Photosensitive resin composition and display device

Abstract

An embodiment of the present invention relates to a photosensitive resin composition and a display device, wherein the photosensitive resin composition contains two or more cardo-based binders to improve residues during development and improve melt flow, and form a pattern layer with a high cone angle, and the display device includes a pattern layer, which includes a polymerized reactant of the photosensitive resin composition.

Description

Technical Field

[0001] Embodiments of the present invention relate to a photosensitive resin composition and a display device. Background Art

[0002] Colored light shielding layers, especially black light shielding layers, are used to improve image quality by preventing color interference between red, green and blue color filters in liquid crystal display devices. In recent years, in organic light emitting display devices, black light shielding layers have been studied for the same purpose as liquid crystal display devices, to prevent color mixing between adjacent pixels and to achieve low reflectivity to increase image visibility. Summary of the invention

[0003] Problems to be solved by the invention

[0004] In manufacturing the color light-shielding layer, colorants and various types of resins are used, but it is necessary to improve the resolution, heat resistance, and adhesion during development.

[0005] Particularly, in the case of a black light shielding layer, a high content of a black pigment is added, but sensitivity and adhesion may be severely deteriorated due to the black pigment.

[0006] Therefore, embodiments of the present invention include two or more cardo binders to improve the residue around the pattern and the developed portion during the development process and reduce the melting flow, and when used as a pixel defining layer, a photosensitive resin composition capable of achieving a high taper angle can be provided.

[0007] In addition, an embodiment of the present invention provides a display device including a pattern layer having a polymerized reactant of the photosensitive resin composition and a pixel defining layer having a high resolution and a high cone angle.

[0008] Solutions for solving problems

[0009] On the one hand, an embodiment of the present invention provides a photosensitive resin composition, which includes: a cardo-based binder (A) containing a repeating unit represented by the following Chemical Formula 1 and having two or more different molecular weights; a reactive unsaturated compound (B); a pigment (C); an initiator (D) and a solvent (E).

[0010] [Chemical formula 1]

[0011]

[0012] Effects of the Invention

[0013] According to an embodiment of the present invention, a photosensitive resin composition is provided. The photosensitive resin composition is represented by Chemical Formula 1 and includes two or more cardo-based binders different from each other to improve residue during development, improve melt flow, and form a pattern layer with a high taper angle.

[0014] In addition, according to an embodiment of the present invention, there is provided a display device which can have a high resolution by having a pattern layer of a polymerized reactant of the above-mentioned photosensitive resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figures 1 to 8 The figures show images of Examples and Comparative Examples of the present invention.

[0016] Figures 9 to 15 The following are scanning electron microscope (SEM) images showing examples of the present invention and comparative examples.

[0017] Figures 16 to 19 The figures show images of Examples and Comparative Examples of the present invention.

[0018] Figure 20 to Figure 22 The figures show images of Examples and Comparative Examples of the present invention.

[0019] Figure 23 to Figure 28 The following are scanning electron microscope (SEM) images showing examples of the present invention and comparative examples. DETAILED DESCRIPTION

[0020] Hereinafter, some embodiments of the present invention will be described in detail with reference to the exemplary drawings. When reference numerals are added to the components of each drawing, they may have the same reference numerals even if the same components are indicated on different drawings. In addition, when describing the present invention, when it is determined that the detailed description of the relevant known configuration or function may make the subject matter of the present invention unclear, its detailed description may be omitted. When "including", "having", "consisting of...", etc. mentioned in this specification are used, other parts may be added unless "only" is used. In the case of a component represented in the singular, unless there is a specific clear description, the case of including the plural number may be included.

[0021] In addition, when describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish a component from other components, and the nature, order, sequence, or number of the components is not limited by the terms.

[0022] In the description of the positional relationship of components, when two or more components are described as being “connected”, “coupled” or “combined”, etc., the two or more components may be directly “connected”, “coupled” or “combined”, but it should be understood that the two or more components may be further “inserted” with other components to be “connected”, “coupled” or “combined”. Here, other components may be included in one or more of the two or more components that are “connected”, “coupled” or “combined” with each other.

[0023] In the description of a time flow relationship related to a component, an operating method, or a production method, for example, when a time predecessor relationship or a flow predecessor relationship is described as "after," "following," "subsequently," "before," etc., it may also include non-continuous cases unless "immediately" or "directly" is used.

[0024] On the other hand, when referring to the numerical value of a component or its corresponding information, even if not explicitly stated, these numerical values ​​or corresponding information can be interpreted as including the error range that may occur due to various factors (e.g., process factors, internal or external influences, noise, etc.).

[0025] Unless otherwise stated, the term "halo" or "halogen" as used in this application includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0026] Unless otherwise specified, the term "alkane" or "alkyl" used in this application has 1 to 60 carbons connected by single bonds and can represent free radicals of saturated aliphatic functional groups of straight chain alkyl, branched chain alkyl, cycloalkyl (alicyclic), alkyl substituted cycloalkyl, cycloalkyl substituted alkyl, etc.

[0027] Unless otherwise stated, the term "haloalkyl" or "halogenalkyl" used in the present application may refer to an alkyl group in which a halogen is substituted.

[0028] Unless otherwise specified, the term "alkenyl" or "alkynyl" used in the present application each has a double bond or a triple bond, includes a straight chain or a branched chain group, and may have 2 to 60 carbon atoms.

[0029] The term "cycloalkyl group" used herein, unless otherwise specified, may mean an alkyl group forming a ring having 3 to 60 carbon atoms.

[0030] The term "alkoxy" or "alkoxyl" as used herein refers to an alkyl group bonded to an oxygen radical and, unless otherwise specified, may have from 1 to 60 carbon atoms.

[0031]

[0026] The terms "alkenoxyl," "alkenoxy," "alkenyloxyl," or "alkenyloxy" as used herein refer to an alkenyl group to which is attached an oxygen radical and, unless otherwise specified, may have from 2 to 60 carbon atoms.

[0032] Unless otherwise indicated, the terms "aryl" and "arylene" used in this application each have 6 to 60 carbon atoms, but are not limited thereto. In this application, aryl or arylene may include monocyclic types, ring assemblies, fused ring systems, compounds, etc. For example, aryl may refer to a monovalent functional group of phenyl, biphenyl, a monovalent functional group of naphthalene, a fluorenyl or a substituted fluorenyl.

[0033] Unless otherwise specified, the term "fluorenyl" or "fluorenylene" used in this application may each represent a monovalent or divalent functional group of fluorene. "Substituted fluorenyl" or "substituted fluorenylene" may represent a monovalent or divalent functional group of substituted fluorene. "Substituted fluorene" may mean that at least one of the following substituents R, R', R" and R'" is a functional group other than hydrogen. It may include the case where R and R' are bonded to each other and form a spiro compound with the carbon to which they are bonded.

