Polyimide resin, negative photosensitive resin composition comprising same, and electronic device

Abstract

The present invention relates to a polyimide resin, a negative-type photosensitive resin composition comprising the same, and an electronic device comprising an organic insulating film or a photosensitive pattern formed from the negative-type photosensitive resin composition.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, and more particularly to a negative-type ring-closed polyimide resin having excellent solubility and not swelling during development, a negative-type photosensitive resin composition including the same, and an electronic device.

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0141533 filed on October 28, 2022, in the Korean Intellectual Property Office, and Korean Patent Application No. 10-2023-0144299 filed on October 26, 2023, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Background Art

[0003] Photosensitive resin is a typical functional polymer material that has been put into practical use in the production of various precision electronic information industry products, and is currently used in cutting-edge technology industries, especially in the production of semiconductors and displays. Generally, photosensitive resin refers to a polymer compound whose molecular structure undergoes chemical changes in a short period of time when irradiated with light, so that physical properties such as solubility in specific solvents, coloring, and curing change. Since the use of photosensitive resin enables micro-precision processing, it can significantly reduce energy and raw materials compared to thermal reaction processes, and can allow work to be performed quickly and accurately in a small installation space, so photosensitive resin has been widely used in various precision electronic information industries, such as advanced printing, semiconductor production, display production, and photocurable surface coating materials.

[0004] Such photosensitive resins can be roughly divided into negative photosensitive resins of a type in which a portion irradiated with light becomes insoluble in a developer and positive photosensitive resins of a type in which a portion irradiated with light becomes soluble in a developer.

[0005] After selective exposure, the polymer used for negative photosensitive resin needs to meet the following requirements: the exposed part needs to have high solubility in the developer, while the unexposed area needs to have low solubility or no solubility in the developer. Such requirements are increasingly needed to form extremely fine patterns in the precision electronic information industry. Summary of the invention

[0006] Technical issues

[0007] The present invention has been made in an effort to provide a polyimide having a closed ring structure, which does not cause swelling in a development process during pattern formation using a negative photosensitive composition and has excellent solubility, and a negative photosensitive resin composition including the same.

[0008] Furthermore, an object of the present invention is to provide an electronic device including an organic insulating film or a photosensitive pattern formed of the negative photosensitive resin composition.

[0009] Technical Solution

[0010] An exemplary embodiment of the present specification provides a polyimide resin including a structure of the following Chemical Formula 1.

[0011] [Chemical formula 1]

[0012]

[0013] In Chemical Formula 1,

[0014] -* means a portion bonded to another substituent or a repeating unit,

[0015] X1 and X2 are the same as or different from each other and are each independently a tetravalent organic group,

[0016] Y is a divalent to tetravalent organic group,

[0017] R3 to R6 are the same as or different from each other and are each independently hydrogen; or represented by the following Chemical Formula 2, provided that the ratio of the structure represented by the following Chemical Formula 2 is 1 mol% or more relative to the total molar number of OH groups contained in the polyimide resin,

[0018] m1, m2, k1 and k2 are each 0 or 1, and 1≤m1+m2+k1+k2≤2,

[0019] Z is a direct bond or a divalent organic group,

[0020] When the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05≤Z≤0.3,

[0021] n is a real number from 1 to 50, and

[0022] m is a real number from 0 to 50,

[0023] [Chemical formula 2]

[0024]

[0025] In chemical formula 2,

[0026] * is a part connected to Chemical Formula 1,

[0027] R7 is hydrogen; or substituted or unsubstituted alkyl, and

[0028] p is an integer from 1 to 10.

[0029] Another exemplary embodiment of the present invention provides a negative photosensitive resin composition including: the polyimide resin; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

[0030] Furthermore, yet another exemplary embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed of the negative photosensitive resin composition.

[0031] Beneficial Effects

[0032] Even during the development process after selective exposure during pattern formation using the negative photosensitive resin composition according to the present specification, the polyimide resin has excellent solubility without swelling. In addition, an electronic device including an organic insulating film or a photosensitive pattern having excellent properties formed by the negative photosensitive resin composition according to the present specification can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 An example of an organic insulating film for a semiconductor including the photosensitive resin composition according to an exemplary embodiment of the present invention is shown.

