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

Abstract

The invention provides a photosensitive resin composition capable of improving flexibility and sensitivity at the same time. At least one of R1 and R2 in general formula 1 and general formula 2 according to the present invention comprises a molecular structure represented by general formula 3.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition, a cured film and a display device comprising the same. Background Art

[0002] Photosensitive resin compositions are representative functional polymer materials that are used in the production of various precision electronic industrial products. They are currently widely used in cutting-edge technology industries, especially in the production of semiconductors and displays. Generally speaking, photosensitive resin compositions refer to compositions whose molecular structures undergo chemical changes in a short period of time through light irradiation, resulting in changes in physical properties such as solubility in specific solvents, coloring, and curing.

[0003] The use of photosensitive resin compositions can achieve precision micro-machining, which can greatly save energy and raw materials compared to thermal reaction processes, and can work quickly and accurately in a smaller setup space. Therefore, it is widely used in various precision electronic industry fields such as cutting-edge printing, semiconductor production, display production, and photocurable surface coating materials. These photosensitive resin compositions can be roughly divided into two categories: negative and positive. Negative photosensitive resin compositions refer to the type in which the light-irradiated part is insoluble in the developer, while positive photosensitive resin compositions refer to the type in which the light-irradiated part is soluble in the developer. In recent years, as electronic devices have become highly integrated and finely patterned, positive photosensitive resin compositions that can minimize defect rates and improve processing efficiency and resolution are mainly used.

[0004] On the other hand, organic light emitting displays (OLEDs) have attracted much attention in the display industry due to their excellent resolution. When OLED devices are used in flexible displays, research is ongoing to develop devices that are excellent in flexibility and do not produce cracks. Summary of the invention

[0005] Problem that the invention aims to solve

[0006] The object of the present invention is to provide a photosensitive resin composition having excellent flexibility, chemical resistance, sensitivity and device reliability.

[0007] Another object of the present invention is to provide a cured film formed by curing the photosensitive resin composition.

[0008] Another object of the present invention is to provide a display device including the cured film.

[0009] The purpose of the present invention is not limited to the purpose mentioned above, and other purposes and advantages of the present invention not mentioned can be understood through the following description, and can be more clearly understood through the embodiments of the present invention. In addition, it can be easily understood that the purpose and advantages of the present invention can be achieved by the means and combinations thereof in the claims.

[0010] Means used to solve problems

[0011] In order to achieve the above-mentioned object, according to a first aspect of the present invention, a photosensitive resin composition is provided, which includes: an alkali-soluble resin comprising a repeating unit represented by the following general formula 1 or general formula 2; a photosensitizer; and a solvent, wherein in the following general formula 1 and general formula 2, at least one of R1 and R2 comprises a molecular structure represented by the following general formula 3.

[0012] [General formula 1]

[0013]

[0014] [General formula 2]

[0015]

[0016] [Formula 3]

[0017] (C1)o-(B)p-(A)-(B)q-(C2)r

[0018] In the above general formula 1 and general formula 2, R1 is a divalent to octavalent organic group having two or more carbon atoms, R2 is a divalent to hexavalent organic group having two 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, and a+b is 1 or more, m and n represent 0 mol% to 100 mol% of general formula 1 and general formula 2, respectively, and m+n=100 mol%. In the above general formula 3, A is a fluorine atom, an oxygen atom, a sulfur atom, and an aromatic organic group containing at least one of a hydroxyl group 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; the molecular structures of C1 and C2 may be the same or different, when the molecular structures of C1 and C2 are the same, C1 and C2 contain heteroatoms, 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 greater than or equal to 1, and o+r is an integer greater than or equal to 1.

[0019] According to a second aspect of the present invention, in the above first aspect, in the above general formula 3, A may be an aromatic organic group containing the above fluorine atom and a hydroxyl group.

[0020] According to a third aspect of the present invention, in the first or second aspect, in the following general formula 1 and general formula 2, R2 may include a molecular structure represented by the above general formula 3.

[0021] According to a fourth aspect of the present invention, in any one of the first to third aspects, in the above-mentioned general formula 3, A may include a molecular structure represented by the following general formula 4.

