Photosensitive resin composition, cured film, and display device including the same

Abstract

A photosensitive resin composition is provided in which flexibility and sensitivity performance are simultaneously improved. In General Formulas 1 and 2 according to the present invention, at least one of R1 and R2 includes a molecular structure represented by the general formula 3.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, and more specifically, to a photosensitive resin composition, a cured film, and a display device including the same.

Background Art

[0002] The photosensitive resin composition is a typical functional polymer material that has been put into practical use in the production of various precision electronic industrial products, and is currently importantly used in the production of advanced technology industries, especially semiconductors and displays. Generally, the photosensitive resin composition means a composition in which a chemical change in the molecular structure occurs within a short time by light irradiation, and physical properties such as solubility in a specific solvent, coloring, and curing change.

[0003] When using the photosensitive resin composition, fine precision processing is possible, energy and raw materials can be greatly reduced compared to the thermal reaction process, work can be carried out quickly and accurately in a small installation space, and it is widely used in various precision electronic industrial fields such as the advanced printing field, semiconductor production, display production, and photocurable surface coating materials. Such photosensitive resin compositions can be broadly classified into negative and positive types. The negative-type photosensitive resin composition is a type in which the irradiated part becomes insoluble in the developer, and the positive-type photosensitive resin composition is a type in which the irradiated part becomes soluble in the developer. Recently, as electronic devices become highly integrated and miniaturized, positive-type photosensitive resin compositions that can minimize the defect rate and improve the processing efficiency and resolution are mainly used.

[0004] On the other hand, an organic light emitting display (hereinafter referred to as "OLED") has attracted attention in the display industry due to its excellent resolution. When the OLED element is applied to a flexible display, research on elements with excellent flexibility and no cracks has been continuously carried out.

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a photosensitive resin composition excellent in flexibility, chemical resistance, sensitivity performance, and element reliability. Another object of the present invention is to provide a cured film obtained by curing the photosensitive resin composition. Still another object of the present invention is to provide a display device including the cured film.

[0006] The objects of the present invention are not limited to the objects mentioned above, and other objects and advantages of the present invention not mentioned will be understood from the following description and will be more clearly understood from the examples of the present invention. Also, it will be easily understood that the objects and advantages of the present invention can be realized by the means shown in the claims and combinations thereof.

Means for Solving the Problems

[0007] According to a first aspect of the present invention for achieving the above object, an alkali-soluble resin containing a repeating unit represented by the following general formula 1 or 2; a photosensitizer; and a solvent are included. In the following general formulas 1 and 2, at least one of R1 and R2 includes a molecular structure represented by the following general formula 3, and a photosensitive resin composition is provided. [General formula 1] JPEG2025523111000002.jpg36170 [General formula 2] JPEG2025523111000003.jpg35170 [General formula 3] (C1)o-(B)p-(A)-(B)q-(C2)r

[0008] In General Formulas 1 and 2, R1 is a divalent to octavalent organic group having 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having 2 or more carbon atoms, R3 and R4 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, a and b are each independently 0 to 4, c and d are each independently 0 to 2, a + b is 1 or more, m and n each represent 0 to 100 mol% of General Formulas 1 and 2, m + n = 100 mol%, in General Formula 3, A is an aromatic organic group containing at least one of a fluorine atom, an oxygen atom, a sulfur atom, and a hydroxyl group, B is an amide group (CONH), C1 and C2 are each independently a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 5 to 12 carbon atoms; C1 and C2 have the same or different molecular structures from each other, when C1 and C2 have the same molecular structure, C1 and C2 contain a heteroatom, o is an integer from 0 to 2, p is 0 or 1, q is 0 or 1, r is an integer from 0 to 2, p + q is an integer of 1 or more, and o + r is an integer of 1 or more.

[0009] According to a second aspect of the present invention, in the first aspect, in General Formula 3, A may be an aromatic organic group containing the fluorine atom and the hydroxyl group.

[0010] According to a third aspect of the present invention, in the first or second aspect, in the following General Formulas 1 and 2, R2 can contain the molecular structure represented by General Formula 3.

[0011] According to a fourth aspect of the present invention, in any one of the first to third aspects, in General Formula 3, A can contain the molecular structure represented by the following General Formula 4. [General Formula 4] JPEG2025523111000004.jpg56170

[0012] In the general formula 4, R5 is any one selected from the group consisting of an oxygen atom, C(CF3)2, C(CH3)2, and SO2, and each R6 is independently any one selected from the group consisting of a hydrogen atom, a thiol group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0013] According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the molecular structure represented by the general formula 3 can include any one of the molecular structures represented by the following chemical formulas 1 to 4.

