Photosensitive resin composition and display device

Abstract

To provide a photosensitive resin composition and a display device.SOLUTION: [Disclosure] [Technical Problem] It is an aspect of the present invention to provide a photosensitive resin composition which includes two or more different kinds of cardo-based binders to improve a residue and a melting flow during development and form a pattern layer having a high taper angle, and a display device having a pattern layer including a polymerization product thereof. In addition, the present invention provides a display device having high resolution by including a pattern layer including a polymerization product of the above-described photosensitive resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] An embodiment of the present invention relates to a photosensitive resin composition and a display device. [Background technology]

[0002] Colored light-shielding layers, particularly black light-shielding layers, are used in liquid crystal display devices to prevent color interference between red, green, and blue color filters and thereby improve image quality. In recent years, research has been conducted into organic light-emitting display devices as well, with the same objectives as liquid crystal display devices, to prevent color mixing between adjacent pixels and achieve low reflectance to improve image visibility. Summary of the Invention [Problem to be solved by the invention]

[0003] Colorants and various resins are used in the production of colored light-shielding layers, but it is necessary to improve the resolution, heat resistance, and adhesion during development.

[0004] Moreover, in the black light-shielding layer, a high content of black pigment is added, which may significantly reduce sensitivity and adhesion.

[0005] Therefore, one embodiment of the present invention provides a photosensitive resin composition that contains two or more Cardo binders, thereby improving residues around patterns and developed areas during development, reducing melting flow, and achieving a high taper angle when used as a pixel defining layer.

[0006] In addition, an embodiment of the present invention provides a display device having a pixel defining layer with high resolution and a high taper angle by including a pattern layer containing a polymerization product of the above-mentioned photosensitive resin composition. [Means for solving the problem]

[0007] One embodiment of the present invention provides a photosensitive resin composition comprising two or more cardo-based binders (A) having different molecular weights and including a repeating unit represented by the following formula 1, a reactive unsaturated compound (B), a pigment (C), an initiator (D), and a solvent (E).

[0008] [ka] [Effects of the Invention]

[0009] According to one embodiment of the present invention, two or more different cardobains represented by Chemical Formula 1 are By including the photosensitive resin composition, it is possible to provide a photosensitive resin composition which can improve residues during development, improve melting flow, and form a pattern layer having a high taper angle.

[0010] Furthermore, according to one embodiment of the present invention, a display device having high resolution can be provided by including a pattern layer containing a polymerization product of the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] Some embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Regarding the reference numerals of components in each drawing, the same components may have the same numerals whenever possible, even if they are shown in different drawings. Furthermore, in the description of the present invention, if a detailed description of related known structures or functions is deemed to obscure the gist of the present invention, such detailed description may be omitted. When "comprises," "has," "consists of," etc. are used in this specification, other parts may be added unless "only" is used. When a component is expressed in the singular, it may also include a plural number unless otherwise specified.

[0012] Furthermore, when describing components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are used to distinguish the components from other components, and do not limit the nature, order, sequence, or number of the components.

[0013] In describing the positional relationship of components, when two or more components are "coupled," "coupled," or "connected," it should be understood that the two or more components may be directly "coupled," "coupled," or "connected," but that the two or more components may be "coupled," "coupled," or "connected" with another component "intervening" between them. Here, the other component may be included in at least one of the two or more components that are "coupled," "coupled," or "connected" to each other.

[0014] In describing a temporal sequence relationship relating to components, methods of operation, or methods of production, for example, when a temporal or sequential sequence relationship is described using terms such as "after," "following," "next," or "before," non-consecutive cases may also be included unless "immediately" or "directly" is used.

[0015] On the other hand, when a numerical value or corresponding information for a component is mentioned, even if there is no specific explicit statement, the numerical value or corresponding information can be interpreted as including an error range that may occur due to various factors (e.g., process factors, internal or external impact, noise, etc.).

[0016] The term "halo" or "halogen" as used herein, unless otherwise specified, is inclusive of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the like.

[0017] As used herein, unless otherwise specified, the term "alkyl" or "alkyl group" refers to the radical of a saturated aliphatic functional group having 1 to 60 carbon atoms connected by a single bond, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.

[0018] As used herein, unless otherwise specified, the term "haloalkyl group" or "haloalkyl group" may refer to an alkyl group substituted with a halogen.

[0019] As used in this application, the terms "alkenyl" or "alkynyl" refer to the alkynyl group unless otherwise specified. Each of them has a double bond or a triple bond, includes a straight-chain or side-chain chain group, and can have 2 to 60 carbon atoms.

[0020] As used herein, unless otherwise specified, the term "cycloalkyl" may refer to an alkyl ring having 3 to 60 carbon atoms.

[0021] The term "alkoxy group" or "alkyloxy group" as used herein means an alkyl group having an oxygen radical attached thereto, and unless otherwise specified, can have 1 to 60 carbon atoms.

[0022] The terms "alkeneoxyl group," "alkenoxy group," "alkenyloxyl group," or "alkenyloxy group" as used herein mean an alkenyl group having an oxygen radical attached thereto, and unless otherwise specified, can have 2 to 60 carbon atoms.

[0023] Unless otherwise specified, the terms "aryl group" and "arylene group" used herein each have 6 to 60 carbon atoms, but are not limited thereto. In this application, an aryl group or arylene group can include a single chain, a ring assembly, a fused polycyclic ring system, a compound, etc. For example, an aryl group can refer to a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, or a substituted fluorenyl group.

[0024] In this application, unless otherwise specified, the terms "fluorenyl group" or "fluorenylene group" can refer to a monovalent or divalent functional group of fluorene, respectively. "Substituted fluorenyl group" or "substituted fluorenylene group" can refer to a monovalent or divalent functional group of substituted fluorene. "Substituted fluorene" can mean that at least one of the following substituents R, R', R" and R'" is a functional group other than hydrogen. This can include cases where R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded.

[0025] [ka] Furthermore, the R, R', R" and R'" may each independently be 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 3 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 a monovalent or divalent functional group of 9,9-dimethylfluoro-N, 9,9-diphenylfluoro-N, and 9,9'-spirobi[9H-fluorene], respectively.

[0026] As used in this application, the term "ring assemblies" refers to two or more ring systems (single rings or joined ring systems) directly connected to each other by single or double bonds, and the number of such direct connections between rings is greater than the total number of ring systems in the compound. The ring assembly may be comprised of identical or different ring systems directly linked to each other by a single or double bond.

[0027] In the present application, the aryl group includes a ring assembly, and therefore includes biphenyl and terphenyl in which a single aromatic ring, a benzene ring, is connected by a single bond. The aryl group also includes a compound in which an aromatic ring system connected to a single aromatic ring is connected by a single bond, and therefore, for example, can include a compound in which an aromatic ring system, a fluorene, is connected to a single aromatic ring, a benzene ring, is connected by a single bond.