[0022] [Formula 4]

[0023]

[0024] In the above general formula 4, R5 can be one selected from the group consisting of oxygen atoms, C(CF3)2, C(CH3)2 and SO2, and R6 can each independently be one selected from the group consisting of hydrogen atoms, thiol groups, alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, cycloalkenyl groups having 3 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms.

[0025] According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the molecular structure represented by the above general formula 3 may include one of the molecular structures represented by the following chemical formulas 1 to 4.

[0026] [Chemical formula 1]

[0027]

[0028] [Chemical formula 2]

[0029]

[0030] [Chemical formula 3]

[0031]

[0032] [Chemical formula 4]

[0033]

[0034] According to a sixth aspect of the present invention, in any one of the first to fifth aspects, in the general formula 3, the heteroaryl group may contain a nitrogen atom or a sulfur atom.

[0035] According to a seventh aspect of the present invention, in any one of the first to sixth aspects, in the general formula 2, n may be greater than 50 mol%.

[0036] According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the content of the molecular structure represented by the general formula 3 may be 5 mol % to 100 mol % based on the total amount of monomers of the alkali-soluble resin.

[0037] According to a ninth aspect of the present invention, in any one of the first to eighth aspects, the content of the molecular structure represented by the general formula 3 may be 30 mol % to 80 mol % based on the diamine monomer of the alkali-soluble resin.

[0038] According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the photosensitizer comprises an esterified quinonediazide compound, and the esterified quinonediazide compound may comprise a phenol structure as a matrix (ballast).

[0039] According to the eleventh aspect of the present invention, in any one of the first to tenth aspects, a photosensitive resin composition may be provided, which further includes an additive, wherein the additive is one selected from the group consisting of a crosslinking agent, a thermal acid generator, a UV absorber and a mixture thereof.

[0040] According to the twelfth aspect of the present invention, in any one of the first to eleventh aspects, the above-mentioned substituted aromatic group having 6 to 12 carbon atoms may include a structure in which at least one hydrogen atom bonded to the aromatic group having 6 to 12 carbon atoms is substituted by an alkyl group, a halogen atom or an alkoxy group, and the above-mentioned substituted heteroaromatic group having 5 to 12 carbon atoms may include a structure in which at least one hydrogen atom bonded to the heteroaromatic group having 5 to 12 carbon atoms is substituted by an alkyl group, a halogen atom or an alkoxy group.

[0041] According to a thirteenth aspect of the present invention in order to achieve the above object, there can be provided a cured film formed by curing the photosensitive resin composition according to any one of the first to twelfth aspects.

[0042] According to a fourteenth aspect of the present invention to achieve the above object, there may be provided a display device including the cured film according to the thirteenth aspect.

[0043] Effects of the Invention

[0044] According to an embodiment of the present invention, a photosensitive resin composition can be provided which improves device flexibility by forming hydrogen bonds between molecules and increasing free volume corresponding to free space between atoms and has excellent chemical resistance, sensitivity performance, adhesion, and device reliability.

[0045] In addition to the above-described effects, specific effects of the present invention will be described while explaining specific details for implementing the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 is a vertical cross-sectional view of a display device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0047] Hereinafter, each configuration of the present invention will be described in more detail so that those skilled in the art can easily implement it, but this is only an example, and the scope of the present invention is not limited to the following contents.

[0048] In the present specification, the meaning of "substituted" is defined as that at least one hydrogen atom is replaced by one selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, ether groups, acetal groups, alkenyl groups, cycloalkyl groups, heterocycloalkyl groups, allyl groups, benzyl groups, aryl groups, heteroaryl groups, derivatives thereof and combinations thereof.

[0049] One embodiment of the present invention provides a photosensitive resin composition, which includes: an alkali-soluble resin comprising a repeating unit represented by the following general formula 1 or general formula 2; a photosensitizer; and a solvent, wherein in the following general formula 1 and general formula 2, at least one of R1 and R2 comprises a molecular structure represented by the following general formula 3.