[0014]

Chemical formula

[0015]

Chemical formula

[0016]

Chemical formula

[0017]

Chemical formula

[0018] According to the sixth aspect of the present invention, in any one of the first to fifth aspects, in the general formula 3, the heteroaryl group can contain a nitrogen atom or a sulfur atom. According to the seventh aspect of the present invention, in any one of the first to sixth aspects, in the general formula 2, n may be more than 50 mol%.

[0019] According to the eighth aspect of the present invention, in any one of the first to seventh aspects, based on the total monomers of the alkali-soluble resin, the molecular structure represented by the general formula 3 may be contained in an amount of 5 to 100 mol%.

[0020] According to the ninth aspect of the present invention, in any one of the first to eighth aspects, based on the diamine monomer of the alkali-soluble resin, the molecular structure represented by the general formula 3 may be contained in an amount of 30 to 80 mol%.

[0021] According to the tenth aspect of the present invention, in any one of the first to ninth aspects, the photosensitizer contains an esterified quinonediazide compound, and the esterified quinonediazide compound can contain a phenol structure as a ballast.

[0022] According to the eleventh aspect of the present invention, in any one of the first to tenth aspects, a photosensitive resin composition further containing an additive, wherein the additive is any one selected from the group consisting of a crosslinking agent, a thermal acid generator, a UV absorber, and a mixture thereof can be provided.

[0023] According to the twelfth aspect of the present invention, in any one of the first to eleventh aspects, the substituted aryl group having 6 to 12 carbon atoms includes a structure in which at least one hydrogen atom bonded to the aryl group having 6 to 12 carbon atoms is replaced with an alkyl group, a halogen atom, or an alkoxy group, and the substituted heteroaryl group having 5 to 12 carbon atoms can include a structure in which at least one hydrogen atom bonded to the heteroaryl group having 5 to 12 carbon atoms is replaced with an alkyl group, a halogen atom, or an alkoxy group.

[0024] According to the thirteenth aspect of the present invention for achieving the above object, a cured film obtained by curing the photosensitive resin composition according to any one of the first to twelfth aspects can be provided. According to the fourteenth aspect of the present invention for achieving the above object, a display device including the cured film according to the thirteenth aspect can be provided.

Advantages of the Invention

[0025] According to one embodiment of the present invention, a photosensitive resin composition can be provided which forms intermolecular hydrogen bonds, increases the free volume corresponding to the free space between atoms to improve the flexibility of the device, and is excellent in chemical resistance, sensitivity performance, adhesion, and device reliability. Along with the above-described effects, the specific effects of the present invention will be described together while explaining the specific content for carrying out the following invention.

Brief Description of the Drawings

[0026]

Figure 1

Embodiments for Carrying Out the Invention

[0027] Hereinafter, each configuration of the present invention will be described in more detail so that those having ordinary knowledge in the technical field to which the present invention pertains can easily implement it. However, this is merely an example, and the scope of the rights of the present invention is not limited by the following content.

[0028] In this specification, the meaning of "substituted" is defined as that at least any one hydrogen atom is substituted with any one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an alkylthiol group, an ether group, an acetal group, an alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, derivatives thereof, and combinations thereof.

[0029] One embodiment of the present invention provides a photosensitive resin composition including an alkali-soluble resin containing a repeating unit represented by the following general formula 1 or 2; a photosensitizer; and a solvent, wherein at least any one of R1 and R2 in the following general formula 1 and 2 includes a molecular structure represented by the following general formula 3. [General Formula 1] JPEG2025523111000009.jpg36170 [General Formula 2] JPEG2025523111000010.jpg35170 [General formula 3] (C1)o-(B)p-(A)-(B)q-(C2)r