[0028] The term "fused polycyclic ring system" as used herein means a fused ring system that shares at least two atoms, including a fused ring system consisting of two or more hydrocarbon ring systems and a fused ring system consisting of at least one heterocyclic ring system containing at least one heteroatom. Such a fused polycyclic ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

[0029] The term "spiro compound" as used in this application has a "spiro union," which means a connection formed by two rings simply sharing one atom. In this case, the atom shared by the two rings is called a "spiro atom." Depending on the number of spiro atoms in a compound, they can be called "monospiro-," "dispiro-," or "trispiro-" compounds, respectively.

[0030] The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl groups" or "heteroarylene groups" but also non-aromatic rings, and unless otherwise specified, refers to a ring having 2 to 60 carbon atoms and containing one or more heteroatoms, but is not limited thereto. The term "heteroatom" as used herein refers to N, O, S, P, or Si, unless otherwise specified, and the heterocyclic group can refer to a single chain, ring assembly, fused polycyclic system, spiro compound, etc. containing a heteroatom.

[0031] "Heterocyclic groups" can also include rings containing SO2 in place of the carbon atoms that form the ring. For example, "heterocyclic groups" can include the following compounds:

[0032] [ka] The term "ring" as used in this application includes single and multiple rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom, and can include aromatic and non-aromatic rings.

[0033] The term "polycyclic" as used herein includes ring assemblies such as biphenyl, terphenyl, etc., fused polycyclic systems, and spiro compounds, and may include aromatic as well as non-aromatic rings, and may include hydrocarbon rings as well as heterocycles containing at least one heteroatom.

[0034] Consecutive prefixes may also mean that the substituents are listed in the order they are listed, for example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Here, the arylcarbonyl group may be a carbonyl group substituted with an aryl group.

[0035] In addition, unless otherwise expressly stated, in the term "substituted or unsubstituted" used in this application, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1-C 20 Alkyl groups, C1-C 20 Alkoxy groups, C1-C 20 Alkylamine groups, C1-C 20 Alkylthiophene group, C6-C 20 Arylthiophene groups, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6-C 20 Aryl groups, deuterium-substituted C6-C 20 Aryl groups of C8-C 20 an arylalkenyl group, a silane group, a boron group, a germanium group, and a C2-C alkyl group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; 20 It can mean that the heterocyclic group is substituted with one or more substituents selected from the group consisting of the heterocyclic groups listed above, but is not limited to these substituents.

[0036] In this application, the 'functional group names' corresponding to aryl groups, arylene groups, heterocyclic groups, etc., which are listed as examples of each symbol and its substituent, may be written as the 'functional group name reflecting the valence' or as the 'name of the parent compound'. For example, in the case of 'phenanthrene', a type of aryl group, the group name may be written by distinguishing the valence, such as 'phenanthryl (group)' for a monovalent 'group' and 'phenanthrylene (group)' for a divalent group, or it may be written as the parent compound name 'phenanthrene' regardless of the valence. Similarly, pyrimidine may be written as 'pyrimidine' regardless of the valence, or it may be written as the 'group name' of the corresponding valence, such as pyrimidinyl (group) for a monovalent group and pyrimidinylene (group) for a divalent group. Therefore, in this application, when the type of substituent is described by the name of the parent compound, it may refer to an n-valent 'group' formed by eliminating hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0037] In addition, unless otherwise specified, the chemical formulas used in this application may be applied in the same manner as the substituent definitions according to the index definitions of the chemical formulas below. [ka] where, when a is 0, the substituent R 1 is absent, and when a is 1, one substituent R 1 is bonded to any one of the carbons forming the benzene ring, and when a is 2 or 3, it is bonded as follows, and in this case, R 1 may be the same or different, and when a is an integer of 4 to 6, they are bonded to the carbon atoms of the benzene ring in a similar manner, while the hydrogen atoms bonded to the carbon atoms forming the benzene ring can be omitted. [ka]

[0038] In the present application, when substituents are bonded to each other to form a ring, it means that the bonded substituents share any atom, for example, at least one atom of a carbon atom or a heteroatom such as O, N, S, Si, or P, to form a saturated or unsaturated ring. For example, in the case of naphthalene, adjacent methyl groups and butadiene groups substituted on one benzene ring are bonded to each other. It can be considered as two phenyl groups sharing one carbon to form an unsaturated ring, or as two vinyl and propylenyl groups sharing one carbon to form an unsaturated ring. Fluorene can be considered itself an aryl group with 13 carbon atoms, or as two methyl groups substituted on a biphenyl group linked together to form a ring, sharing one carbon.

[0039] In this application, an organic electric element can mean a component between an anode and a cathode, or can mean an organic light-emitting diode including an anode, a cathode and a component located therebetween.

[0040] In addition, in some cases, the organic electrical element in this application may refer to an organic light-emitting diode and a panel including the organic light-emitting diode, or an electronic device including a panel and a circuit. Here, for example, the electronic device may include, but is not limited to, a display device, a lighting device, a solar cell, a portable or mobile terminal (e.g., a smartphone, a tablet, a PDA, an electronic dictionary, a PMP, etc.), a navigation terminal, a game console, various TVs, various computer monitors, etc., as long as it includes the above components.

[0041] The photosensitive resin composition according to the embodiment of the present invention comprises two or more cardo-based binders (A) having different molecular weights, a reactive unsaturated compound (B), a pigment (C), an initiator (D), and a solvent (E).

[0042] The two or more cardo-based binders (A) each contain a repeating unit represented by the following Chemical Formula 1: [ka]

[0043] The above-mentioned Chemical Formula 1 will now be described.

[0044] The "*" indicates the portion of the repeating unit where a bond is connected. Therefore, the repeating units shown in Formula 1 may be interconnected at the portions shown in brackets.

[0045] R1 and R2 are each independently a deuterium atom; a halogen atom; a C6-C 60 aryl groups of C2-C containing at least one heteroatom selected from O, N, S, Si and P; 60 Heterocyclic group; C3-C 60 Aliphatic rings and C6-C 60 Aromatic fused ring group; C1-C 60 Alkyl groups of C2 to C 60 Alkenyl group; C2-C 60 Alkynyl group; C1-C 60 Alkoxy groups of C6 to C 30an aryloxy group represented by the formula:

[0046] R1 and R2 are each independently C1 to C 40 or C1-C alkyl group 20 The alkyl group may be:

[0047] R3 to R6 are each independently hydrogen; deuterium; a halogen group; C6 to C 60 Ally C2-C groups containing at least one heteroatom selected from O, N, S, Si, and P 60 Heterocyclic group; C3-C 60 Aliphatic rings and C6-C 60 Aromatic fused ring group; C1-C 60 Alkyl groups of C2 to C 60 Alkenyl group; C2-C 60 Alkynyl group; C1-C 60 Alkoxy groups of C6 to C 30 an aryloxy group represented by the formula:

[0048] R3 to R6 are each independently C1 to C 40 or C1-C alkyl group 20 The alkyl group may be:

[0049] R7 is hydrogen; deuterium; C1-C 60 Alkyl groups of C2 to C 60 an alkenyl group; an acrylic group; and a methacrylic group.