[0050] [General formula 1]

[0051]

[0052] [General formula 2]

[0053]

[0054] [Formula 3]

[0055] (C1)o-(B)p-(A)-(B)q-(C2)r

[0056] In the above general formula 1 and general formula 2, R1 is a divalent to octavalent organic group having two or more carbon atoms, R2 is a divalent to hexavalent organic group having two 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, and a+b is 1 or more, m and n represent 0 mol% to 100 mol% of general formula 1 and general formula 2, respectively, and m+n=100 mol%. In the above general formula 3, A is 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; the molecular structures of C1 and C2 may be the same or different, and when the molecular structures of C1 and C2 are the same, C1 and C2 contain heteroatoms, 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 greater than or equal to 1, and o+r is an integer greater than or equal to 1. According to one embodiment of the present invention, since A is an aromatic organic group containing at least one of a fluorine atom, an oxygen atom, a sulfur atom and a hydroxyl group, the chemical resistance and sensitivity performance can be further improved, and 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 with an amino group (-NH2), and since the molecular structures of C1 and C2 can be the same or different, the problem of decreased sensitivity due to existing diamine monomers can be solved, while improving sensitivity and flexibility. That is, according to one embodiment of the present invention, a photosensitive resin composition can be provided that improves the flexibility of a device by forming hydrogen bonds between molecules and increasing the free volume corresponding to the free space between atoms, and has excellent chemical resistance, sensitivity, adhesion, and device reliability.

[0057] Hereinafter, the constitution of the present invention will be described in more detail.

[0058] 1. Photosensitive resin composition

[0059] The photosensitive resin composition according to the present invention includes an alkali-soluble resin including a repeating unit represented by Formula 1 or Formula 2 below.

[0060] [General formula 1]

[0061]

[0062] [General formula 2]

[0063]

[0064] In the above-mentioned general formula 1 and general formula 2, R1 is a divalent to octavalent organic group having two or more carbon atoms, R2 is a divalent to hexavalent organic group having two 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, and a+b is 1 or more, m and n represent 0 mol% to 100 mol% of general formula 1 and general formula 2, respectively, and m+n=100 mol%.

[0065] Specifically, the alkali-soluble resin may include a polyamic acid (ester) repeating unit represented by the general formula 1 or a polyimide repeating unit represented by the general formula 2. With the increase of the polyimide repeating unit, flexibility, sensitivity performance, residual performance, chemical resistance and device reliability can be improved.

[0066] The imidization index of the alkali-soluble resin may be more than 50% to 100%, specifically, 60% to 100%, and more specifically, 70% to 100%. The imidization index of the alkali-soluble resin may be adjusted by changing the synthesis temperature and the synthesis time. For example, the synthesis temperature and the synthesis time of the polyimide resin may be 100° C. to 180° C. and 2 hours to 6 hours, respectively. When the imidization index of the polyimide resin satisfies the above numerical range, the flexibility, sensitivity performance, residual performance, chemical resistance and device reliability may be further improved.

[0067] At least one of R1 and R2 in the above-mentioned Formula 1 and Formula 2 includes a molecular structure represented by the following Formula 3.

[0068] [Formula 3]

[0069] (C1)o-(B)p-(A)-(B)q-(C2)r

[0070] In the above general formula 3, A may be an aromatic organic group containing at least one of a fluorine atom, an oxygen atom, a sulfur atom and a hydroxyl group, and specifically, may be an aromatic organic group containing the above fluorine atom and a hydroxyl group. In the above general formula 3, since A is an aromatic organic group containing both a fluorine atom and a hydroxyl group, chemical resistance and sensitivity can be improved at the same time. In particular, the fluorine atom can help improve chemical resistance, and the hydroxyl group can help improve sensitivity.

[0071] In the above general formula 3, since B is an amide group (CONH), compared with an amino group (-NH2), the flexibility of the device can be significantly improved.