[0030] In General Formulas 1 and 2, R1 is a divalent to octavalent organic group having 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having 2 or more carbon atoms, R3 and R4 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, a and b are each independently 0 to 4, c and d are each independently 0 to 2, a + b is 1 or more, m and n each represent 0 to 100 mol% of General Formulas 1 and 2, m + n = 100 mol%, in General Formula 3, A is an aromatic organic group containing at least one or more of a fluorine atom, an oxygen atom, a sulfur atom, and a hydroxyl group, B is an amide group (CONH), C1 and C2 are each independently a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 5 to 12 carbon atoms; C1 and C2 have the same or different molecular structures from each other. When C1 and C2 have the same molecular structure, C1 and C2 contain a heteroatom, o is an integer from 0 to 2, p is 0 or 1, q is 0 or 1, r is an integer from 0 to 2, p + q is an integer of 1 or more, and o + r is an integer of 1 or more. According to one embodiment of the present invention, since A is an aromatic organic group containing at least one or more of a fluorine atom, an oxygen atom, a sulfur atom, and a hydroxyl group, chemical resistance and sensitivity performance can be further improved. In particular, the hydroxyl group (-OH) can adjust the sensitivity performance. Since B is an amide group (CONH), the flexibility can be significantly improved compared to an amine group (-NH2). Since C1 and C2 have the same or different molecular structures from each other, the problem of sensitivity performance degradation caused by existing diamine monomers can be solved, and the sensitivity performance and flexibility can be improved simultaneously. That is, according to one embodiment of the present invention, it is possible to provide a photosensitive resin composition that forms intermolecular hydrogen bonds, increases the free volume corresponding to the free space between atoms to improve the flexibility of the element, and is excellent in chemical resistance, sensitivity performance, adhesion, and element reliability.

[0031] Hereinafter, the configuration of the present invention will be described in more detail.

[0032] 1. Photosensitive resin composition The photosensitive resin composition according to the present invention contains an alkali-soluble resin including a repeating unit represented by the following general formula 1 or 2. [General formula 1] JPEG2025523111000011.jpg36170 [General formula 2] JPEG2025523111000012.jpg35170

[0033] In the general formulas 1 and 2, R1 is a divalent to octavalent organic group having 2 or more carbon atoms, R2 is a divalent to hexavalent organic group having 2 or more carbon atoms, R3 and R4 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, a and b are each independently 0 to 4, c and d are each independently 0 to 2, a + b is 1 or more, m and n each represent 0 to 100 mol% of the general formulas 1 and 2, and m + n = 100 mol%.

[0034] Specifically, the alkali-soluble resin may contain a polyamic acid (ester) repeating unit represented by the general formula 1 or a polyimide repeating unit represented by the general formula 2. As the polyimide repeating unit increases, flexibility, sensitivity performance, residue performance, chemical resistance, and device reliability can be further improved.

[0035] The imidization index of the alkali-soluble resin may exceed 50% and be 100% or less, specifically may be 60% to 100%, and more specifically may be 70% to 100%. The imidization index of the alkali-soluble resin can be adjusted by varying the synthesis temperature and synthesis time. For example, the synthesis temperature and synthesis time of the polyimide resin may be 100 to 180°C for 2 to 6 hours. When the imidization index of the polyimide resin satisfies the numerical range, flexibility, sensitivity performance, residue performance, chemical resistance, and device reliability can be further improved.

[0036] In the general formulas 1 and 2, at least one of R1 and R2 includes a molecular structure represented by the following general formula 3. [General formula 3] (C1)o-(B)p-(A)-(B)q-(C2)r

[0037] In the general formula 3, A may be an aromatic organic group containing at least one or more of a fluorine atom, an oxygen atom, a sulfur atom, and a hydroxyl group. Specifically, it may be an aromatic organic group containing the fluorine atom and the hydroxyl group. By A in the general formula 3 being an aromatic organic group containing all of the fluorine atom and the hydroxyl group, the chemical resistance performance and the sensitivity performance can be improved simultaneously. In particular, the fluorine atom can contribute to the chemical resistance performance, and the hydroxyl group can contribute to the sensitivity performance.

[0038] In the general formula 3, by B being an amide group (CONH), the flexibility of the element can be significantly improved compared to an amine group (-NH2).

[0039] In the general formula 3, C1 and C2 are each independently a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 5 to 12 carbon atoms. For example, the heteroaryl group may be a 5-membered or 6-membered ring, and specifically, it may be pyridine. Also, C1 and C2 may have the same or different molecular structures from each other, and specifically, they may be different from each other. When C1 and C2 have the same molecular structure, C1 and C2 contain a heteroatom and, for example, can contain a heteroaryl group. When C1 and C2 have different molecular structures from each other, flexibility and sensitivity performance can be improved simultaneously. For example, in C1 and C2, the "substituted aryl group having 6 to 12 carbon atoms" can include a structure in which at least one hydrogen atom bonded to the aryl group having 6 to 12 carbon atoms is replaced by an alkyl group, a halogen atom, or an alkoxy group. As another example, the "substituted heteroaryl group having 5 to 12 carbon atoms" can include a structure in which at least one hydrogen atom bonded to the heteroaryl group having 5 to 12 carbon atoms is replaced by an alkyl group, a halogen atom, or an alkoxy group. For example, the alkyl group may be an alkyl group having 1 to 5 carbon atoms, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and the alkoxy group may be an alkoxy group having 1 to 5 carbon atoms. When such substituents are further included, cross-linking between resin molecules is possible and further improvement in flexibility can be expected.