[0050] R7 is C1~C 40 or C1-C 20 The alkyl group may be:

[0051] R7 is C2~C 40 or an alkenyl group of C2 to C 20 The alkenyl group may be:

[0052] m and n each independently represent an integer of 0 to 4.

[0053] When m is 2 or more, adjacent R1's can be bonded to each other to form a monocyclic or polycyclic ring.

[0054] When n is 2 or greater, R2 can be bonded to each other to form a monocyclic or polycyclic ring.

[0055] X2 is an acid anhydride residue or an acid dianhydride residue.

[0056] X1 is represented by the following chemical formula 2. Chemical formula 2 will be described later.

[0057] Y1 and Y2 are each independently selected from the group consisting of hydrogen, deuterium, the following chemical formula 3, and the following chemical formula 4. Chemical formula 3 and chemical formula 4 will be described later.

[0058] The above-mentioned Chemical Formula 2 will now be described. [ka]

[0059] * means the portion where X1 is connected to two benzene rings in Chemical Formula 1.

[0060] R8 and R9 are each independently a deuterium atom; a halogen atom; a C6-C 60 aryl groups of C2-C containing at least one heteroatom selected from O, N, S, Si and P; 60 Heterocyclic group; C3-C 60 Aliphatic rings and C6-C 60 Aromatic fused ring group; C1-C 60 Alkyl groups of C2 to C 60 Alkenyl group; C2-C 60 Alkynyl group; C1-C 60 Alkoxy groups of C2 to C 60 The alkenyl group is selected from the group consisting of:

[0061] R8 and R9 are each independently C1 to C 40 or C1-C 20The alkyl group may be:

[0062] R8 and R9 are each independently C1 to C 40 or an alkenyl group of C1 to C 20 The alkenyl group may be:

[0063] R8 and R9 are each independently C1 to C 40 Alkoxy group or C1-C 20 The alkoxy group may be:

[0064] o and p each independently represent an integer of 0 to 4;

[0065] When o is 2 or more, adjacent R8's can be bonded to each other to form a monocyclic or polycyclic ring.

[0066] When p is 2 or more, adjacent R9s can be bonded to each other to form a monocyclic or polycyclic ring.

[0067] Hereinafter, Chemical Formula 3 and Chemical Formula 4 will be described. [ka]

[0068] [ka]

[0069] The broken bond in the wavy notation represents the bond between Y1 and Y2 and oxygen in Chemical Formula 1.

[0070] L1 to L3 each independently represent a single bond; C1 to C 60 alkylene groups; and C6-C 60 The arylene group is selected from the group consisting of:

[0071] L1 to L3 are independently C1 to C 40 or an alkylene group of C1 to C 20 It can be an alkylene group of the formula:

[0072] L1 to L3 are independently C1 to C 40 or an arylene group of C1-C 20 The arylene group may be:

[0073] R 10 ~R 12 are each independently hydrogen; deuterium; halogen group; C6-C 60 aryl groups of C2-C containing at least one heteroatom selected from O, N, S, Si and P; 60 Heterocyclic group; C3-C 60 Aliphatic rings and C6-C 60 Aromatic fused ring group; C1-C 60 alkyl groups; and C1-C 60 an alkoxy group selected from the group consisting of:

[0074] R 10 ~R 12 are independently C1 to C 40 or C1-C 20 The alkyl group may be:

[0075] R 10 ~R 12 are independently C1 to C 40 Alkoxy group or C1-C 20 The alkoxy group may be:

[0076] Z1 is S or O.

[0077] q and r each independently represent an integer of 0 to 3, and q+r=3.

[0078] In at least one of the two or more cardo-based binders containing a repeating unit represented by Formula 1, at least one of Y1 and Y2 may be represented by Formula 3.

[0079] At least one of the two or more cardo-based binders containing a repeating unit represented by Formula 1 may have at least one of Y1 and Y2 represented by Formula 4 and a weight average molecular weight of 5,000 to 7,000.

[0080] The photosensitive resin composition according to the embodiment of the present invention contains two or more cardo-based binders represented by the above-mentioned Chemical Formula 1, thereby forming a pattern layer without residue and exhibiting excellent adhesion.

[0081] The two or more cardo type binders can include a low molecular weight cardo type binder and a high molecular weight cardo type binder.

[0082] The low molecular weight cardo-based binder contains the repeating unit represented by Chemical Formula 1 above and may have a weight average molecular weight of 3,000 to 5,000 or 3,000 to 4,800.

[0083] The high molecular weight cardo binder includes repeating units represented by Chemical Formula 1 above and may have a weight average molecular weight of 7,000 to 9,000, 7,000 to 8,800, or 7,000 to 8,000.

[0084] The photosensitive resin composition according to the embodiment of the present invention, which includes a low molecular weight cardo binder and a high molecular weight cardo binder, may contain a higher ratio of the low molecular weight cardo binder than the high molecular weight cardo binder.

[0085] For example, the photosensitive resin composition may contain 50 to 90% by weight, 51 to 90% by weight, 60 to 85% by weight, or 70 to 80% by weight of the low-molecular-weight cardo binder relative to the sum of the weight of the low-molecular-weight cardo binder and the weight of the high-molecular-weight cardo binder. When the content of the low-molecular-weight cardo binder is within the above range, when a pattern layer is produced using the photosensitive resin composition, a pattern is formed without residue, and loss of film thickness during development can be prevented.

[0086] The photosensitive resin composition according to the embodiment of the present invention may further contain at least one of an acrylic binder and a polyimide binder in addition to the two or more cardo-based binders.

[0087] The acrylic binder 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.

[0088] The polyimide binder adjusts the solubility by copolymerizing polyimide, which is the main structure of the polymer, to prevent the excessive solubility of polyamic acid, a polyimide precursor, in an alkaline aqueous solution. This allows for an appropriate difference in solubility between exposed and unexposed areas during the patterning process, thereby realizing a black pixel partition layer (so-called black matrix) with excellent heat resistance and pattern formability.