[0072] In the above 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 above heteroaryl group may be a 5-membered ring or a 6-membered ring, specifically, pyridine. In addition, C1 and C2 may have the same or different molecular structures, specifically, they may be different from each other. When C1 and C2 have the same molecular structure, C1 and C2 may contain heteroatoms, for example, heteroaryl groups. When C1 and C2 have different molecular structures, flexibility and sensitivity performance may be improved at the same time. For example, in the above C1 and C2, the "substituted aryl group having 6 to 12 carbon atoms" may include a structure in which at least one hydrogen atom bonded to the aryl group having 6 to 12 carbon atoms is substituted by an alkyl group, a halogen atom or an alkoxy group. As another example, the above-mentioned "substituted heteroaryl group having 5 to 12 carbon atoms" may include a structure in which at least one hydrogen atom bonded to the heteroaryl group having 5 to 12 carbon atoms is substituted by an alkyl group, a halogen atom or an alkoxy group. For example, the above-mentioned alkyl group may be an alkyl group having 1 to 5 carbon atoms, the above-mentioned halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the above-mentioned alkoxy group may be an alkoxy group having 1 to 5 carbon atoms. If these substituents are further included, crosslinking can be formed between resin molecules, and further improvement in flexibility can be expected.

[0073] Specifically, in the following General Formula 1 and General Formula 2, R2 may include a molecular structure represented by the above General Formula 3. The above R2 may be a part of a molecular structure derived from a diamine monomer used to synthesize a polyimide-based resin.

[0074] In the above general formula 3, A may include a molecular structure represented by the following general formula 4,

[0075] [Formula 4]

[0076]

[0077] In the above general formula 4, R5 can be one selected from the group consisting of oxygen atoms, C(CF3)2, C(CH3)2 and SO2, and specifically, can be C(CF3)2. When the above R5 is C(CF3)2, since it contains fluorine atoms, the chemical resistance can be further improved.

[0078] In the above general formula 4, since R6 is each independently 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.

[0079] For example, the molecular structure represented by the above general formula 3 may include one of the molecular structures represented by the following general formulas 1 to 4. As another example, the molecular structure represented by the above general formula 3 includes the molecular structures represented by the following chemical formulas 1 to 4 as a parent, and may have a molecular structure in which at least one hydrogen atom bonded to an aryl group or a heteroaryl group is substituted by one of an alkyl group, a halogen atom, and an alkoxy group,

[0080] [Chemical formula 1]

[0081]

[0082] [Chemical formula 2]

[0083]

[0084] [Chemical formula 3]

[0085]

[0086] [Chemical formula 4]

[0087]

[0088] According to one embodiment of the present invention, a photosensitive resin composition can be provided. Since the photosensitive resin composition includes one of the molecular structures represented by the above chemical formulas 1 to 4 as a parent structure, a diamine monomer that forms hydrogen bonds between molecules and increases the free volume corresponding to the free space between atoms can be used to improve the flexibility of the device and provide excellent chemical resistance, sensitivity performance, adhesion and device reliability.

[0089] For example, in the general formula 3, the heteroaryl group may include a nitrogen atom or a sulfur atom, and specifically, may include a nitrogen atom. In the general formula 3, since the heteroaryl group includes a nitrogen atom with a large electronegativity in the ring, the sensitivity and high transparency performance can be further improved.

[0090] According to another embodiment of the present invention, in the above general formula 2, n may exceed 50 mol%. In the above general formula 2, n is the molar percentage of the polyimide repeating unit. When it exceeds 50 mol%, the flexibility, sensitivity, chemical resistance and reliability of the device can be significantly improved.

[0091] According to another embodiment of the present invention, based on the total monomers of the alkali-soluble resin, the content of the molecular structure represented by the general formula 3 may be 5 mol% to 100 mol%, specifically, 5 mol% to 90 mol%. The total monomers of the alkali-soluble resin may refer to diamine monomers and anhydride monomers. When the content of the molecular structure represented by the general formula 3 satisfies the above numerical range, the flexibility, chemical resistance and sensitivity performance of the device can be further improved.

[0092] According to another embodiment of the present invention, the content of the molecular structure represented by the general formula 3 based on the diamine monomer of the alkali-soluble resin may be 30 mol % to 100 mol %, specifically, 30 mol % to 80 mol %. When the content of the molecular structure represented by the general formula 3 based on the diamine monomer satisfies the above numerical range, the flexibility, chemical resistance and sensitivity performance of the device may be further improved.