[0040] Specifically, in the following general formulas 1 and 2, R2 can include the molecular structure represented by the general formula 3. R2 may be a part of the molecular structure derived from the diamine monomer used to synthesize the polyimide-based resin.

[0041] In the general formula 3, A can include the molecular structure represented by the following general formula 4. [General formula 4] JPEG2025523111000013.jpg56170

[0042] In the general formula 4, R5 may be any one selected from the group consisting of an oxygen atom, C(CF3)2, C(CH3)2, and SO2, and specifically, it may be C(CF3)2. When R5 is C(CF3)2, the chemical resistance performance can be further improved by including a fluorine atom.

[0043] In the general formula 4, each R6 may independently be any one selected from the group consisting of a hydrogen atom, a thiol group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0044] For example, the molecular structure represented by the general formula 3 can include any one of the molecular structures represented by the following chemical formulas 1 to 4. As another example, the molecular structure represented by the general formula 3 may include, as a parent, the molecular structures represented by the following chemical formulas 1 to 4, and a molecular structure in which at least one or more hydrogen atoms bonded to an aryl group or a heteroaryl group are replaced by any one of an alkyl group, a halogen atom, and an alkoxy group.

[0045]

Chemical formula

[0046]

Chemical formula

[0047]

Chemical formula

[0048]

Chemical formula

[0049] According to one embodiment of the present invention, by including any one of the molecular structures represented by Chemical Formulas 1 to 4 as a parent structure, intermolecular hydrogen bonding occurs, and a diamine monomer capable of increasing the free volume corresponding to the free space between atoms can be used to improve the flexibility of the device, and a photosensitive resin composition excellent in chemical resistance, sensitivity performance, adhesive strength, and device reliability can be provided.

[0050] For example, in General Formula 3, the heteroaryl group may contain a nitrogen atom or a sulfur atom, and specifically, it may contain a nitrogen atom. In General Formula 3, the heteroaryl group contains a nitrogen atom with a high electronegativity in the ring, whereby the sensitivity and high transparency performance can be further improved.

[0051] According to another embodiment of the present invention, in General Formula 2, n may exceed 50 mol%. When n exceeds 50 mol% in terms of the mol% of the polyimide repeating unit in General Formula 2, the flexibility, sensitivity performance, chemical resistance performance, and device reliability of the device can be significantly improved.

[0052] According to still another embodiment of the present invention, based on the total monomers of the alkali-soluble resin, the molecular structure represented by General Formula 3 may be contained in an amount of 5 to 100 mol%, and specifically, it may be contained in an amount of 5 to 90 mol%. The total monomers of the alkali-soluble resin can mean diamine monomers and acid anhydride monomers. When the content of the molecular structure represented by General Formula 3 satisfies the above numerical range, the flexibility, chemical resistance, and sensitivity performance of the device can be further improved.

[0053] According to still another embodiment of the present invention, based on the diamine monomer of the alkali-soluble resin, the molecular structure represented by General Formula 3 may be contained in an amount of 30 to 100 mol%, and specifically, it may be contained in an amount of 30 to 80 mol%. When the content of the molecular structure represented by General Formula 3 satisfies the above numerical range based on the diamine monomer, the flexibility, chemical resistance, and sensitivity performance of the device can be further improved. The photosensitive resin composition according to the present invention contains a photosensitizer that imparts alkali developability to the exposed area after exposure.

[0054] The photosensitizer contains an esterified quinonediazide compound, and the esterified quinonediazide compound can contain a phenol structure as a parent body (ballast). The parent body may be any one selected from the structures represented by the following chemical formulas a to h, for example. At least one hydroxyl group in the parent body may undergo an esterification reaction by reacting with an acid compound containing a carboxyl group.