[0089] For example, the polyamic acid-polyimide copolymer may comprise a polyamic acid repeating unit and a polyimide repeating unit. The polyamic acid repeating unit and the polyimide repeating unit may be present in a molar ratio of 5:5 to 9:1, for example, 2:8 to 8:2. When the polyamic acid repeating unit and the polyimide repeating unit are present in a molar ratio within this range, the composition can be soluble in a solvent used in the composition and can exhibit suitable developability in a patterning process. A usable polyimide-polyamic acid copolymer has a structure represented by the following formula 5:

[0090] [ka]

[0091] The above-mentioned Chemical Formula 5 will now be described.

[0092] X2 to X4 are each independently selected from the group consisting of a substituted or unsubstituted tetravalent alicyclic organic group; and a substituted or unsubstituted tetravalent aromatic organic group;

[0093] L3 to L6 each independently represent a single bond; 10 Alkylene group; substituted or unsubstituted C3-C 10 Cycloalkylene groups; and substituted or unsubstituted C6-C 20 arylene groups;

[0094] R 15 and R 16 are each independently selected from the group consisting of hydrogen; and a substituted or unsubstituted norbornene group.

[0095] o and p each independently represent an integer of 1 to 10,000.

[0096] The photosensitive resin composition according to the embodiment of the present invention contains a reactive unsaturated compound (B).

[0097] The reactive unsaturated compound is (meth)acrylic acid having at least one ethylenically unsaturated double bond, and one or more monofunctional or polyfunctional esters may be used. The reactive unsaturated compound may be a monomer or an oligomer. In this specification, "(meth)acrylic acid" may mean methacrylic acid, acrylic acid, or a mixture of methacrylic acid and acrylic acid.

[0098] The reactive unsaturated compound may be a photopolymerizable compound. Since the reactive unsaturated compound is a photopolymerizable compound, the photosensitive resin composition undergoes sufficient polymerization upon exposure in the pattern formation step, and a pattern having excellent heat resistance, light resistance, and chemical resistance can be formed.

[0099] 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, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethyl The compound may be one or more selected from the group consisting of methylpropane triacrylate and trisacryloylethyl phosphate, but is not limited thereto.

[0100] Commercially available photopolymerizable monomers include the following: Examples of the monofunctional esters of (meth)acrylic acid include Aronix M-101, M-111, and M-114 manufactured by Toagosei Chemical Industry Co., Ltd., KAYARAD TC-110S (registered trademark) and TC-120S manufactured by Nippon Kayaku Co., Ltd., and V-158 and V-2311 manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples of the bifunctional esters of (meth)acrylic acid include Aronix M-210, M-240, and M-6200 manufactured by Toagosei Chemical Industry Co., Ltd., KAYARAD HDDA, HX-220, and R-604 manufactured by Nippon Kayaku Co., Ltd., and V-260, V-312, and V-335HP manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples of the trifunctional esters of (meth)acrylic acid include Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M-8060 manufactured by Toagosei Chemical Industry Co., Ltd., KAYARAD TMPTA, DPCA-20, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and V-295, V-300, and V-360 manufactured by Osaka Organic Chemical Industry Co., Ltd. These products can be used alone or in combination of two or more.

[0101] The reactive unsaturated compounds may be treated with an acid anhydride to provide better developability.

[0102] The reactive unsaturated compound may be contained in an amount of 1 wt % to 40 wt % or 1 wt % to 20 wt % based on the total amount of the photosensitive resin composition. When the reactive unsaturated compound is contained in the above range, sufficient curing occurs upon exposure in the pattern formation step, resulting in excellent reliability, and excellent heat resistance, light resistance, and chemical resistance of the pattern, as well as excellent resolution and adhesion.

[0103] The photosensitive resin composition according to the embodiment of the present invention contains a pigment.

[0104] The pigment may be at least one of an organic pigment and an inorganic pigment.

[0105] The pigment may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

[0106] Examples of the red pigment include CI Red Pigment 254, CI Red Pigment 255, CI Red Pigment 264, CI Red Pigment 270, CI Red Pigment 272, CI Red Pigment 177, CI Red Pigment 89, and the like.

[0107] Examples of the green pigment include halogen-substituted copper phthalocyanine pigments such as CI Green Pigment 36 and CI Green Pigment 7.

[0108] Examples of the blue pigment include copper phthalocyanine pigments such as CI Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3, CI Blue Pigment 15:4, CI Blue Pigment 15:5, CI Blue Pigment 16, and the like.

[0109] Examples of the yellow pigment include isoindoline pigments such as CI Yellow Pigment 139, quinophthalone pigments such as CI Yellow Pigment 138, and nickel composite pigments such as CI Yellow Pigment 150.

[0110] Examples of the black pigment include lactam black, aniline black, perylene black, Examples of suitable black pigments include titanium black and carbon black.

[0111] The pigments may be used alone or in combination of two or more, and are not limited to these examples.

[0112] When a pattern layer formed from the photosensitive resin composition requires high light-blocking properties, the black pigment may be used to efficiently block light. When the black pigment is used, it may be used together with a color correction agent such as an anthraquinone-based pigment, a perylene-based pigment, a phthalocyanine-based pigment, or an azo-based pigment.

[0113] A dispersant may be used to disperse the pigment in the photosensitive resin composition. The pigment may be surface-treated with a dispersant before use, or the dispersant may be added together with the pigment during preparation of the photosensitive resin composition.

[0114] The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. 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, sulfonic acid salts, carboxylate esters, carboxylate salts, alkylamide alkylene oxide adducts, and alkylamines, which may be used alone or in combination of two or more.

[0115] Examples of commercially available products of the dispersant include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like manufactured by BYK; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 manufactured by BASF; and Solsperse 5000, Solsperse 6000, and Solsperse 7001 manufactured by Zeneka. 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc., or PB711 and PB821 manufactured by Ajinomoto Co., Ltd.

[0116] The dispersant may be contained in an amount of 0.1 to 15 wt % based on the total amount of the photosensitive resin composition. When the dispersant is contained in this range, the photosensitive resin composition has excellent dispersibility, and therefore, the light-shielding layer has excellent stability, developability, and patternability when produced.

[0117] The pigment may be pretreated with a water-soluble inorganic salt and a wetting agent before use. When the pigment is pretreated, the primary particle size of the pigment can be reduced. The pretreatment can be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the pigment obtained from the kneading step. The kneading can be performed at a temperature of 40°C to 100°C, and the filtration and washing can be performed by washing the inorganic salt with water, etc., followed by filtration. Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride.

[0118] The wetting agent acts as a medium for uniformly mixing the pigment and the water-soluble inorganic salt, making it easier to grind the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and propylene glycol monoethyl ether. Examples of the alkylene glycol monoalkyl ether include alkylene glycol monomethyl ether such as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether; and alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin polyethylene glycol, and these can be used alone or in combination of two or more.