[0034]

[0035] In addition, R, R', R" and R'" are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 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 and fluorenyl groups are monovalent functional groups or divalent functional groups of 9,9-dimethylfluorene, 9,9-diphenylfluorene and 9,9'-spirobi[9H-fluorene], respectively.

[0036] The term "ring assemblies" as used in this application refers to two or more ring systems (single ring or fused ring systems) directly connected to each other through a single bond or a double bond, and the number of direct connections between such rings is one less than the total number of ring systems in the compound. In the ring assemblies, the same or different ring systems can be directly connected to each other through a single bond or a double bond.

[0037] In the present application, since the aryl group includes a ring aggregate, the aryl group includes biphenyl and terphenyl, in which the benzene ring as a single aromatic ring is connected by a single bond. In addition, since the aryl group also includes a compound in which an aromatic ring system condensed with an aromatic monocyclic ring is connected by a single bond, for example, a compound in which fluorene (which is an aromatic ring system condensed with a benzene ring of an aromatic monocyclic ring) is connected by a single bond can also be included.

[0038] The term "fused ring system" as used in this application refers to a fused ring form having at least two atoms in common, including a fused form of two or more hydrocarbon ring systems, and a fused form of at least one heterocyclic ring system including at least one heteroatom. These fused ring systems can be aromatic rings, heteroaromatic rings, aliphatic rings, or a combination of these rings.

[0039] The term "spiro compound" used in the present application has a "spiro union", and a spiro union refers to a connection formed by two rings that share only one atom. In this case, the atom shared by the two rings is called a "spiro atom", and depending on the number of spiro atoms in a compound, it can be called a "monospiro compound", "bispiro compound", or "trispiro compound".

[0040] The term "heterocyclic group" used in the present application includes not only aromatic rings such as "heteroaryl" or "heteroarylidene", but also non-aromatic rings, and unless otherwise specified, refers to a ring having 2 to 60 carbon atoms, each ring including one or more heteroatoms, but is not limited thereto. Unless otherwise specified, the term "heteroatom" used in the present application refers to N, O, S, P or Si, and the heterocyclic group may represent a monocyclic type, a ring aggregate, a fused ring system, a spirocyclic compound, etc. including a heteroatom.

[0041] In addition, the "heterocyclic group" may also include SO 2 For example, the "heterocyclic group" may include the following compounds.

[0042]

[0043] The term "ring" as used herein includes monocyclic and polycyclic rings, including heterocyclic rings having at least one heteroatom as well as hydrocarbon rings, and may include aromatic and non-aromatic rings.

[0044] The term "polycyclic" used in the present application includes ring assemblies such as biphenyl, terphenyl, etc., fused ring systems and spiro compounds, and includes not only aromatic but also non-aromatic, and includes heterocyclic rings having at least one heteroatom as well as hydrocarbon rings.

[0045] Furthermore, when prefixes are named consecutively, it means that the substituents are listed in the order in which they are first described.

[0046] For example, in the case of arylalkoxy, it refers to an alkoxy group substituted with an aryl group, in the case of alkoxycarbonyl, it refers to a carbonyl group substituted with an alkoxy group, and in the case of arylcarbonylalkenyl, it refers to an alkenyl group substituted with an arylcarbonyl group. Here, the arylcarbonyl group may be a carbonyl group substituted with an aryl group.

[0047] In addition, unless otherwise specified, in the term "substituted or unsubstituted" used in the present application, "substituted" refers to a radical selected from deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylamino, C 1 -C 20 Alkylthiophene, C 6 -C 20 Arylthienyl, C 2 -C 20 Alkenyl, C 2 -C 20 Alkynyl, C 3 -C 20 Cycloalkyl, C 6 -C 60 Aryl, C substituted by deuterium 6 -C 20 Aryl, C 8 -C 20 Aryl, alkenyl, silane, boron, germanium and C 2 -C 20 The present invention is substituted by at least one substituent selected from the group consisting of a heterocyclic group (which includes at least one heteroatom selected from O, N, S, Si and P), but is not limited to these substituents.

[0048] In the present application, the "functional group name" corresponding to the aryl group, arylene group, heterocyclic group, etc., which are examples of each symbol and its substituent, may be described as "the name of the functional group reflecting the valence", but may also be described as "the name of the parent compound". For example, in the case of "phenanthrene" which is a kind of aryl group, the monovalent "group" is "phenanthryl (group)", and the divalent group is "phenanthryl (group)", and the name of the group is described by distinguishing the valence. However, regardless of the valence, it can also be described as the parent compound name "phenanthrene".

[0049] Similarly, in the case of pyrimidine, regardless of its valence, it is described as "pyrimidine", in the case of monovalence, it is described as pyrimidinyl (group), in the case of divalence, it is described as pyrimidinyl (group), that is, it is described as a "group name" of the corresponding valence. Therefore, in the present application, when the type of substituent is described as the name of the parent compound, it can represent an n-valent "group" formed by desorption of hydrogen atoms bonded to carbon atoms and / or heteroatoms of the parent compound.

[0050] In addition, unless otherwise specified, the chemical formulae used in the present application may be applied in the same manner as the definition of substituents defined by the index definition of the following chemical formulae.

[0051]

[0052] When a is 0, there is no substituent R 1 ; When a is 1, a substituent R 1 When a is 2 or 3, they are combined as follows, in which case R 1 may be the same as or different from each other; when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, and the marking of hydrogen bonded to the carbon forming the benzene ring may be omitted.

[0053]

[0054] In the present application, substituents bonded to each other to form a ring refers to that multiple substituents bonded to each other share any atom (e.g., carbon atom and at least one atom in heteroatom O, N, S, Si and P) to form a saturated or unsaturated ring. For example, in the case of naphthalene, adjacent methyl and butadienyl groups substituted on any one benzene ring share a carbon to form an unsaturated ring, or vinyl and propenyl groups share a carbon to form an unsaturated ring. In addition, in the case of fluorene, itself can be considered to be an aryl group with 13 carbon atoms, but it can be considered that two methyl groups substituted on biphenyl are bonded to each other to share a carbon to form a ring.

[0055] In the present application, the organic electronic element may refer to one or more components between an anode and a cathode, or may refer to an organic light emitting diode including an anode, a cathode, and one or more components therebetween.

[0056] In addition, in some cases, the organic electronic element in the present application may refer to an organic light emitting diode and a panel including the organic light emitting diode, or may refer to an electronic device including a panel and a circuit. Among them, for example, the electronic device may include a display device, a lighting device, a solar cell, a portable or mobile terminal (for example, a smart phone, a tablet computer, a PDA, an electronic dictionary, a PMP, etc.), a navigation terminal, a game console, various televisions, various computer displays, etc., but the present invention is not limited thereto, and the electronic device may be any type of device as long as it includes one or more of the components.