[0055]

Chemical formula

[0056]

Chemical formula

[0057]

Chemical formula

[0058]

Chemical formula

[0059]

Chemical formula

[0060]

Chemical formula

[0061]

Chemical formula

[0062]

Chemical formula

[0063] In the chemical formulas a to h above, R7, R8 and R 11 ~R 55 are each independently a hydrogen atom, a halogen, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, X3 and X4 are each independently a hydrogen atom, a halogen, or an alkyl group having 1 to 4 carbon atoms, and R9 and R 10 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0064] The content of the photosensitizer may be 5 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin, and specifically may be 10 to 30 parts by weight. When the content of the photosensitizer satisfies the numerical range, the pattern shape can be appropriately maintained, and at the same time, appropriate photosensitivity and heat resistance can be ensured.

[0065] The photosensitive resin composition according to the present invention contains a solvent. The solvent may be, for example, any one selected from the group consisting of gamma-Butyrolactone (GBL), N-methylpyrrolidone (NMP), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl 3-methoxypropionate (MMP), propylene glycol monomethyl ether (PGME), diethylene glycol ethyl methyl ether (MEDG), diethylene glycol butyl methyl ether (MBDG), diethylene glycol dimethyl ether (DMDG), diethylene glycol diethyl ether (DEDG), and mixtures thereof.

[0066] The photosensitive resin composition according to another embodiment of the present invention may further contain an additive. The additive may be any one selected from the group consisting of a crosslinking agent, a thermal acid generator, a UV absorber, and mixtures thereof. The crosslinking agent can effectively control the shape of the pattern by promoting a crosslinking reaction with the alkali-soluble resin by heat in the thermosetting step. The crosslinking agent may be, for example, a crosslinking agent having an alkoxymethyl group or a crosslinking agent having an epoxy group. The thermal acid generator serves as a catalyst for the crosslinking reaction and can effectively control the flow-down of the pattern. The thermal acid generator and the UV absorber are not particularly limited and may be commercial products in the art.

[0067] 2. Cured Film and Display Device Other embodiments of the present invention can provide a cured film obtained by curing the photosensitive resin composition and a display device including the same. Here, when the photosensitive resin composition is cured, the solvent contained in the photosensitive resin composition can be volatilized and removed. Therefore, the "cured film obtained by curing the photosensitive resin composition" can mean a state of a cured film from which the solvent has been removed. FIG. 1 is a vertical cross-sectional view of a display device according to an embodiment of the present invention.

[0068] Referring to FIG. 1, the cured film according to the present invention may be an interlayer insulating layer. The interlayer insulating layer may be disposed on an ILD (Interlayer Dielectric) layer or may be disposed between a first electrode and a second electrode facing each other. As another example, the interlayer insulating layer can also cover a part of the electrode. In addition, the photosensitive resin composition according to the present invention can be widely applied to semiconductor elements, elements for flexible displays, OLED (organic light emitting diode) elements, and the like.

[0069] Hereinafter, the embodiments of the present invention will be described in detail so that those having ordinary knowledge in the technical field to which the present invention pertains can easily implement them. However, this is merely an example, and the scope of the rights of the present invention is not limited by the following content.

[0070] [Synthesis Example: Synthesis of Alkali-Soluble Resin] <Synthesis Example 1: Synthesis of Polyamic Acid> Under a stream of dry nitrogen, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane; bis-APAF; 70 mol), which is a diamine, and a compound represented by the following Chemical Formula 1-1 (30 mol) were dissolved in γ-butyrolactone at 60°C. 4,4’-Oxydiphthalic anhydride (4,4’-oxydiphthalic anhydride; ODPA; 68 mol) was added to the dissolved mixture and dissolved, and then stirred at 70°C for 4 hours. Thereafter, phthalic anhydride (phthalic anhydride; PA; 64 mol) was added to the stirred resultant, and then stirred at 70°C for 2 hours to terminate the reaction, thereby synthesizing a polyamic acid.

[0071] [Chemical Formula]

[0072] <Comparative Synthesis Example 1: Synthesis of Polyimide> A polyamic acid was synthesized in the same manner as in Synthesis Example 1, and 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane; bis-APAF; 100 mol) was used except for the compound represented by Chemical Formula 1-1. Thereafter, it was additionally stirred at 180°C for 4 hours to synthesize a polyimide.

[0073] <Synthesis Examples 2 to 11: Synthesis of Polyimide> Polyamic acids were respectively synthesized in the same manner as in Synthesis Example 1, and the content of the diamine was adjusted according to Table 1 below. Thereafter, it was additionally stirred at 180°C for 4 hours to synthesize a polyimide.