[0119] The pigment after 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 this range, it is possible to effectively form a fine pattern while having excellent heat resistance and light resistance.

[0120] The pigment may be contained in an amount of 1 to 40% by weight, 1 to 30% by weight, or 2 to 30% by weight relative to the total amount of the photosensitive resin composition. When the pigment is contained in the above range, the photosensitive resin composition can form a pattern layer that is excellent in color reproduction, curability, and adhesion.

[0121] The photosensitive resin composition contains an initiator (D).

[0122] The initiator may be a photopolymerization initiator, a radical polymerization initiator, or a combination thereof.

[0123] The photopolymerization initiator may be, for example, one or more of an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an oxime ester-based compound, and a triazine-based compound.

[0124] Examples of 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one. Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0125] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0126] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc. Examples of the triazine-based compounds 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, 4,6-bis(trichloromethyl)-s-triazine, 2-(naphth1-yl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth1-yl)-4,6-s(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like can be mentioned.

[0127] In addition to the above compounds, the photopolymerization initiator may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, etc. The radical polymerization initiator may also include peroxide compounds, azobis compounds, etc.

[0128] Examples of the peroxide compounds include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,2,3,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; Examples of the alkyl peroxides include dialkyl peroxides such as 2,3-bis(t-butyloxyisopropyl)benzene and t-butylperoxyvaleric acid n-butyl ester; alkyl peresters such as 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylperoxybenzoate and di-t-butylperoxytrimethyladipate; and percarbonates such as di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis-4-t-butylcyclohexylperoxydicarbonate, diisopropylperoxydicarbonate, acetylcyclohexylsulfonyl peroxide and t-butylperoxyarylcarbonate.

[0129] Examples of the azobis-based compound 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(isobutylnitrile), and 4,4'-azobis(4-cyanovaleric acid). The initiator may be used together with a photosensitizer that absorbs light, becomes levitated, and then transfers the energy to initiate a chemical reaction. Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol tetrakis-3-mercaptopropionate.

[0130] The initiator may be contained in an amount of 0.01 to 10 wt % or 0.1 to 5 wt % based on the total amount of the photosensitive resin composition. When the initiator is contained within this range, sufficient curing occurs upon exposure in a pattern formation process using the photosensitive resin composition, excellent reliability can be obtained, the pattern has excellent heat resistance, light resistance, and chemical resistance, and also has excellent resolution and adhesion, and a decrease in transmittance due to unreacted initiator can be prevented.

[0131] The photosensitive resin composition according to the embodiment of the present invention contains a solvent.

[0132] The solvent contains the cardo-based binder, the reactive unsaturated compound, the pigment, and the Any material can be used that is compatible with, but does not react with, the initiator.

[0133] 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, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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 2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 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, methyl 3-ethoxypropionate, etc.; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.2-Alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, and monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, 2-hydroxy esters such as methyl 3-methylbutanoate; ketone acid esters such as ethyl pyruvate; and 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, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0134] Among the 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; and propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate may be used in consideration of compatibility and reactivity. The solvent may be contained in the remaining amount relative to the total amount of the photosensitive resin composition, specifically, in an amount of 50 to 90 wt %. When the solvent is contained within the above range, the photosensitive resin composition can be appropriately Because of its viscosity, it has excellent processability when producing the light-shielding layer.

[0135] Another embodiment of the present invention can provide a display device.

[0136] A display device according to an embodiment of the present invention includes a pattern layer containing a polymerized product of a photosensitive resin composition.

[0137] In the display device according to the embodiment of the present invention, the matters relating to the photosensitive resin composition are the same as those of the photosensitive resin composition according to the embodiment of the present invention described above, and therefore, the description thereof will be omitted.

[0138] The polymerization reaction product of the photosensitive resin composition can be formed, for example, by a process of applying a photosensitive resin composition onto a TFT substrate and curing the applied photosensitive resin composition.

[0139] The pattern layer may have excellent resolution and a high taper angle by containing the polymerization product of the photosensitive resin composition.

[0140] The display device may include a plurality of sub-pixels, and the pattern layer may be a pixel definition layer that defines the plurality of sub-pixels.

[0141] For example, a light-emitting element may be located in a subpixel of the display device, and the light-emitting element may be an organic light-emitting element. The organic light-emitting element may have, for example, a first electrode, an organic layer, and a second electrode stacked in sequence. In this example, the pattern layer may be located on the first electrode, and the pattern layer may have an opening on the first electrode. The organic layer may be located in the opening and on the first electrode, and the second electrode may be located on the organic layer. Since the light-emitting area of ​​the subpixel is determined by the opening area of ​​the pattern layer, the pattern layer may be a pixel-defining layer. Alternatively, the pattern layer may be a light-blocking layer that blocks light.

[0142] The pattern layer according to the embodiment of the present invention may have a high taper angle. For example, the pattern layer according to the embodiment of the present invention may have a slope angle of 20° to 40°. The slope angle may be the slope angle relative to a direction parallel to the display surface at the point where the slope starts.

[0143] The pattern layer, which is the pixel definition layer described above, has openings, and the inclined portions connecting the openings and non-openings have an inclination angle. The pattern layer according to an embodiment of the present invention includes a polymerization reaction product of the photosensitive resin composition described above. The photosensitive resin composition described above can form a pattern layer without residue, and melt flow is suppressed during the pattern formation process, thereby achieving a high inclination angle. Therefore, by having the high inclination angle described above, the length of the inclined portions can be reduced, and the distance between openings can be shortened. Therefore, subpixels can be densely arranged, resulting in high resolution of the display device.

[0144] The above description merely exemplifies the technical concept of the present invention, and various modifications and variations may be made by those skilled in the art without departing from the essential characteristics of the present invention. Furthermore, the embodiments disclosed herein are for illustrative purposes only and do not limit the technical concept of the present invention. The scope of the present invention should be interpreted in accordance with the appended claims, and any technical concept within the scope equivalent thereto is deemed to be within the scope of the present invention.

[0145] Synthesis examples and working examples of the present invention will be specifically described below. The examples are not limited to these.