[0093] The photosensitive resin composition according to the present invention includes a photosensitizer that imparts alkali developability to an exposed portion after exposure.

[0094] The photosensitizer includes an esterified quinone diazide compound, and the esterified quinone diazide compound may include a phenol structure as a matrix (ballast). For example, the matrix may be one selected from the structures represented by the following chemical formulas a to h. At least one hydroxyl group in the matrix may react with an acid compound containing a carboxyl group to perform an esterification reaction.

[0095] [Chemical formula a]

[0096]

[0097] [Chemical formula b]

[0098]

[0099] [Chemical formula c]

[0100]

[0101] [Chemical formula d]

[0102]

[0103] [Chemical formula e]

[0104]

[0105] [Chemical formula f]

[0106]

[0107] [Chemical formula g]

[0108]

[0109] [Chemical formula h]

[0110]

[0111] In the above chemical formulas a to h, R7, R8 and R 11 To R55 Each of X3 and X4 is 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, and each of R9 and R 10 Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0112] Based on 100 parts by weight of the alkali-soluble resin, the content of the photosensitizer may be 5 parts by weight to 50 parts by weight, specifically, 10 parts by weight to 30 parts by weight. When the content of the photosensitizer satisfies the above numerical range, the pattern shape can be properly maintained while ensuring appropriate photosensitivity and heat resistance.

[0113] The photosensitive resin composition according to the present invention includes a solvent. For example, the solvent may be 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 a mixture thereof.

[0114] The photosensitive resin composition according to another embodiment of the present invention may further include an additive. The above-mentioned additive may be one selected from the group consisting of a cross-linking agent, a thermal acid generator, a UV absorber and a mixture thereof. The above-mentioned cross-linking agent undergoes a cross-linking reaction with an alkali-soluble resin by heat in a thermal curing process, thereby effectively controlling the shape of the pattern. For example, the above-mentioned cross-linking agent may be a cross-linking agent having an alkoxymethyl group or a cross-linking agent having an epoxy group. The above-mentioned thermal acid generator acts as a catalyst for the above-mentioned cross-linking reaction, and can effectively control the downstream of the pattern. The above-mentioned thermal acid generator and the above-mentioned UV absorber are not particularly limited, but may be commercial products in the relevant technical field.

[0115] 2. Cured film and display device

[0116] Another embodiment of the present invention can provide a cured film formed by curing the above-mentioned 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, "a cured film formed by curing the photosensitive resin composition" can refer to a cured film state from which the solvent has been removed.

[0117] Figure 1 is a vertical cross-sectional view of a display device according to an embodiment of the present invention.

[0118] Reference Figure 1 , the cured film according to the present invention may be an interlayer insulating layer. The interlayer insulating layer may be arranged on an interlayer dielectric (ILD) layer, and may be arranged between a first electrode and a second electrode facing each other. As another example, the interlayer insulating layer may cover a portion of the electrode. In addition, the photosensitive resin composition according to the present invention may be widely used in semiconductor devices, devices for flexible displays, OLED devices, and the like.

[0119] Hereinafter, an embodiment of the present invention will be described in more detail so that those skilled in the art can easily implement it, but this is only an example, and the scope of the present invention is not limited to the following contents.

[0120] [Synthesis Example: Synthesis of Alkali-Soluble Resin]

[0121] <Synthesis Example 1: Synthesis of polyamic acid>

[0122] Under a dry nitrogen stream, 2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (bis-APAF; 70 mol) as 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 (ODPA; 68 mol) was added and dissolved in the dissolved above mixture, and then stirred at 70°C for 4 hours. Then, phthalic anhydride (PA; 64 mol) was added to the stirred product, and the reaction was terminated by stirring at 70°C for 2 hours to synthesize polyamic acid,

[0123] [Chemical formula 1-1]

[0124]

[0125] <Comparative Synthesis Example 1: Synthesis of Polyimide>

[0126] Polyamic acid was synthesized in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (bis-APAF; 100 mol) was used instead of the compound represented by the above Chemical Formula 1-1. Then, the mixture was further stirred at 180° C. for 4 hours to synthesize polyimide.