[0074] <Synthesis Examples 12 to 21: Synthesis of Polyimide> Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, and a compound represented by the following Chemical Formula 2-1 was used instead of the compound represented by the above Chemical Formula 1-1, and the diamine content was adjusted according to Table 1 below.

[0075]

Chem.

[0076] <Synthesis Examples 22 - 31: Synthesis of Polyimide> Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, and a compound represented by the following Chemical Formula 3-1 was used instead of the compound represented by the above Chemical Formula 1-1, and the diamine content was adjusted according to Table 1 below.

[0077]

Chem.

[0078] <Synthesis Examples 32 - 41: Synthesis of Polyimide> Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, and a compound represented by the following Chemical Formula 4-1 was used instead of the compound represented by the above Chemical Formula 1-1, and the diamine content was adjusted according to Table 1 below.

[0079]

Chem.

[0080]

Table 1

[0081] <Synthesis Examples 42 - 49: Synthesis of Polyimide> Synthesis Examples 42 and 43 were synthesized in the same manner as Synthesis Example 6, Synthesis Examples 44 and 45 were synthesized in the same manner as Synthesis Example 16, Synthesis Examples 46 and 47 were synthesized in the same manner as Synthesis Example 26, and Synthesis Examples 48 and 49 were synthesized in the same manner as Synthesis Example 36.

[0082]

Table 2

[0083] <Comparative Synthesis Examples 2 - 15: Synthesis of Polyimide> Polyimides were synthesized respectively in the same manner as Synthesis Examples 2 - 11, and instead of the compound represented by the chemical formula 1 - 1, any one of diamine compounds with a symmetric structure such as the compound represented by the following chemical formula 5 - 1, ODA, APB, BAPP, or 6FODA was used, and the diamine content was adjusted according to Table 3 below.

[0084]

Chemical formula

[0085]

Table 3

[0086] [Production Example: Production of Photosensitive Resin Composition] <Examples 1 - 41: When PAC is TPPA> Photosensitive resin compositions each containing 100 parts by weight of the alkali - soluble resin according to each of Synthesis Examples 1 - 41, 25 parts by weight of a compound containing a 5 - naphthoquinonediazidosulfonyl group (TPPA), and 20 parts by weight of a cross - linking agent containing an alkoxymethyl group (HMOM - TPHAP) were produced respectively.

[0087] <Examples 42, 44, 46, and 48: When PAC is THPE> 100 parts by weight of the alkali-soluble resin according to each of the above Synthesis Examples 42, 44, 46, and 48; 25 parts by weight of a compound containing a 5-naphthoquinonediazidosulfonyl group (THPE), and 20 parts by weight of a crosslinking agent containing an alkoxymethyl group (HMOM-TPHAP) were each used to produce a photosensitive resin composition.

[0088] <Examples 43, 45, 47, and 49: When the crosslinking agent contains an epoxy structure> 100 parts by weight of the alkali-soluble resin according to each of the above Synthesis Examples 43, 45, 47, and 49; 25 parts by weight of a compound containing a 5-naphthoquinonediazidosulfonyl group (THPE), and 20 parts by weight of a crosslinking agent containing an epoxy group (Epiclon HP-820) were each used to produce a photosensitive resin composition.

[0089] <Comparative Examples 1 to 15: Corresponding to Comparative Synthesis Examples 1 to 15> 100 parts by weight of the alkali-soluble resin according to each of the above Comparative Synthesis Examples 1 to 15; 25 parts by weight of a compound containing a 5-naphthoquinonediazidosulfonyl group (TPPA), and 20 parts by weight of a crosslinking agent containing an alkoxymethyl group (HMOM-TPHAP) were each used to produce a photosensitive resin composition.

[0090] [Experimental Example: Physical Property Evaluation and Measurement of Imidization Index] 1) Flexibility and Crack Evaluation The photosensitive resin composition according to the above Production Example was coated on a 100-μm polyimide film to a thickness of 3 μm, and then infolding was performed 200,000 times with a curvature radius of 1R size. When cracks of 3 mm or more were observed before 100,000 repetitions, it was marked as X; when cracks were observed at 100,000 repetitions, it was marked as Δ; when cracks were observed at 150,000 repetitions, it was marked as O; when no cracks were observed until 200,000 repetitions, it was marked as ◎, and these were shown in Tables 4 and 5 below. For this purpose, visual inspection and observation were performed at a magnification of 100 times with a microscope.