[0146] Synthesis Example 1 (Production of 9,9-Bis[4-(glycidyloxy)phenyl]fluorine of Chemical Formula 6) 20 g of 9,9'-bisphenolfluorene (Sigma Aldrich), 8.67 g of glycidyl chloride (Sigma Aldrich), and 30 g of anhydrous potassium carbonate were placed in a 300 ml three-neck round-bottom flask equipped with a distillation column and 100 ml of dimethylformamide. The mixture was heated to 80°C and reacted for 4 hours. After that, the temperature was lowered to 25°C and the reaction mixture was filtered. The filtrate was added dropwise to 1000 ml of water with stirring. 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]fluorine of Formula 6. The resulting powder was analyzed by HPLC and showed a purity of 98%. [ka]

[0147] Synthesis Example 2: Preparation of low molecular weight cardo-based binder resin (Polymer A-1) (Production of low molecular weight cardo-based binder resin of the following chemical formula 7: A-1) 25 g (54 mmol) of the compound 1 obtained in Synthesis Example 1, 8 g of acrylic acid (Oi Chemical Industries, Ltd.), 0.2 g of benzyltriethylammonium chloride (Oi Chemical Industries, Ltd.), and 0.2 g of hydroquinone (Oi Chemical Industries, Ltd.) were dissolved in 52 g of propylene glycol methyl ether acetate (Sigma-Aldrich). The mixture was placed in a 300ml three-necked round-bottom flask equipped with a distillation column (Sigma Aldrich) and stirred at 110°C for 6 hours. After the reaction was complete, 8g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 1.8g of tetrahydrophthalic acid (Sigma Aldrich) were added and stirred for an additional 6 hours at 110°C. After the reaction was complete, the reaction liquid was recovered and analyzed, and a cardo-based binder resin with a weight-average molecular weight of 4,500 and a solids content of 45% was obtained, which has the structure shown in Chemical Formula 7. [ka]

[0148] Synthesis Example 3: Preparation of high molecular weight cardo-based binder resin (Polymer A-2) 25g (54mmol) of compound 1 obtained in the same experiment as in Synthesis Example 1, 8g of acrylic acid (Oi Chemicals), 0.2g of benzyltriethylammonium chloride (Oi Chemicals), and 0.2g of hydroquinone (Oi Chemicals) were added to 52g of propylene glycol methyl ether acetate (Sigma-Aldrich) in a 300ml three-neck round-bottom flask equipped with a distillation column and stirred at 110°C for 6 hours. After the reaction was complete, 10g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 0.8g of tetrahydrophthalic acid (Sigma-Aldrich) were added and the mixture was stirred for an additional 6 hours at 110°C. After the reaction was complete, the reaction solution was recovered and analyzed. A cardo-based binder resin with a weight-average molecular weight of 8,500 and a solids content of 44% and the structure represented by Formula 7 was obtained.

[0149] Synthesis Examples 4 to 9: Silane Derivative Synthesis Synthesis Example 4 (Production of Compound 1-1': 6-(Trimethoxysilyl)-1-hexanethiol) [ka]

[0150] In a three-necked round-bottom flask equipped with a distillation tube connected to cooling water, 20 g (0.147 mol) of trichlorosilane (Gelest) and 17.51 ​​g (0.147 mol) of 6-chloro-1-hexene (Aldrich) were dissolved in 200 ml of ethyl acetate, and 0.02 g of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (2 wt% in xylene / Aldrich) was added. The mixture was heated to 75°C while introducing nitrogen and reacted for 5 hours. The solution was then filtered through a 0.1 μm Teflon membrane to remove the platinum catalyst. Then, 15.6 g (0.487 mol) of methanol was added dropwise at room temperature for 30 minutes, and the mixture was heated to 50°C and reacted for an additional 2 hours. The reaction mixture was then distilled under reduced pressure to remove the solvent. The resulting 6-chlorohexyltrimethoxysilane was then added. 24 g (0.1 mol) of silane, 8 g (0.15 mol) of sodium methoxide (Aldrich), 187 ml (0.15 mol) of hydrogen sulfide THF solution (0.8 M concentration), and 100 ml of methanol were placed in an autoclave and reacted at 100°C for 2 hours. After cooling the reaction solution, 100 ml of hydrogen chloride in methanol (1.25 M concentration) was added dropwise at room temperature over 30 minutes. The salt formed was removed by filtration and then distilled under reduced pressure to obtain 23 g of 6-(trimethoxysilyl)-1-hexanethiol.

[0151] Synthesis Example 5 (Production of Compound 1-2': 9-(Trimethoxysilyl)-1-nonanethiol) [ka]

[0152] The same procedure as in Synthesis Example 4 was repeated except that 23.7g (0.147mol) of 9-chloro-1-nonene (AK Scientific) was used instead of 6-chloro-1-hexene.

[0153] Synthesis Example 6 (Production of Compound 1-3': 12-(Trimethoxysilyl)-1-dodecanethiol) [ka]

[0154] The same procedure as in Synthesis Example 4 was repeated except that 30 g (0.147 mol) of 12-chloro-1-dodecene (Atomax Chemicals) was used instead of 6-chloro-1-hexene.

[0155] Synthesis Example 7 (Production of Compound 1-4': 6-(Triethoxysilyl)-1-hexanethiol) [ka]

[0156] The same procedure as in Synthesis Example 4 was repeated except that 22.4 g (0.487 mol) of ethanol (Aldrich) was used instead of the methanol added after platinum removal.

[0157] Synthesis Example 8 (Production of Compound 1-5': 6-(Tributhoxysilyl)-1-hexanethiol) [ka]

[0158] The same procedure as in Synthesis Example 4 was repeated except that 36 g (0.487 mol) of 1-butanol (manufactured by Aldrich) was used instead of the methanol added after platinum removal.

[0159] Synthesis Example 9 (Production of Compound 1-6': 6-(Dimethoxymethylsilyl)-1-hexanethiol) [ka]

[0160] The same procedure as in Synthesis Example 4 was repeated except that 18 g (0.147 mol) of dichloromethylsilane was used instead of trichlorosilane.

[0161] Synthesis Example 10 (Production of a cardo-based binder resin containing a silane derivative of polymer B-1) Synthesis Example 10-1: Preparation of Cardo-based binder resin (Polymer B) Compound 1 (25 g, 54 mmol) obtained in the same experiment as in Synthesis Example 1, acrylic acid 8 0.2g of propylene glycol methyl ether acetate (Oi Chemical Co., Ltd.), 0.2g of benzyltriethylammonium chloride (Oi Chemical Co., Ltd.), and 0.2g of hydroquinone (Oi Chemical Co., Ltd.) were added to a 300ml three-neck round-bottom flask equipped with a distillation column and 52g of propylene glycol methyl ether acetate (Sigma Aldrich), and the mixture was stirred at 110°C for 6 hours. After the reaction was complete, 8.5g of biphenyltetracarboxylic acid dianhydride (Mitsubishi Gas Co., Ltd.) and 1.55g of tetrahydrophthalic acid (Sigma Aldrich) were added, and the mixture was stirred for an additional 6 hours at 110°C. After the reaction was complete, the reaction solution was recovered and analyzed, and a cardo-based binder resin with a weight-average molecular weight of 5,500 and a solids content of 40% was obtained, which has the structure shown in Formula 7 above.