[0127] <Synthesis Examples 2 to 11: Synthesis of Polyimide>

[0128] Polyamic acids were respectively synthesized in the same manner as in Synthesis Example 1, except that the diamine content was adjusted according to the following Table 1. Then, the mixture was further stirred at 180° C. for 4 hours to synthesize a polyimide.

[0129] <Synthesis Examples 12 to 21: Synthesis of polyimide>

[0130] Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, except that the 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 the following Table 1.

[0131] [Chemical formula 2-1]

[0132]

[0133] <Synthesis Examples 22 to 31: Synthesis of Polyimide>

[0134] Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, except that the 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 the following Table 1.

[0135] [Chemical formula 3-1]

[0136]

[0137] <Synthesis Examples 32 to 41: Synthesis of Polyimide>

[0138] Polyimides were synthesized in the same manner as in Synthesis Examples 2 to 11, except that the 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 the following Table 1.

[0139] [Chemical formula 4-1]

[0140]

[0141] Table 1

[0142]

[0143]

[0144] <Synthesis Examples 42 to 49: Synthesis of polyimide>

[0145] 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.

[0146] Table 2

[0147]

[0148]

[0149] <Comparative Synthesis Examples 2 to 15: Synthesis of Polyimide>

[0150] The polyimide was synthesized in the same manner as in Synthesis Examples 2 to 11, except that the compound represented by the above Chemical Formula 1-1 was replaced by a compound represented by the following Chemical Formula 5-1, ODA, APB, BAPP or one of the diamine compounds having a symmetrical structure such as 6FODA, and the diamine content was adjusted according to Table 3 below.

[0151] [Chemical formula 5-1]

[0152]

[0153] Table 3

[0154]

[0155]

[0156] [Preparation Example: Preparation of Photosensitive Resin Composition]

[0157] <Examples 1 to 41: Case where PAC is TPPA>

[0158] Photosensitive resin compositions containing 100 parts by weight of the alkali-soluble resin according to each of the above Synthesis Examples 1 to 41; 25 parts by weight of a compound containing a 5-naphthoquinonediazidesulfonyl group (TPPA); and 20 parts by weight of a crosslinking agent containing an alkoxymethyl group (HMOM-TPHAP) were prepared respectively.

[0159] <Examples 42, 44, 46 and 48: PAC is THPE>

[0160] Photosensitive resin compositions were prepared respectively including 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 5-naphthoquinonediazidesulfonyl (THPE); and 20 parts by weight of a crosslinking agent containing an alkoxymethyl group (HMOM-TPHAP).

[0161] <Examples 43, 45, 47 and 49: When the crosslinking agent contains an epoxy structure>

[0162] Photosensitive resin compositions were prepared respectively including 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 5-naphthoquinonediazidesulfonyl (THPE); and 20 parts by weight of an epoxy-containing crosslinking agent (Epiclon HP-820).

[0163] <Comparative Examples 1 to 15: Corresponding to Comparative Synthesis Examples 1 to 15>

[0164] Photosensitive resin compositions containing 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-naphthoquinonediazidesulfonyl group (TPPA); and 20 parts by weight of a crosslinking agent containing an alkoxymethyl group (HMOM-TPHAP) were prepared respectively.

[0165] [Experimental example: Physical property evaluation and imidization index measurement]

[0166] 1) Flexibility and crack evaluation

[0167] The photosensitive resin composition according to the above preparation example was coated on a 100 μm polyimide film with a thickness of 3 μm, and then folded inward 200,000 times with a radius of curvature of 1R. If a crack larger than 3 mm was observed during less than 100,000 repetitions, it was marked as X, if a crack was observed at 100,000 repetitions, it was marked as △, if a crack was observed at 150,000 repetitions, it was marked as O, if no crack was observed at 200,000 repetitions, it was marked as ◎, and the results are shown in the following Tables 4 and 5. For this purpose, observation was performed by visual inspection and 100 times magnification of a microscope.