[0091] 2) Sensitivity After applying the photosensitive resin composition according to the production example on a glass substrate using a slit coater, it was advanced at a pressure of 40 Pa by a vacuum dry process, and then pre-baked on a hot plate at 120 °C for 2 minutes to form a pre-cured film with a thickness of 3.0 μm. A predetermined pattern mask was used for the pre-cured film, and ultraviolet rays with an intensity of 20 mW / cm 2 (Dose amount based on the critical dimension of a 2.5-μm contact hole) were irradiated. After that, it was developed at 23 °C for 1 minute with an aqueous solution of tetramethylammonium hydroxide (N(CH3)4 + OH - ; 2.38 wt%) and washed with ultrapure water for 1 minute. Then, the washed product was cured in an oven at 250 °C for 60 minutes to form a cured film with a thickness of 2.0 μm. For the cured film, when the sensitivity is less than 100 mJ / cm 2 , it is marked as "O", when it is 100 - 150 mJ / cm 2 , it is marked as "Δ", and when it is 150 mJ / cm or more 2 , it is marked as "X", and is shown in Tables 4 and 5 below.

[0092] 3) Scum (residue) The inside of the cured film formed during the sensitivity evaluation was observed with an SEM (scanning electron microscope). When there is residue in the line & space and contact hole, it is marked as "X", and when there is no residue, it is marked as "O", and is shown in Tables 4 and 5 below.

[0093] 4) Chemical resistance The cured film was immersed in the evaluation solvent at 25°C for 120 seconds, and the thickness change rate of the cured film before and after immersion was measured. The evaluation solvent is a mixture of propylene glycol methyl ether and propylene glycol methyl ether acetate mixed at a molar ratio of 7:3. At this time, when the thickness change rate of the cured film is 200 Å or less, it is marked as "◎"; when it exceeds 200 and is 300 Å or less, it is marked as "O"; when it exceeds 300 and is 500 Å or less, it is marked as "Δ"; when it exceeds 500 Å, it is marked as "X", and is shown in Tables 4 and 5 below.

[0094] 5) Adhesion In the cured film formed during the sensitivity evaluation, with a line width of 10 μm and a slit width of 1:1 as the reference, the adhesion according to the baking temperature was compared. At this time, when the adhesion is ensured at a pre-baking temperature of 90°C to 120°C, it is marked as "O"; when the adhesion is ensured at a pre-baking temperature of 125 - 130°C, it is marked as "△"; when the adhesion is ensured or not ensured at a pre-baking temperature of 130°C or higher, it is marked as "X".

[0095] 6) OLED Reliability After forming a pattern film on an ITO (indium tin oxide) substrate (anode electrode) in the same way as the sensitivity analysis method, an organic light-emitting layer was deposited. After forming an aluminum thin film as the cathode electrode on the top, the encapsulation process was carried out to manufacture an OLED element. The time (T97) when the luminance of the OLED element decreased by 3% in the On state was evaluated based on 85°C and 85% R.H. When it is ensured for 1000 hours or more, it is marked as "◎"; when it is ensured for 500 hours or more and less than 1000 hours, it is marked as "O"; when it is less than 200 - 500 hours, it is marked as "Δ"; when it is less than 200 hours, it is marked as "X", and is shown in Tables 4 and 5 below.

[0096] 7) Imidization Index (%) The photosensitive resin composition obtained in the above production example was applied onto a substrate. Thereafter, on a glass substrate, after thin film coating using a slit coater, it was dried on a hot plate at 120 °C for 2 minutes and cured at 250 °C and 350 °C for 1 hour each to form a film with a thickness of 3.0 μm, and then IR was measured for the film. Based on the C=C stretching peak intensity of benzene which does not change during the progress of the imidization reaction, the imidization index was confirmed by the C-N-C peak intensity due to the imide reaction (Peak of C-N-C / Peak of C=C@aromatic). Assuming that the imide ratio at 350 °C cure was 100%, the imide ratio at 250 °C cure was calculated. As for the evaluation results, when the imide ratio was less than 51%, it was indicated as <, and when it was 51% or more, it was indicated as ≧, as shown in Tables 4 and 5 below.

[0097]

Table 4

[0098]

Table 5

[0099] Referring to Tables 4 and 5 above, it can be confirmed that Examples 2 to 49 have the same level or improved sensitivity performance, flexibility, or device reliability compared to the Comparative Examples. Also, by comparing Example 1 with the remaining Examples, it can be confirmed that when the imidization index exceeds 50%, the flexibility, sensitivity, chemical resistance, and device reliability performance are overall improved. When comprehensively considering the above experimental results, it can be inferred that various examples of the present invention can form intermolecular hydrogen bonds and increase the free volume corresponding to the free space between atoms by including the molecular structure represented by the general formula 3 as a matrix. Thereby, it is possible to provide a photosensitive resin composition that improves the flexibility of the device and is excellent in chemical resistance, sensitivity performance, adhesion, and device reliability.

