trademark), Fluorad FC-431 (registered trademark), etc. of Sumitomo 3M Limited; Surfron S-112 (registered trademark), Surfron S-113 (registered trademark), Surfron S-131, Surfron S-141, Surfron S-145, etc. of Asahi Glass Co., Ltd.; fluorosurfactants commercially available under the names of SH-28PA (registered trademark), SH-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark), etc. of Drey Silicon Co., Ltd. may be used.

[0228] 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 has excellent wettability to the glass substrate. Also, other additives such as antioxidants and stabilizers may be added in a certain amount within a range that does not inhibit the physical properties of the photosensitive resin composition.

[0229] Another embodiment can pattern the pixel separation part of the organic light-emitting element electrode using the aforementioned photosensitive resin composition.

[0230] 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.

[0231] (Manufacture of black photosensitive composition)

[0232] Synthesis Example 1: Production of 9,9 - Bis[4-(glycidyloxy)phenyl]fluorene of Chemical Formula 8

[0233] 20 g of 9,9'-bisphenol fluorene (Sigma aldrich), 8.67 g of glycidyl chloride (Sigma aldrich), and 30 g of anhydrous potassium carbonate 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 purity analysis, it showed a purity of 98%.

[0234]

Chemical Formula

[0235] Synthesis Example 2: Production of Cardo-based Binder Resin

[0236] 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 recovered 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.

[0237] Production Example 1: Production of Black Pigment Dispersion

[0238] 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.

[0239] A photosensitive composition was produced with the composition as shown in Table 1 below.

[0240] 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, the colorant and other additives were added to the obtained reactant and stirred at room temperature. Subsequently, the product was filtered three times to remove impurities, thereby producing a photosensitive resin composition.

[0241] [Table 1]

[0242] The method for producing a negative pixel definition layer (negative PDL) using the photosensitive composition is as follows.

[0243] (1) Coating and Coating Step

[0244] 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.

[0245] (2) Pre-bake Step

[0246] To remove the solvent contained in the obtained coating film, heat it 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 step, mask contamination in the form of pixels can be reduced during the next step (exposure), and a clean pattern can be created.

[0247] (3) Exposure step

[0248] 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.

[0249] (4) Development step

[0250] Following the exposure step, 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.

[0251] (5) Post-heat treatment step

[0252] To obtain the image pattern obtained by the development, post-baking is performed at 210~300°C for 30 minutes to 120 minutes using an oven to completely remove the solvent and the ultrapure water (DI water, moisture) absorbed by the coating film during the development step, and to cure the pattern to form a film.

[0253] (6) Optical density measurement

[0254] After forming a pattern on a substrate through the steps (1) to (5) using the photosensitive composition, the optical density was measured. After coating and post-heat treating a 10 cm × 10 cm bare glass substrate with the photosensitive composition, the optical density of the substrate was measured using a 361T Transmission Densitometer manufactured by X-Rite.

[0255] (7) Reflectance measurement

[0256] For reflectance measurement, an evaluation substrate including a negative pixel definition layer formed by coating, exposing, developing, and post-heat treating a composition containing a colorant on the glass surface was manufactured. The physical properties of the evaluation substrate were measured for SCI reflectance at a wavelength of 550 nm using a reflectance meter (CM-26d manufactured by Konica Minolta).

[0257]

Table 2

[0258] The reflectance and transmittance corresponding to the optical density were measured and compared for the coating films of the photosensitive compositions produced in Examples 1 to 3 and Comparative Examples 1 to 4.

[0259] Referring to Comparative Examples 1 to 4 in Table 2, it can be confirmed that when the optical density is 0.8 / μm or less or 1.5 / μm or more, the reflectance exceeds 6.5% and external reflected light cannot be sufficiently blocked. Also, referring to Comparative Examples 1 to 2 in Table 2, it can be seen that when the optical density is 0.8 / μm or less, the transmittance is too large and it is not suitable for the role as a light-shielding film.

[0260] Referring to Examples 1 to 2, when the optical density corresponds to the preferable range of 0.8 to 1.50 / μm, it can be confirmed that external reflected light is prevented with a reflectance of 6.5% or less and a transmittance of 3.0% or less, enhancing the visibility of the display and meeting the requirements for the light-shielding layer and pixel definition layer.

[0261] The above description is merely illustrative of the present invention, and those having 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.

[0262] 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 construed according to the claims, and all technologies within the equivalent scope should be construed 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 after the post-heat treatment step, the optical density of the coating film is 0.80 / μm to 1.5 / μm, and the reflectance satisfies more than 0.01% and less than 6.5%.

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