[0057] The photosensitive resin composition according to an embodiment of the present invention includes two or more kinds of cardo-based binders (A) having molecular weights different from each other, a reactive unsaturated compound (B), a pigment (C), an initiator (D), and a solvent (E).

[0058] The two or more cardo-based binders (A) include a repeating unit represented by Chemical Formula 1 below.

[0059] [Chemical formula 1]

[0060]

[0061] Hereinafter, Chemical Formula 1 will be described.

[0062] "*" indicates a portion of a bond connected through a repeating unit. Therefore, in the repeating unit represented by the chemical formula 1, portions indicated by curly brackets may be connected to each other.

[0063] R 1 and R 2 Each independently selected from deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 6 ~C 30 A group consisting of aryloxy groups.

[0064] R 1 and R 2Each independently is C 1 -C 40 Alkyl or C 1 -C 20 alkyl.

[0065] R 3 To R 6 Each independently selected from hydrogen; deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 6 ~C 30 A group consisting of aryloxy groups.

[0066] R 3 To R 6 Each independently is C 1 -C 40 Alkyl or C 1 -C 20 alkyl.

[0067] R 7 Selected from hydrogen; deuterium; C 1 -C 60 Alkyl; C 2 ~C 60 The group consisting of alkenyl; acrylic acid; methacrylic acid.

[0068] R 7 Can be C 1 -C 40 Alkyl or C 1 -C 20 alkyl.

[0069] R 7 Can be C 2 -C 40 Alkenyl or C 2 -C 20 Alkenyl.

[0070] m and n are each independently an integer from 0 to 4.

[0071] When m is 2 or greater, the adjacent R 1 They may be combined with each other to form a monocyclic or polycyclic ring. When n is 2 or more, R 2 They may be bonded to each other to form a single ring or multiple rings.

[0072] X 2 It is an acid anhydride residue or an acid dianhydride residue.

[0073] X 1 It is represented by the following Chemical Formula 2. Chemical Formula 2 will be described later.

[0074] Y 1 and Y 2 Each is independently selected from the group consisting of hydrogen; deutrium; the following Chemical Formula 3; and the following Chemical Formula 4. Chemical Formula 3 and Chemical Formula 4 will be described later.

[0075] Hereinafter, Chemical Formula 2 will be described.

[0076] [Chemical formula 2]

[0077]

[0078] * refers to X in chemical formula 1 1 The part that connects two benzene rings.

[0079] R 8 and R 9 Each independently selected from deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 2 ~C 60 A group consisting of alkenyl groups.

[0080] R 8 and R 9 Each independently is C 1 -C 40 Alkyl or C 1 -C 20 alkyl.

[0081] R 8 and R 9 Each independently is C 1 -C 40 Alkenyl or C 1 -C 20 Alkenyl.

[0082] R 8 and R 9 Each independently is C 1 -C 40 Alkoxy or C 1 -C 20 Alkoxy.

[0083] o and p are each independently an integer from 0 to 4.

[0084] When o is 2 or greater, the adjacent R 8 They may be bonded to each other to form a single ring or multiple rings.

[0085] When p is 2 or greater, the adjacent R 9 They may be bonded to each other to form a single ring or multiple rings.

[0086] Hereinafter, Chemical Formula 3 and Chemical Formula 4 will be described.

[0087]

[0088] The bonded portion cut by the wavy mark represents Y in Chemical Formula 1. 1 and Y 2 The portion bonded to oxygen.

[0089] L 1 To L 3 Each independently selected from a single bond; C 1 ~C 60 Alkylene; C 6 ~C 60 A group consisting of arylene groups.

[0090] L 1 To L 3 Each independently is C 1 -C 40 Alkylene or C 1 -C 20 Alkylene.

[0091] L 1 To L 3 Each independently is C 1 -C 40 Arylene or C 1 -C 20 Arylene.

[0092] R10 To R 12 Each independently selected from hydrogen; deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 1 -C 60 The group consisting of alkoxy groups.

[0093] R 10 To R 12 Each independently is C 1 -C 40 Alkyl or C 1 -C 20 alkyl.

[0094] R 10 To R 12 Each independently is C 1 -C 40 Alkoxy or C 1 -C 20 Alkoxy.

[0095] Z 1 It is S or O.

[0096] q and r are each independently an integer from 0 to 3, and q+r=3.

[0097] In at least one of the two or more cardo-based binders comprising the repeating unit represented by Chemical Formula 1, Y 1 and Y 2 At least one of them can be the Chemical Formula 3.

[0098] In at least one of the two or more cardo-based binders comprising the repeating unit represented by Chemical Formula 1, Y 1 and Y 2 At least one of them may be the Chemical Formula 4, and the weight average molecular weight is 5000 to 7000.

[0099] The photosensitive resin composition according to the embodiment of the present invention may form a pattern layer without residue and has excellent adhesion by including two or more kinds of cardo-based binders represented by the Chemical Formula 1.

[0100] The two or more cardo-based binders may include a low molecular weight cardo-based binder

[0101] and high molecular weight cardo-based adhesives.

[0102] The low molecular weight cardo-based binder may include a repeating unit represented by the above Chemical Formula 1, and may have a weight average molecular weight of 3,000 to 5,000 or 3,000 to 4,800.

[0103] The high molecular weight cardo-based binder may include a repeating unit represented by the above Chemical Formula 1, and may have a weight average molecular weight of 7000 to 9000, 7000 to 8800, or 7000 to 8000.

[0104] According to the photosensitive resin composition of the embodiment of the present invention including the low molecular weight cardo-based binder and the high molecular weight cardo-based binder, the cardo-based binder with a high molecular weight can be used as the binder.

[0105] Higher proportions include low molecular weight cardo-based binders.

[0106] For example, the photosensitive resin composition contains 50 to 90 wt %, 51 to 90 wt %, 60 to 85 wt %, or 70 to 80 wt % of the low molecular weight cardo-based binder relative to the sum of the mass of the low molecular weight cardo-based binder and the mass of the high molecular weight cardo-based binder. When the content of the low molecular weight cardo-based binder is within the above range, when a pattern layer is manufactured using the photosensitive resin composition, a pattern without residue can be formed, and film thickness loss during development can be prevented.

[0107] The photosensitive resin composition according to the embodiment of the present invention may further include at least one of an acrylic adhesive and a polyimide adhesive in addition to two or more cardo-based adhesives.

[0108] The acrylic adhesive is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including one or more acrylate repeating units.

[0109] In order to prevent the excessive solubility of polyamic acid as a polyimide precursor in an alkaline aqueous solution, the polyimide binder can adjust the solubility by copolymerizing the main structure polyimide of the polymer so that an appropriate solubility difference can be obtained between the exposed and unexposed parts during the composition process, and thereby a black pixel separation layer with excellent heat resistance and pattern formation can be realized.