[0168] 2) Sensitivity

[0169] After coating the photosensitive resin composition according to the above preparation example on a glass substrate using a slit coater, the glass substrate was treated at a pressure of 40 Pa according to a vacuum drying 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. The pre-cured film was irradiated with an intensity of 20 mW / cm2 using a predetermined pattern mask. 2 UV light (based on the dose of 2.5 μm contact hole critical size) and then tetramethylammonium hydroxide aqueous solution (N(CH3)4 + OH - ; 2.38 wt %) was developed at 23°C for 1 minute and washed with ultrapure water for 1 minute. Subsequently, the washed reactant 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 above cured film, when the sensitivity is less than 100 mJ / cm 2 When the sensitivity is 100mJ / cm 2 Up to 150mJ / cm 2 When the sensitivity is greater than or equal to 150mJ / cm 2 The results are shown in Tables 4 and 5 below.

[0170] 3) Scum (residue)

[0171] The inside of the cured film formed in the above sensitivity evaluation process was observed using a scanning electron microscope (SEM). If there was residue in the Line & Space and the contact hole, it was marked as "X", and if not, it was marked as "O". The results are shown in Tables 4 and 5 below.

[0172] 4) Chemical resistance

[0173] 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 the immersion was measured. The evaluation solvent was a mixture of propylene glycol methyl ether and propylene glycol methyl ether acetate in a molar ratio of 7:3. At this time, if the thickness change rate of the cured film is less than or equal to If the thickness change rate is greater than and less than or equal to If the thickness change rate is greater than and less than or equal to If the thickness change rate is greater than The results are shown in Tables 4 and 5 below.

[0174] 5) Adhesion

[0175] In the cured film formed during the sensitivity evaluation, the adhesive force according to the baking temperature was compared based on the case where the line width of 10 μm and the slit width were 1:1. At this time, the case where the adhesiveness was ensured at the pre-baking temperature of 90°C to 120°C was marked as "O", the case where the adhesiveness was ensured at the pre-baking temperature of 125°C to 130°C was marked as "△", and the case where the adhesiveness was ensured or not ensured at the pre-baking temperature of 130°C or more was marked as "X".

[0176] 6) OLED reliability

[0177] After forming a pattern film on an indium tin oxide (ITO) substrate (anode electrode) in the same manner as the above sensitivity analysis method, an organic light-emitting layer is deposited. After forming an aluminum thin film on the upper part as a cathode electrode, an encapsulation process is performed to manufacture an OLED device. Under conditions of 85°C and 85% relative humidity (RH), the time (T97) for the brightness of the OLED device to decrease by 3% in the on state is evaluated. When a time of more than 1000 hours is ensured, it is marked as "◎", when a time of more than 500 hours and less than 1000 hours is ensured, it is marked as "O", when a time of more than 200 hours and less than 500 hours is ensured, it is marked as "△", and when a time of less than 200 hours is ensured, it is marked as "X", and the results are shown in Tables 4 and 5 below.

[0178] 7) Imidization index (%)

[0179] The photosensitive resin composition according to the above preparation example is coated on a substrate. Subsequently, after thin film coating on a glass substrate using a slit coater, it is 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, which is then subjected to IR measurement. Based on the C=C stretching peak intensity of the benzene ring that does not change during the imidization reaction, the imidization index (Peak of CNC / Peak of C=C@aromatic) is determined according to the CNC peak intensity of the imidization reaction, and the imidization rate when cured at 350°C is assumed to be 100%, and the imidization rate when cured at 250°C is calculated. As an evaluation result, when the imidization rate is less than 51%, it is marked as <, and when the imidization rate is more than 51%, it is marked as ≥, and the results are shown in Tables 4 and 5 below.