[0162] Synthesis Example 10-2: To the cardo binder solution obtained in Synthesis Example 10-1, 6.36 g (34 mmol) of KBM 803 (3-(trimethoxysilyl)-1-propanethiol) (Shinetsu Co., Ltd.) as shown in the following compound 1-7' was added, and the mixture was heated to 60°C and stirred for 4 hours to obtain cardo binder resin B-1 substituted with a silane group as shown in Chemical Formula 8. [ka] [ka]

[0163] Synthesis Example 11 (Production of Cardo-based Binder Resin of Polymer B-2) 8.1 g (34 mmol) of 6-(trimethoxysilyl)-1-hexanethiol (Compound 1-1') was added to the cardo binder solution obtained in Synthesis Example 10-1, and the mixture was heated to 60°C and stirred for 4 hours to obtain silane-substituted cardo binder resin B-2 as shown in Chemical Formula 9. [ka]

[0164] Synthesis Example 12 (Production of Cardo-based Binder Resin of Polymer B-3) 9.53 g (34 mmol) of 6-(triethoxysilyl)-1-hexanethiol (Compound 1-4') was added to the cardo binder solution obtained in Synthesis Example 10-1, and the mixture was heated to 60°C and stirred for 4 hours to obtain silane-substituted cardo binder resin B-3 as shown in Chemical Formula 10. [ka]

[0165] Photosensitive resin composition production evaluation 1 [Table 1]

[0166] In Table 1 above, Polymer C and Polymer D are as follows: Polymer C (Polyimide / Mw: 3,200) [ka]

[0167] Polymer D (Acrylate polymer / Mw: 12,000) [ka]

[0168] The method for producing the light-shielding layer using the above liquid composition is as follows. (1) Coating and film formation stage The black photosensitive resin composition described above is applied to a cleaned 10 cm x 10 cm glass substrate using a spin coater to a thickness of 1.5 μm, and then heated at 100°C for 1 minute to remove the solvent, thereby forming a coating film. (2) Exposure stage After a mask of a predetermined shape is placed on the obtained coating film to form a necessary pattern, the film is irradiated with actinic radiation of 190 nm to 500 nm using an exposure machine MA-6 (SUSS) at an exposure dose of 100 mJ / cm. 2 and irradiated. (3) Development stage Following the exposure step, the film is developed by immersion in AZEM AX 300 MIF developer at 25°C for 1 minute, and then washed with water to dissolve and remove the unexposed areas, leaving only the exposed areas, thereby forming an image pattern. (4) Post-processing stage The image pattern obtained by the development is post-baked at 230°C for 30 minutes to obtain a pattern that is excellent in heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability. The patterns obtained through the above steps were imaged using an optical microscope (Nicon) and the taper angles of the patterns were compared using an SEM (Hitachi).

[0169] [Table 2]

[0170] [Table 3]

[0171] Referring to the results of Tables 2 and 3, which are analysis results of the pattern images of the light-shielding layers prepared with the compositions of Table 1, it was confirmed that when polymer A-1, polymer A-2, polymer B-1, polymer C, and polymer D were used alone, the patterns prepared had significantly more residue or the size of the patterns was smaller (decreased adhesion) than in Examples 1 to 3 of the present invention, which contain a mixed composition of a cardo-based binder having a low molecular weight and a cardo-based binder having a high molecular weight.

[0172] Looking at the above results in more detail, it was found that when polymer A-1 (a cardo-based binder with a low molecular weight) was used alone, the black pigment was not completely washed out of the image after development, leaving a large amount of residue, confirming that the linearity of the pattern edges was very good.

[0173] When polymer A-2 (a cardo-based binder with a high molecular weight) was used alone, the development time was about twice as long as polymer A-1, resulting in poor development. Since relatively little development occurred in the same time, the size of the hole pattern was confirmed to be smaller. However, it was confirmed that the residue in the center of the pattern was improved compared to polymer A-1. (The breaking point of A-1 was 10-15 seconds, while the breaking point of A-2 was 50 seconds or more, resulting in poor development.)

[0174] When polymer B-1 (a cardo-based binder containing silane) was used alone, it was confirmed to have pattern formation properties intermediate between those of polymers A-1 and A-2, and it was also confirmed that a large amount of residue remained on the edges (the breaking point of polymer B-1 was less than 10 seconds).

[0175] When polymer C (polyimide) was used alone, the breaking point was slower than that of polymer A-2, and it was confirmed to be a very difficult material to develop, and it was confirmed to be the material that was least developed among the compounds of comparative examples 1 to 5 (very large amounts of residue were left at the edges and center of the pattern).

[0176] When polymer D (acrylic derivative) was used alone, the development time was about 12 seconds, which was intermediate between polymer A-1 and polymer B, and the adhesion was lower than that of the cull binders (polymers A-1, A-2, and B-1), and there was a lot of residue on the edges.

[0177] Comparing the pattern images of Example 1, which uses a mixture of polymers A-1 and A-2 of the present invention, with those of Comparative Examples 1 and 2, which use polymers A-1 and A-2 alone, it can be seen that the pattern of Example 1 of the present invention has excellent developability, and a clean pattern was obtained without residues, especially at the edges and center.

[0178] Furthermore, in Example 2 of the present invention (a mixture of Example 1 and Polymer B-1), although there was a slight difference in the pattern size, it was confirmed that there was no pattern residue and that the developability and adhesion were very excellent.

[0179] In Example 3 of the present invention (Example 1 + Polymer D), the pattern size was smaller than in Examples 1 and 2, but a very good pattern was obtained without problems with developability or residue.

[0180] The results of comparing the taper angles of Examples 1 to 3 using SEM images are shown in Table 4 below.

[0181] [Table 4]

[0182] Table 4 shows pattern images of Examples 1 to 3 and SEM cross-sectional images of Examples 1 to 3 after developing and after curing.

[0183] In Table 4, the taper angle was measured as follows: JPEG2026004500000029.jpg61106

[0184] As can be seen from the results in Tables 1 to 4, the main reason for the different performances (pattern developability, residue problems, low taper angle) depending on the resin (binder) is overflow. This is thought to be due to a difference in the flow and taper angle.

[0185] When a post-baking (thermal hardening) process is performed after developing in an alkaline solution to form a pattern, the pattern flows due to heat at 250°C. At this time, the edge of the pattern flows. The development is called melting flow.

[0186] Overflow refers to the phenomenon in which a pattern flows excessively during the melting flow. When overflow occurs after thermal curing, a hole pattern is significantly destroyed, and the opening of the pattern becomes smaller, resulting in a smaller opening area of ​​the subpixel.