[0110] For example, the polyamic acid-polyimide copolymer includes a polyamic acid repeating unit and a polyimide repeating unit, and the polyamic acid repeating unit and the polyimide repeating unit may be included 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 included in a molar ratio in the above range, solubility in a solvent used in the composition can be ensured, and appropriate developability can be exhibited in a patterning process. The polyimide-polyamic acid copolymer that can be used has a structure shown in the following chemical formula 5.

[0111] [Chemical formula 5]

[0112]

[0113] Hereinafter, Chemical Formula 5 will be described.

[0114] X 2 and X 4 Each is independently selected from the group consisting of a substituted or unsubstituted tetravalent alicyclic organic group; and a substituted or unsubstituted tetravalent aromatic organic group.

[0115] L 3 To L 6 are each independently selected from a single bond; substituted or unsubstituted C 1 -C 10 Alkylene; substituted or unsubstituted C 3 -C 10 Cycloalkylene; substituted or unsubstituted C 6 -C 20 A group consisting of arylene groups.

[0116] R 15 and R 16 Each is independently selected from the group consisting of hydrogen; and substituted or unsubstituted norbornene.

[0117] o and p are each independently an integer from 1 to 10,000.

[0118] The photosensitive resin composition according to an embodiment of the present invention includes a reactive unsaturated compound (B).

[0119] The reactive unsaturated compound may be (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 refer to methacrylic acid, acrylic acid, or a mixture of methacrylic acid and acrylic acid.

[0120] The reactive unsaturated compound may be a photopolymerizable compound. Since the reactive unsaturated compound is a photopolymerizable compound, the photosensitive resin composition is sufficiently polymerized during exposure in the pattern forming process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0121] The reactive unsaturated compound is, for example, one or more selected from 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, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, and triacryloxyethyl phosphate, but is not limited thereto.

[0122] Commercially available products of photopolymerizable monomers are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M-101, M-111, M-114, etc. from Toagosei Co., Ltd.; KAYARAD from Nippon Kayaku Co., Ltd. TC-120S, etc.; V-158, V-2311, etc. of Osaka Organic Chemical Industry Co., Ltd. Examples of difunctional esters of (meth)acrylic acid are Aronix M-210, M-240, M-6200, etc. of Toagosei Co., Ltd.; KAYARADHDDA, HX-220, R-604, etc. of Nippon Kayaku Co., Ltd.; V-260, V-312, V-335HP, etc. of Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid are Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, etc. from Toagosei Co., Ltd., KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc. from Nippon Kayaku Co., Ltd., V-295, V-300, V-360, etc. from Osaka Organic Chemical Industry Co., Ltd. These products can be used alone or in combination of two or more.

[0123] In order to impart better developability, a reactive unsaturated compound may be used after the treatment with anhydride.

[0124] The content of the reactive unsaturated compound may be 1 wt % to 40 wt % or 1 wt % to 20 wt % relative to the total amount of the photosensitive resin composition. When the reactive unsaturated compound is included in the above range, hardening occurs sufficiently during exposure in the pattern formation process, reliability is excellent, and the pattern has excellent heat resistance, light resistance and chemical resistance, and also has excellent resolution and adhesion.

[0125] The photosensitive resin composition according to an embodiment of the present invention includes a pigment.

[0126] The pigment may be one or more of an organic pigment and an inorganic pigment.

[0127] The pigment may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

[0128] 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.

[0129] Examples of green pigments include halogen-substituted copper phthalocyanine pigments such as CI green pigment 36, CI green pigment 7, and the like.

[0130] Examples of the blue pigment include copper phthalocyanine pigments such as CI blue pigment 15:6, CI blue pigment 15, CI blue pigment 15:1, CI blue pigment 15:2, CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, and CI blue pigment 16.

[0131] Examples of the yellow pigment include isoindoline pigments such as CI yellow pigment 139; quinophthalone pigments such as CI yellow pigment 138; nickel complex pigments such as CI yellow pigment 150, and the like.

[0132] Examples of the black pigment include lactam black, aniline black, perylene black, titanium black, carbon black, and the like.

[0133] The pigment may be used alone or in combination of two or more, and is not limited to these examples.

[0134] When the pattern layer formed of the photosensitive resin composition requires high light shielding properties, black pigments can be used to effectively shield the light. When black pigments are used, they can be used together with color correctors (anthraquinone pigments, perylene black pigments, phthalocyanine pigments, azo pigments, etc.).

[0135] In order to disperse the pigment in the photosensitive resin composition, a dispersant may be used together. The pigment may be surface-treated with the dispersant in advance, or may be used by adding the dispersant together with the pigment when preparing the photosensitive resin composition.

[0136] Nonionic dispersants, anionic dispersants, cationic dispersants, etc. can be used as the dispersant. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyol alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylates, carboxylates, alkylamide alkylene oxide adducts, alkylamines, etc., which can be used alone or in combination of two or more.

[0137] For example, commercially available products of the dispersant are DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK -170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFK from BASF Co., Ltd. A-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc.; Zeneka Co., Ltd.’s Solsperse5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or Ajinomoto Co., Ltd.'s PB711, PB821, etc.

[0138] The dispersant may be included in an amount of 0.1 to 15 wt % based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the photosensitive resin composition has excellent dispersibility and thus has excellent stability, developability, and patternability when manufacturing a light shielding layer.

[0139] The pigment can be used after pretreatment with a water-soluble inorganic salt and a wetting agent. When the pigment is used after pretreatment, the primary particle size of the pigment can be refined. The pretreatment can be carried out by the following steps: kneading the pigment with the water-soluble inorganic salt and the wetting agent, and filtering and washing the pigment obtained in the kneading step. Kneading can be carried out at a temperature of 40° C. to 100° C., and filtering and washing can be carried out by washing the inorganic salt with water and then filtering. Examples of water-soluble inorganic salts include sodium chloride and potassium chloride, but are not limited thereto.

[0140] The wetting agent is used as a medium for uniformly mixing the pigment and the water-soluble inorganic salt so that the pigment can be easily pulverized, and examples of the wetting agent include alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether, etc.; alcohols, such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, etc. These can be used alone or in combination of two or more.

[0141] The pigment subjected to the kneading step may have an average particle diameter of 20 nm to 110 nm. When the average particle diameter of the pigment is within the above range, a fine pattern may be effectively formed while having excellent heat resistance and light resistance.

[0142] The photosensitive resin composition may include the pigment in an amount of 1 to 40 wt %, 1 to 30 wt %, or 2 to 30 wt % based on the total amount thereof. When the pigment is included within the above range, the photosensitive resin composition has excellent color reproducibility and can form a pattern layer having excellent curability and adhesion.

[0143] The photosensitive resin composition contains an initiator (D).

[0144] The initiator may be a photopolymerization initiator, a free radical polymerization initiator, or a combination thereof.

[0145] As the photopolymerization initiator, for example, one or more of acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, oxime ester compounds, and triazine compounds can be used.

[0146] Examples of the acetophenone compound include 2,2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like. Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic 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.