[0180] Table 4

[0181]

[0182]

[0183] Table 5

[0184]

[0185]

[0186] Referring to Tables 4 and 5 above, it can be confirmed that Examples 2 to 49 have the same or improved sensitivity performance, flexibility or device reliability compared to the comparative examples. In addition, when Example 1 is compared with the remaining examples, it can be confirmed that when the imidization index exceeds 50%, the flexibility, sensitivity, chemical resistance and device reliability are generally improved. Taking the above experimental results into consideration, it can be inferred that the various embodiments of the present invention can form intermolecular hydrogen bonds and increase the free volume between atoms by including the molecular structure represented by the above general formula 3 as a matrix. Therefore, a photosensitive resin composition that improves the flexibility of the device and has excellent chemical resistance, sensitivity performance, adhesion and device reliability can be provided.

[0187] The preferred embodiments of the present invention are described in detail above, but the scope of the present invention is not limited thereto. Various modifications and improvements by ordinary technicians in the technical field of the present invention using the basic concepts of the present invention defined in the scope of protection of the attached invention claims also fall within the scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: include: An alkali-soluble resin comprising a repeating unit represented by the following general formula 1 or general formula 2; Photosensitizers; and Solvents, In the following general formula 1 and general formula 2, at least one of R1 and R2 includes a molecular structure represented by the following general formula 3: [General formula 1] [General formula 2] [Formula 3] (C1)o-(B)p-(A)-(B)q-(C2)r In the above general formula 1 and general formula 2, R1 is a divalent to octavalent organic group having two or more carbon atoms, R2 is a divalent to hexavalent organic group having two 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, and a+b is 1 or more, m and n represent 0 mol% to 100 mol% of Formula 1 and Formula 2, respectively, 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), 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; the molecular structures of C1 and C2 are the same or different. When the molecular structures of C1 and C2 are the same, C1 and C2 contain heteroatoms. 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 greater than or equal to 1, and o+r is an integer greater than or equal to 1.

2. The photosensitive resin composition according to claim 1, characterized in that: In the above general formula 3, A is an aromatic organic group containing the above fluorine atom and a hydroxyl group.

3. The photosensitive resin composition according to claim 1, characterized in that: In the following general formulas 1 and 2, R2 includes the molecular structure represented by the above general formula 3.

4. The photosensitive resin composition according to claim 1, characterized in that: In the above general formula 3, A comprises a molecular structure represented by the following general formula 4: [Formula 4] In the above general formula 4, R5 is one selected from the group consisting of oxygen atoms, C(CF3)2, C(CH3)2 and SO2, R6 is each independently 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 photosensitive resin composition according to claim 1, characterized in that: The molecular structure represented by the above general formula 3 includes one of the molecular structures represented by the following chemical formulas 1 to 4: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] 6. The photosensitive resin composition according to claim 1, characterized in that: In the above general formula 3, the above heteroaryl group contains a nitrogen atom or a sulfur atom.

7. The photosensitive resin composition according to claim 1, characterized in that: In the above general formula 2, n is greater than 50 mol%.

8. The photosensitive resin composition according to claim 1, characterized in that: The content of the molecular structure represented by the above General Formula 3 is 5 mol % to 100 mol % based on the total amount of monomers of the above alkali-soluble resin.

9. The photosensitive resin composition according to claim 1, characterized in that: The content of the molecular structure represented by the above General Formula 3 is 30 mol % to 80 mol % based on the diamine monomer of the above alkali-soluble resin.

10. The photosensitive resin composition according to claim 1, characterized in that: The photosensitizer comprises an esterified quinone diazide compound, The above-mentioned esterified quinonediazide compound contains a phenol structure as a parent body, that is, a ballast.

11. The photosensitive resin composition according to claim 1, characterized in that: Also includes: The additive is one selected from the group consisting of a cross-linking agent, a thermal acid generator, a UV absorber and a mixture thereof.

12. The photosensitive resin composition according to claim 1, characterized in that: The above-mentioned 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 substituted with an alkyl group, a halogen atom or an alkoxy group, The above-mentioned substituted heteroaryl group having 5 to 12 carbon atoms includes a structure in which at least one hydrogen atom bonded to the heteroaryl group having 5 to 12 carbon atoms is substituted with an alkyl group, a halogen atom or an alkoxy group.

13. A cured film, characterized in that: The method is formed by curing the photosensitive resin composition according to any one of claims 1 to 12.

14. A display device, characterized in that: Comprising the cured film according to claim 13.

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