[0187] It was also found that the taper angle increases as the melting flow decreases, and conversely, decreases as the melting flow increases (overflow).If the taper angle is too low, the pattern opening becomes smaller, resulting in a smaller opening area for the subpixel.

[0188] Images of the fine patterns formed in the examples and comparative examples are shown in Table 5 below.

[0189] [Table 5]

[0190] From Table 5, it can be seen that Examples 1 and 2 of the present invention, which used a mixture of Polymer A-1 and Polymer A-2, had better adhesion and formed finer patterns than Comparative Examples 1 and 2, which used Polymer A-1 and Polymer A-2 alone.

[0191] Adhesion is a measure of how finely square and line patterns can be developed, from 1 μm to 11 μm. When polymer A-1 or polymer A-2 was used alone, patterns were formed to a resolution of approximately 8 μm, when A-1 and A-2 were mixed, patterns were formed to 5 to 6 μm, and when three cull binders including polymer B were mixed, patterns were formed to the 1 μm level.

[0192] Photosensitive resin composition production evaluation 2 Examples 4 to 6: Performance (taper angle) evaluation depending on the ratio of polymer A-1 (low molecular weight) to A-2 (high molecular weight)

[0193] [Table 6]

[0194] [Table 7]

[0195] Referring to Tables 6 and 7, the developability, residue, and taper angle of the pattern depending on the mixing ratio of polymer A-1 and polymer A-2 were compared (Examples 4 to 6).

[0196] In Examples 4 to 6, a low molecular weight (MW: 4,500) cardo-based binder A-1 and a high molecular weight (MW: 8,500) cardo-based binder A-2 were mixed in a ratio of 7:3, It is used in 5:5 and 3:7 ratios.

[0197] In Examples 4 to 6, the pattern size was the largest at 17.5 μm in Example 4, which used the most polymer A-1, and it was confirmed that there was no residue and the taper angle was excellent at 33° (resolution: 5 μm, breaking point: 17 seconds).

[0198] In Example 5, in which polymers A-1 and A-2 were used in equal proportions, the pattern size was 16.9 μm, and no residue was found in the center of the pattern, but residue was found at the edge of the pattern (the breaking point increased to 21 seconds as the amount of A-2 increased compared to Example 4).

[0199] In Example 6, the pattern size was the smallest at 14.7 μm, and it was confirmed that there was a lot of residue both in the center and the edge of the pattern. This is because A-2 was used more than A-1, and the breaking point was the slowest at over 40 seconds, which is confirmed to have resulted in a large amount of residue and a small hole pattern size.

[0200] Therefore, it has been confirmed that the compound of the present invention is a photosensitive resin composition containing a larger amount of polymer A-1, a low molecular weight cardo binder, than polymer A-2, a high molecular weight cardo binder, and has excellent pattern developability and adhesion.

Claims

[Claim 1] A photosensitive resin composition comprising: (A) two or more cardo-based binders having repeating units represented by the following chemical formula 1 and different molecular weights; (B) a reactive unsaturated compound; (C) a pigment; (D) an initiator; and (E) a solvent: 【Chemistry 1】 1) "*" represents the bond linking portion of the repeat unit; 2) R １ and R ２ are each independently deuterium; a halogen group; C ６ ~C ６０ aryl groups of the formula: C, containing at least one heteroatom of O, N, S, Si and P; ２ ~C ６０ a heterocyclic group represented by the formula C ３ ~C ６０ and the aliphatic ring C ６ ~C ６０ A fused ring group of an aromatic ring represented by C １ ~C ６０ an alkyl group of C ２ ~C ６０ an alkenyl group of C ２ ~C ６０ an alkynyl group represented by C １ ~C ６０ an alkoxy group of the formula C; ６ ~C ３０ an aryloxy group selected from the group consisting of 3) R ３ ~R ６ are each independently hydrogen; deuterium; a halogen group; C ６ ~C ６０ aryl groups of the formula: C, containing at least one heteroatom of O, N, S, Si and P; ２ ~C ６０ a heterocyclic group represented by the formula C ３ ~C ６０ and the aliphatic ring C ６ ~C ６０ A fused ring group of an aromatic ring represented by C １ ~C ６０ an alkyl group of C ２ ~C ６０ an alkenyl group of C ２ ~C ６０ an alkynyl group represented by C １ ~C ６０ an alkoxy group of the formula C; ６ ~C ３０ an aryloxy group selected from the group consisting of 4) R ７ is hydrogen; deuterium; C １ ~C ６０ an alkyl group of C ２ ~C ６０ an alkenyl group; an acrylic group; and a methacrylic group, 5) m and n are each independently an integer of 0 to 4, and when m is 2 or more, adjacent R １ can be bonded to each other to form a single ring or multiple rings, and when n is 2 or more, R ２ can be linked together to form a single or multiple rings; 6) X ２ is an acid anhydride residue or an acid dianhydride residue, 7) X １ is represented by the following chemical formula 2: 8) Y １ and Y ２ are each independently selected from the group consisting of hydrogen; deuterium; Formula 3 below; and Formula 4 below: 【Chemistry 2】 9) R ８ and R ９ are each independently deuterium; a halogen group; C ６ ~C ６０ aryl groups of the formula: C, containing at least one heteroatom of O, N, S, Si and P; ２ ~C ６０ a heterocyclic group represented by the formula C ３ ~C ６０ and the aliphatic ring C ６ ~C ６０ A fused ring group of an aromatic ring represented by C １ ~C ６０ of Alkyl group; C ２ ~C ６０ an alkenyl group of C ２ ~C ６０ an alkynyl group represented by C １ ~C ６０ an alkoxy group of the formula C; ２ ~C ６０ and is selected from the group consisting of alkenyl groups 10) o and p are each independently an integer of 0 to 4, and when o is 2 or more, adjacent R ８ can be bonded to each other to form a single ring or multiple rings, and when p is 2 or more, adjacent R ９ can be linked together to form a single or multiple rings: 【Transformation 3】 【Chemistry 4】 11) L １ ~L ３ are each independently a single bond; C １ ~C ６０ an alkylene group of the formula: ６ ~C ６０ and an arylene group selected from the group consisting of 12) R １０ ~R １２ are each independently hydrogen; deuterium; a halogen group; C ６ ~C ６０ aryl groups of the formula: C, containing at least one heteroatom of O, N, S, Si and P; ２ ~C ６０ a heterocyclic group represented by the formula C ３ ~C ６０ and the aliphatic ring C ６ ~C ６０ A fused ring group of an aromatic ring represented by C １ ~C ６０ an alkyl group of the formula: １ ~C ６０ an alkoxy group selected from the group consisting of: 13) Z １ is S or O, 14) q and r are each independently an integer from 0 to 3, and q+r=3.

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