[0147] Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0148] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc. Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, methyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-s(trichloromethyl)-s-triazine, 2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxyphenylvinyl)-6-triazine, etc.

[0149] In addition to the above compounds, the photopolymerization initiator may include a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, etc. The radical polymerization initiator may include a peroxide compound, an azobis compound, etc.

[0150] Examples of the peroxide compound include: ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, etc.; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, etc.; hydrogen peroxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, etc.; dialkyl peroxides such as dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, etc. ,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,3-bis(tert-butoxyisopropyl)benzene, tert-butyl peroxyvalerate, etc.; alkyl peresters, such as 2,4,4-trimethylpentyl peroxyphenoxyacetate, α-cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, di-tert-butyl peroxytrimethyladipate, etc.; percarbonates, such as di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-4-tert-butylcyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, acetyl peroxycyclohexylsulfonyl, tert-butyl peroxyaryl carbonate, etc.

[0151] Examples of azobis compounds include: 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(methyl isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α'-azobis(isobutyronitrile), 4,4'-azobis(4-cyanovaleric acid), etc. The initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light and being excited and then transferring energy. Examples of photosensitizers include: tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc.

[0152] The initiator may be included 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 content of the initiator is within the above range, curing may occur sufficiently during exposure in a pattern forming process using the photosensitive resin composition, thereby obtaining excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion, and the reduction in transmittance due to unreacted initiator may be prevented.

[0153] The photosensitive resin composition according to an embodiment of the present invention includes a solvent.

[0154] The solvent is compatible with the cardo-based adhesive, the reactive unsaturated compound, the pigment and the initiator, but a non-reactive material may be used.

[0155] 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, diethyl cellosolve acetate, etc.; 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, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxybenzoic acid, 1-[4-(2-nitropropene)-1-yl]-dextrin; ethyl acetate, isobutyl acetate, etc.; alkyl esters of saturated aliphatic monocarboxylic acids, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetates, such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetates, such as methyl methoxyacetate, ethyl ethoxyacetate, methoxybutyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; alkyl 3-oxypropionates, such as methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.; alkyl 3-alkoxypropionates, such as methyl 3-methoxypropionate, 3- ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionates, such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; alkyl 2-alkoxypropionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxo-2-methylpropionic acid esters, such as methyl 2-oxo-2-methylpropionic acid, ethyl 2-oxo-2-methylpropionic acid, etc.; monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionic acid, such as methyl 2-methoxy-2-methylpropionic acid, ethyl 2-ethoxy-2-methylpropionic acid, etc.; esters, such as 2 -hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, hydroxyethyl acetate, 2-hydroxy-3-methylbutyric acid methyl ester, etc.; ketoesters such as ethyl pyruvate, etc.; and examples thereof include high boiling point 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, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc.

[0156] Considering the compatibility and reactivity between solvents, glycol ethers such as ethylene glycol monoethyl ether, etc., glycol alkyl ether acetates such as ethyl cellulose acetate solvents, etc., esters such as ethyl 2-hydroxypropionate, etc., carbitols such as diethylene glycol monomethyl ether, etc., propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc. can be used. The solvent may be included in the balance, specifically 50 to 90% by weight, relative to the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus has excellent processability when manufacturing the light-shielding layer.

[0157] Another embodiment of the present invention may provide a display device.

[0158] A display device according to an embodiment of the present invention includes a pattern layer including a polymerized reactant of a photosensitive resin composition.

[0159] In the display device according to the embodiment of the present invention, since matters regarding the photosensitive resin composition are the same as those of the aforementioned photosensitive resin composition according to the embodiment of the present invention, they are omitted.

[0160] The polymerized reactant of the photosensitive resin composition may be formed by, for example, coating the photosensitive resin composition on a TFT substrate and curing it.

[0161] By including the polymerized reactant of the photosensitive resin composition, the pattern layer may have excellent resolution and a high taper angle.

[0162] The display device may include a plurality of sub-pixels, and the pattern layer may be a pixel defining layer dividing the plurality of sub-pixels.

[0163] For example, the light emitting device may be located in a sub-pixel of a display device, and the light emitting device may be an organic light emitting device. In an organic light emitting device, for example, a first electrode, an organic layer, and a second electrode may be stacked sequentially. In this example, a 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 sub-pixel is determined by the opening area of ​​the pattern layer, the above-mentioned pattern layer may be a pixel definition layer. In addition, the pattern layer may be a light shielding layer that blocks light.

[0164] The pattern layer according to an embodiment of the present invention may have a high taper angle. For example, the pattern layer according to an embodiment of the present invention may have an inclination angle of 20 to 40 degrees. The inclination angle may be an inclination angle in a direction parallel to the display surface at a point where the inclination begins.

[0165] The pattern layer as the above-mentioned pixel defining layer has an opening, and the inclined portion connecting the opening and the non-opening has an inclination angle. The pattern layer according to an embodiment of the present invention includes a polymerized reactant of the above-mentioned photosensitive resin composition, and the photosensitive resin composition can form a pattern layer without residue, and since the melting flow is suppressed during the pattern formation process, a high inclination angle can be achieved. Therefore, as described above, the pattern layer has a large inclination angle, so that the length of the inclined portion can be shortened, so that the length of the inclined portion can be reduced, so that the distance between the openings can be reduced, so that the sub-pixels can be densely arranged, and the display device can have a high resolution.

[0166] The above description is only an example of the technical idea of ​​the present invention, and a person skilled in the art to which the present invention belongs will be able to make various modifications and variations without departing from the essential features of the present invention. In addition, the embodiments disclosed in the present invention are not intended to limit the technical idea of ​​the present invention, but are used to explain the technical idea, so the scope of the technical idea of ​​the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the attached claims, and all technical ideas within the scope equivalent thereto should be interpreted as included within the scope of the present invention.

[0167] Hereinafter, Synthesis Examples and Examples according to the present invention will be described in detail, but the Synthesis Examples and Examples of the present invention are not limited thereto.

[0168] Synthesis example 1

[0169] (Preparation of 9,9-bis[4-(epoxypropoxy)phenyl]fluoride of Chemical Formula 6)

[0170] 20 g of 9,9'-bisphenolfluorene (Sigma aldrich), 8.67 g of glycidyl chloride (Sigma aldrich) and 30 g of anhydrous potassium carbonate were added to a 300 ml 3-necked round-bottom flask filled with 100 ml of dimethylformamide and equipped with a distillation tube, the temperature was raised to 80°C and reacted for 4 hours, the temperature was lowered to 25°C to filter the reaction solution, the filtrate was stirred in 1000 ml of water, added dropwise, and 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-(epoxypropoxy)phenyl]fluoride of Chemical Formula 6. The purity of the obtained powder was 98% by purity analysis of HPLC.