[0100] As described above in detail for the preferred embodiments of the present invention, the scope of the rights of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also belong to the scope of the rights of the present invention.

Claims

1. An alkali-soluble resin containing a repeating unit represented by the following general formula 1 or 2; a photosensitizer; and a solvent, In the following general formulas 1 and 2, R １ and R ２ At least one of the following: containing a molecular structure represented by the following general formula 3, a photosensitive resin composition: [General formula 1] [General formula 2] [General formula 3] (C1)o-(B)p-(A)-(B)q-(C2)r In the above general formulas 1 and 2, R １ is a divalent to octavalent organic group having 2 or more carbon atoms, R ２ is a divalent to hexavalent organic group having 2 or more carbon atoms, R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, a and b are each independently 0 to 4, c and d are each independently 0 to 2, a + b is 1 or more, m and n each represent 0 to 100 mol% of General Formulas 1 and 2, and m + n = 100 mol%, In the above general formula 3, A is an aromatic organic group containing at least one of a fluorine atom, an oxygen atom, a sulfur atom, and a hydroxyl group, B is an amide group (CONH), and C1 and C2 are each independently a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 5 to 12 carbon atoms; C1 and C2 have the same or different molecular structures from each other. When C1 and C2 have the same molecular structure, C1 and C2 contain a heteroatom, o is an integer from 0 to 2, p is 0 or 1, q is 0 or 1, r is an integer from 0 to 2, p + q is an integer of 1 or more, and o + r is an integer of 1 or more.

2. In the above general formula 3, A is an aromatic organic group containing the above fluorine atom and hydroxyl group, The photosensitive resin composition according to Claim 1.

3. In the following general formulas 1 and 2, R ２ is Containing the molecular structure represented by the above general formula 3, The photosensitive resin composition according to Claim 1.

4. In the above general formula 3, A is containing a molecular structure represented by the following general formula 4, The photosensitive resin composition according to Claim 1: [General formula 4] In the above general formula 4, R ５ is any one selected from the group consisting of an oxygen atom, C(CF ３ ), C(CH ２ ), and SO ３ ), ２ and is ２ any one selected from the group consisting of R ６ is each independently any one selected from the group consisting of a hydrogen atom, a thiol group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

5. The molecular structure represented by the above general formula 3 contains any one of the molecular structures represented by the following chemical formulas 1 to 4, The photosensitive resin composition according to Claim 1. 【Chemical 1】 [Chemical 2] 【Chemical Formula 3】 【Chemical Formula 4】

6. In the above general formula 3, The heteroaryl group contains a nitrogen atom or a sulfur atom, The photosensitive resin composition according to Claim 1.

7. In the above general formula 2, n is more than 50 mol%, The photosensitive resin composition according to Claim 1.

8. Based on the total monomers of the alkali-soluble resin, the molecular structure represented by the above general formula 3 is contained in an amount of 5 to 100 mol%, The photosensitive resin composition according to Claim 1.

9. Based on the diamine monomers of the alkali-soluble resin, the molecular structure represented by the above general formula 3 is contained in an amount of 30 to 80 mol%, The photosensitive resin composition according to Claim 1.

10. The photosensitizer contains an esterified quinonediazide compound, The esterified quinonediazide compound contains a phenol structure as a ballast. The photosensitive resin composition according to claim 1.

11. Further comprising an additive, The additive is Any one selected from the group consisting of a crosslinking agent, a thermal acid generator, a UV absorber, and a mixture thereof. The photosensitive resin composition according to claim 1.

12. The substituted aryl group having 6 to 12 carbon atoms contains a structure in which at least one hydrogen atom bonded to the aryl group having 6 to 12 carbon atoms is replaced by an alkyl group, a halogen atom, or an alkoxy group. The substituted heteroaryl group having 5 to 12 carbon atoms contains a structure in which at least one hydrogen atom bonded to the heteroaryl group having 5 to 12 carbon atoms is replaced by an alkyl group, a halogen atom, or an alkoxy group. The photosensitive resin composition according to claim 1.

13. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 12.

14. A display device including the cured film according to claim 13.

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