[0171] [Chemical formula 6]

[0172]

[0173] Synthesis Example 2: Preparation of Low Molecular Weight Carbohydrate Binder Resin (Polymer A-1)

[0174] (Preparation of the low molecular weight carbomer-based binder resin of the following chemical formula 7: A-1)

[0175] 25 g of compound 1 (54 mmol) obtained in Synthesis Example 1, 8 g of acrylic acid (Oi Kakin), 0.2 g of benzyltriethylammonium chloride (Oi Kakin), and 0.2 g of hydroquinone (Oi Kakin) were added to a 300 ml 3-necked round-bottom flask equipped with 52 g of propylene glycol methyl ether acetate (Sigma aldrich) and a distillation tube, and stirred at 110° C. for 6 hours. After the reaction was completed, 8 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 1.8 g of tetrahydrophthalic acid (Sigmaaldrich) were added, and the mixture was stirred at 110° C. for 6 hours. After the reaction was completed, the reaction solution was recovered, and as a result of analysis, a cardo-based binder resin having a molecular weight of 4,500 and a solid content of 45% having a structure shown in Chemical Formula 7 was obtained.

[0176] [Chemical formula 7]

[0177]

[0178] Synthesis Example 3: Preparation of High Molecular Weight Carbomer Binder Resin (Polymer A-2)

[0179] 25 g of compound 1 (54 mmol) obtained by the same experiment as in Synthesis Example 1, 8 g of acrylic acid (Oi Kakin), 0.2 g of benzyltriethylammonium chloride (Oi Kakin), and 0.2 g of hydroquinone (Oi Kakin) were added to a 300 ml 3-necked round-bottom flask equipped with 52 g of propylene glycol methyl ether acetate (Sigma aldrich) and a distillation tube, and stirred at 110° C. for 6 hours. After the reaction was completed, 10 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 0.8 g of tetrahydrophthalic acid (Sigma aldrich) were added, and then stirred at 110° C. for 6 hours. After the reaction was completed, the reaction solution was recovered, and as a result of analysis, a cardo-based binder resin having a molecular weight of 8,500 and a solid content of 44% having the structure shown in Chemical Formula 7 was obtained.

[0180] Synthesis Examples 4 to 9: Synthesis of Silane Derivatives

[0181] Synthesis Example 4 (Preparation of Compound 1-1': 6-(trimethoxysilyl)-1-hexanethiol)

[0182] [Compound 1-1']

[0183]

[0184] In a 3-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 a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution (2 wt% in xylene / Aldrich) was added, nitrogen was added, the temperature was raised to 75°C, the reaction was continued for 5 hours, and then the solution was filtered through a 0.1 μm Teflon membrane to remove the platinum catalyst. Thereafter, 15.6 g (0.487 mol) of methanol was added dropwise at room temperature for 30 minutes, the temperature was raised to 50°C, the reaction was continued for another 2 hours, and the reaction solution was distilled off under reduced pressure to remove the solvent. 24 g (0.1 mol) of 6-chlorohexyltrimethoxysilane thus obtained, 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 the reaction solution was cooled, 100 ml of a methanol solution of hydrogen chloride (1.25 M concentration) was added dropwise at room temperature for 30 minutes, the resulting salt was removed by filtration, and distilled under reduced pressure to obtain 23 g of 6-(trimethoxysilyl)-1-hexanethiol.

[0185] Synthesis Example 5 (Preparation of Compound 1-2': 9-(trimethoxysilyl)-1-nonanethiol)

[0186] [Compound 1-2']

[0187]

[0188] In Synthesis Example 4, the same procedures were followed except that 23.7 (0.147 mol) of 9-chloro-1-nonene (AK Scientific) was used instead of 6-chloro-1-hexene.

[0189] Synthesis Example 6 (Preparation of Compound 1-3': 12-(Trimethoxysilyl)-1-dodecanethiol)

[0190] [Compound 1-3']

[0191]

[0192] In Synthesis Example 4, the same procedures were followed except that 30 g (0.147 mol) of 12-chloro-1-dodecene (Atomax Chemicals) was used instead of 6-chloro-1-hexene.

[0193] Synthesis Example 7 (Preparation of Compound 1-4': 6-(triethoxysilyl)-1-hexanethiol)

[0194] [Compound 1-4']

[0195]

[0196] In Synthesis Example 4, the same procedures were followed except that 22.4 g (0.487 mol) of ethanol (Aldrich) was used instead of the methanol added after the removal of platinum.

[0197] Synthesis Example 8 (Preparation of Compound 1-5': 6-(tributoxysilyl)-1-hexanethiol)

[0198] [Compound 1-5']

[0199]

[0200] In Synthesis Example 4, the same procedures were followed except that 36 g (0.487 mol) of 1-butanol (Aldrich) was used instead of the methanol added after the removal of platinum.

[0201] Synthesis Example 9 (Preparation of Compound 1-6': 6-(dimethoxymethylsilyl)-1-hexanethiol)

[0202] [Compound 1-6']

[0203]

[0204] In Synthesis Example 4, except that 18 g (0.147 mol) of dichloromethylsilane was used instead of trichlorosilane, the other steps were the same.

[0205] Synthesis Example 10 (Preparation of Cardo-based Binder Resin Containing Silane Derivative of Polymer B-1)

[0206] Synthesis Example 10-1: Preparation of Cardo-based Binder Resin (Polymer B)

[0207] 25 g (54 mmol) of compound 1 obtained by the same experiment as in Synthesis Example 1, 8 g of acrylic acid (Oi Kakin), 0.2 g of benzyltriethylammonium chloride (Oi Kakin), and 0.2 g of hydroquinone (Oi Kakin) were added to a 300 ml 3-necked round-bottom flask equipped with 52 g of propylene glycol methyl ether acetate (Sigma aldrich) and a distillation tube, and stirred at 110° C. for 6 hours. After the reaction was completed, 8.5 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas) and 1.55 g of tetrahydrophthalic acid (Sigma aldrich) were added, and then stirred at 110° C. for 6 hours. After the reaction was completed, the reaction solution was recovered, and as a result of analysis, a cardo-based binder resin having a molecular weight of 5500 and a solid content of 40% having the structure shown in the chemical formula 7 was obtained.

[0208] Synthesis Example 10-2: In the cardo-based adhesive solution obtained in Synthesis Example 10-1, 6.36 g (34 mmol) of KBM 803 (3-(trimethoxysilyl)-1-propanethiol (Shinetsu) such as compound 1-7' was added, heated to 60°C and stirred for 4 hours to obtain a cardo-based adhesive resin B-1 in which the silyl group is substituted such as chemical formula 8.

[0209] [Compound 1-7']

[0210]

[0211] [Chemical formula 8]

[0212]

[0213] Synthesis Example 11 (Preparation of Cardo-based Binder Resin of Polymer B-2)

[0214] In the cardo-based binder solution obtained in Synthesis Example 10-1, 8.1 g (34 mmol) of 6-(trimethoxysilyl)-1-hexanethiol (Compound 1-1') was added, heated to 60°C and stirred for 4 hours to obtain a cardo-based binder resin B-2 in which the silyl group is substituted such as Chemical Formula 9.

[0215] [Chemical formula 9]

[0216]

[0217] Synthesis Example 12 (Preparation of Cardo-based Binder Resin of Polymer B-3)

[0218] In the cardo-based binder solution obtained in Synthesis Example 10-1, 9.53 g (34 mmol) of 6-(triethoxysilyl)-1-hexanethiol (Compound 1-4') was added, heated to 60°C and stirred for 4 hours to obtain a cardo-based binder resin B-3 in which the silyl group is substituted such as Chemical Formula 10.

[0219] [Chemical formula 10]

[0220]

[0221] Preparation and evaluation of photosensitive resin composition 1

[0222] [Table 1]

[0223]

[0224] In Table 1, polymer C and polymer D are as follows.

[0225] Polymer C (polyimide / molecular weight: 3200)

[0226]

[0227] Polymer D (Acrylate polymer / molecular weight: 12000)

[0228]

[0229] The method for preparing the light-shielding layer using the above composition is as follows.

[0230] (1) Coating and film coating steps

[0231] The black photosensitive resin composition was coated on a washed glass substrate of 10 cm×10 cm in thickness using a spin coater, and then heated at 100° C. for 1 minute to remove the solvent, thereby forming a coating film.

[0232] (2) Exposure Step

[0233] After inserting a mask of a predetermined shape into the obtained coating film to form a desired pattern, the film was irradiated with actinic rays of 190 nm to 500 nm. An exposure machine MA-6 (SUSS) was used at 100 mJ / cm 2 Exposure amount.

[0234] (3) Development step

[0235] After the exposure step, the film was developed in AZEM's AX 300 MIF developer at 25° C. for 1 minute by immersion, and then washed with water to dissolve and remove the unexposed portion, leaving only the exposed portion to form an image pattern.

[0236] (4) Post-processing steps

[0237] In order to obtain a pattern excellent in heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability, the image pattern obtained by the above-mentioned development process was post-baked at 230° C. for 30 minutes.

[0238] Regarding the patterns obtained through the above steps, the pattern images were depicted as pictures by using an optical microscope (Nicon), and the taper angles of the patterns were compared using SEM (Hitachi).

[0239] [Table 2]

[0240]

[0241] [Table 3]

[0242]

[0243] Referring to the results of Tables 1 and 2, which analyze the pattern images of the shading layer prepared with the composition of Table 1, it can be confirmed that when polymer A-1, polymer A-2, polymer B-1, polymer C and polymer D are used alone, the resulting patterns have more residues or the size of the patterns is reduced (adhesion is reduced) compared to Examples 1 to 3 of the present invention comprising a cardo-based adhesive with a low molecular weight and a cardo-based adhesive with a high molecular weight.

[0244] If the above results are examined in more detail, it can be seen that when polymer A-1 (a cardo-based binder with a low molecular weight) is used alone, the black pigment is not completely washed away in the image after development, so a large amount of residue remains, and it can be confirmed that the straightness of the pattern edge is also very excellent.

[0245] When polymer A-2 (a cardo-based binder with a high molecular weight) was used alone, the development time was reduced by about 2 times compared to polymer A-1, so the development effect was not good, and it was confirmed that the size of the hole pattern was reduced due to less development in the same development time. However, it was confirmed that the residue in the center of the pattern was improved compared to the residue of polymer A-1 (the breaking point of A-1 was between 10 seconds and 15 seconds, while the breaking point of A-2 was more than 50 seconds, so the phenomenon was not good).

[0246] When polymer B-1 (silane-containing cardo-based binder) was used alone, it was confirmed that its pattern forming properties were intermediate between polymers A-1 and A-2, and a large amount of residue remained at the edge (the breaking point of polymer B-1 was less than 10 seconds).

[0247] When polymer C (polyimide) was used alone, its breaking point was slower than that of polymer A-2, and therefore it was confirmed to be a material that was very difficult to develop, and among the compounds of comparative examples 1-5, it was confirmed to be the least developable material (there were many residues at the edge and center of the pattern).

[0248] When polymer D (acrylic acid derivative) is used alone, the development time is about 12 seconds, which is in the middle of polymer A-1 and polymer B. Its adhesion is lower than that of cardo series adhesives (polymers A-1, A-2, B-1), and there are many residues at the edges.

[0249] When comparing Example 1 in which polymers A-1 and A-2 of the present invention are mixed and Comparative Examples 1 and 2 in which polymers A-1 and A-2 are used alone, it can be seen that the pattern of Example 1 of the present invention is excellent in developability, and in particular, a clean pattern is obtained with no residue at the edge and center.

[0250] In addition, in the case of Example 2 of the present invention (mixture of Example 1+polymer B-1), the size of the pattern showed a small difference, but it was confirmed that there was no developability and pattern residue, and the adhesiveness was very excellent.

[0251] When using Example 3 of the invention (Example 1 + Polymer D), the size of the pattern is reduced compared to Examples 1 and 2, but a very good pattern can be obtained without problems with developability and residue.

[0252] The results of comparing the taper angles of Example 1 to Example 3 by using SEM images are shown in Table 4 below.

[0253] [Table 4]

[0254]

[0255] 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.

[0256] In Table 4, Fig.15 The taper angle is measured as shown in FIG.

[0257] As shown in the results of Tables 1 to 4, a typical reason for exhibiting different performances (pattern development, residue problem, low taper angle) depending on the resin (binder) is due to the difference between the over flow angle and the taper angle.

[0258] When a pattern is formed by development in an alkali aqueous solution and then subjected to a post-baking (thermosetting) treatment, the pattern flows under the heat of 250° C. At this time, the phenomenon that the end of the pattern flows downward is called melting flow.

[0259] Overflow refers to a phenomenon in which a pattern flows in large quantities in a molten flow. When overflow occurs after thermal curing, the pattern collapses in large quantities in a hole pattern, so that it can be confirmed that the opening of the pattern becomes smaller and the opening area of ​​the sub-pixel becomes smaller.

[0260] In addition, it can be confirmed that the taper angle increases as the melt flow decreases, and conversely decreases as the melt flow increases. When the taper angle is very low, the opening of the pattern becomes smaller and the opening area of ​​the sub-pixel becomes smaller.

[0261] Images of fine patterns formed in Examples and Comparative Examples are shown in Table 5 below.

[0262] [Table 5]

[0263]

[0264] As can be seen from Table 5, compared with Comparative Examples 1 and 2 using polymer A-1 and polymer A-2 alone, Examples 1 and 2 of the present invention using the two types in combination have more excellent adhesion and form fine patterns.

[0265] Adhesion is a measure of how finely square and line patterns can be developed from 1 μm to 11 μm. When polymer A-1 and polymer A-2 were used alone, patterns with a resolution of about 8 μm were formed; when polymer A-1 and polymer A-2 were mixed, patterns with a resolution of about 1 μm were formed. When three cardo-based binders including polymer B are mixed and used, a pattern with a resolution of 1 μm is formed.

[0266] Preparation and evaluation of photosensitive resin composition 2

[0267] Examples 4 to 6: Evaluation of performance (cone angle) according to the ratio of polymer A-1 (low molecular weight) and A-2 (high molecular weight)

[0268] [Table 6]

[0269] Example 4 Example 5 Example 6 Black pigment dispersion (SKC Ht&m) 37 37 37 Miraemer M600 (Miraemer Specialty Chemicals Co., Ltd.) 3.5 3.5 3.5 Oxe-02 (BASF) 0.5 0.5 0.5 Polymer A-1 (low molecular weight cardo-based adhesive) 7 5 3 Polymer A-2 (polymer cardo-based adhesive) 3 5 7 Propylene glycol methyl ether acetate 49 49 49

[0270] [Table 7]

[0271]

[0272] Referring to Table 6 and Table 7 above, developability, residue, and taper angle of patterns according to the mixing ratio of the polymer A-1 and the polymer A-2 were compared and confirmed (Example 4 to Example 6).

[0273] In Examples 4 to 6, low molecular weight (molecular weight: 4500) cardo-based binder A-1 and high molecular weight (molecular weight: 8500) cardo-based binder A-2 were used at ratios of 7:3, 5:5, and 3:7, respectively.

[0274] In Examples 4 to 6, it can be confirmed that the pattern size is the largest in Example 4, which uses the most polymer A-1, which is 17.5 μm, and the cone angle is 33 degrees, with no residue and excellent display (resolution: 5 μm, breaking point: 17 seconds).

[0275] In the case of Example 5 using polymer A-1 and polymer A-2 in the same proportion, the size of the pattern was 16.9 μm, and there was no residue in the center of the pattern, while there was residue at the edge of the pattern (compared with Example 4, the breaking point increased to 21 seconds as the amount of polymer A-2 increased).

[0276] In the case of Example 6, it was confirmed that the pattern size was the smallest at 14.7 μm, and there were many residues in the center and edge of the pattern. This is because the amount of polymer A-2 used was larger than that of polymer A-1, and the breaking point was the slowest at more than 40 seconds, resulting in a large amount of residues and a small hole pattern size.

[0277] Therefore, it can be confirmed that the compound of the present invention is a photosensitive resin composition containing more polymer A-1 as a low molecular weight cardo-based binder than polymer A-2 as a high molecular weight cardo-based binder, and has very excellent pattern developability and adhesion.

Claims

1. A photosensitive resin composition, comprising: A cardo-based binder (A) containing a repeating unit represented by the following Chemical Formula 1 and having two or more different molecular weights, comprising a low molecular weight cardo-based binder having a weight average molecular weight of 3000 to 5000 and a high molecular weight cardo-based binder having a weight average molecular weight of 7000 to 9000, in, Based on the sum of the masses of the low molecular weight carbo-based binder and the high molecular weight carbo-based binder, the content of the low molecular weight carbo-based binder is 50 wt % to 90 wt %; reactive unsaturated compound (B); 1 wt % to 40 wt % of pigment (C); initiator (D) and solvent (E): [Chemical formula 1] 1) "*" indicates the part of the bond connected by the repeating unit, 2) R 1 and R 2 Each independently selected from deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 6 ~C 30 The group consisting of aryloxy groups, 3) R 3 To R 6 Each independently selected from deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 6 ~C 30 The group consisting of aryloxy groups, 4) R 7 Selected from hydrogen; deuterium; C 1 -C 60 Alkyl; C 2 ~C 60 The group consisting of alkenyl, acrylic acid, and methacrylic acid, 5) m and n are each independently an integer from 0 to 4. When m is 2 or greater, adjacent R 1 Combined with each other to form a monocyclic or polycyclic ring, when n is 2 or more, R 2 Combined with each other to form a single ring or multiple rings, 6)X 2 is an acid anhydride residue or an acid dianhydride residue, 7)X 1 It is represented by the following chemical formula 2, 8) Y 1 and Y 2 Each independently selected from the group consisting of hydrogen; deuterium; and the following chemical formula 3, [Chemical formula 2] 9) R 8 and R 9 Each independently selected from deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 2 ~C 60 Alkenyl; C 2 ~C 60 Alkynyl; C 1 -C 60 Alkoxy; C 2 ~C 60 The group consisting of alkenyl groups, 10) o and p are each independently an integer from 0 to 4. When o is 2 or greater, the adjacent R 8 When p is 2 or more, the adjacent R 9 Combined with each other to form a single ring or multiple rings, [Chemical formula 3] 11) L 1 Each independently selected from a single bond; C 1 ~C 60 Alkylene; C 6 ~C 60 The group consisting of arylene groups, 12) R 10 Each independently selected from hydrogen; deuterium; halogen; C 6 ~C 60 Aryl; C containing at least one heteroatom selected from O, N, S, Si and P 2 ~C 60 Heterocyclic group; C 3 ~C 60 Aliphatic ring and C 6 ~C 60 Aromatic ring fused ring group; C 1 -C 60 Alkyl; C 1 -C 60 The group consisting of alkoxy groups.

2. The photosensitive resin composition according to claim 1, It is characterized in that In the two or more cardo-based adhesives, Y 1 and Y 2 At least one of them is the chemical formula 3.

3. The photosensitive resin composition according to claim 1, It is characterized in that The photosensitive resin composition further includes at least one of an acrylic binder and a polyimide binder.

4. The photosensitive resin composition according to claim 3, It is characterized in that The weight average molecular weight of the acrylic adhesive is 9,000 to 13,000, and the weight average molecular weight of the polyimide adhesive is 1,500 to 3,900.

5. The photosensitive resin composition according to claim 1, It is characterized in that The photosensitive resin composition comprises 1 wt % to 30 wt % of the two or more cardo-based binders (A), 1 wt % to 40 wt % of the reactive unsaturated compound (B), 1 wt % to 30 wt % of the pigment (C), and 0.01 wt % to 10 wt % of the initiator (D).

6. The photosensitive resin composition according to claim 1, It is characterized in that The initiator includes at least one of a photopolymerization initiator and a radical polymerization initiator. 7 . A display device comprising a pattern layer, wherein the pattern layer comprises a polymerized reactant of the photosensitive resin composition of claim 1 .

8. The display device according to claim 7, It is characterized in that The display device includes a plurality of sub-pixels, and the pattern layer is a pixel defining layer that divides the plurality of sub-pixels.

9. The display device according to claim 7, It is characterized in that The pattern layer includes an inclined portion having an inclined angle of 20° to 40°.

Images