[0034] Figure 2 An example of an organic insulating film for an organic light emitting device including the photosensitive resin composition according to an exemplary embodiment of the present invention is shown.

[0035] Figure 3 and Figure 4 is a photograph of a photosensitive pattern according to an exemplary embodiment of the present invention.

[0036] [Explanation of Reference Numerals]

[0037] 1: Silicon wafer (Si wafer)

[0038] 2: First photosensitive pattern (PID1)

[0039] 3, 8: pad

[0040] 4: Solder balls

[0041] 5: Second photosensitive pattern (PID2)

[0042] 6: Base

[0043] 7: First photosensitive pattern (RDL)

[0044] 9: Second photosensitive pattern (PDL)

[0045] 10: OLED layer DETAILED DESCRIPTION

[0046] Hereinafter, a polyimide resin, a negative photosensitive resin composition, and an electronic device according to specific exemplary embodiments of the present invention will be described in detail.

[0047] In the present specification, when a part “includes” a constituent element, unless specifically described otherwise, this does not mean excluding the other constituent elements but means that the other constituent elements may further be included.

[0048] An exemplary embodiment of the present invention provides a polyimide resin including a structure of Chemical Formula 1 below.

[0049] [Chemical formula 1]

[0050]

[0051] In Chemical Formula 1,

[0052] -* means a portion bonded to another substituent or a repeating unit,

[0053] X1 and X2 are the same as or different from each other and are each independently a tetravalent organic group,

[0054] Y is a divalent to tetravalent organic group,

[0055] R3 to R6 are the same as or different from each other and are each independently hydrogen; or represented by the following Chemical Formula 2, provided that the ratio of the structure represented by the following Chemical Formula 2 is 1 mol% or more relative to the total molar number of OH groups contained in the polyimide resin,

[0056] m1, m2, k1 and k2 are each 0 or 1, and 1≤m1+m2+k1+k2≤2,

[0057] Z is a direct bond or a divalent organic group,

[0058] When the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05≤Z≤0.3,

[0059] n is a real number from 1 to 50, and

[0060] m is a real number from 0 to 50,

[0061] [Chemical formula 2]

[0062]

[0063] In chemical formula 2,

[0064] * is a part connected to Chemical Formula 1,

[0065] R7 is hydrogen; or substituted or unsubstituted alkyl, and

[0066] p is an integer from 1 to 10.

[0067] The inventors have experimentally determined that a photosensitive resin including a polyimide resin having the aforementioned specific structure can achieve high adhesion and adhesion to a substrate used in a semiconductor device or a display device (e.g., a metal substrate such as Au, Cu, Ni, and Ti, or an inorganic substrate such as SiO2 and SiNx), has improved mechanical properties such as excellent heat resistance or chemical resistance, and can easily form an ultra-fine pattern, thereby completing the present invention.

[0068] Furthermore, the present inventors were able to secure fine patterns and excellent physical properties by imparting an acrylate group (—COO—) to the polyimide resin including the structure of the above Chemical Formula 1.

[0069] In particular, for the negative photosensitive resin composition, instead of using a polyimide precursor requiring a high temperature thermosetting process (imidization process), a polyimide resin that can undergo a solution process at a low temperature is used, and the high temperature imidization process can be omitted.

[0070] The present inventors have revealed that when a polyimide having a structure in which a photopolymerizable unsaturated group is bonded to a side chain of a polyimide having a closed-loop structure is used as an existing polyimide, the solubility is reduced during development, resulting in a reduction in the swelling phenomenon. In addition, the present inventors have also revealed that there is a problem that when a closed-loop polyimide and a monomer having a photopolymerizable multifunctional group are used together, high energy is generated during the curing process due to exposure, making it difficult to achieve precise patterning and increasing process costs because the polymer itself does not have a photopolymerizable group. In addition, although attempts have been made to introduce a polyamide ester structure (polyamide ester type) by attaching a photopolymerizable group (R) to an open-loop position after opening the anhydride closed-loop structure of the closed-loop polyimide, the present inventors have also revealed that there is a problem that the photopolymerizable group (R) is desorbed during the closed-loop period, resulting in poor dimensional stability and gas generation.

[0071]

[0072] However, the polyimide resin according to the above exemplary embodiment of the present invention imparts such a feature that since a photopolymerizable unsaturated group (represented by Chemical Formula 2) is included at a portion of the main chain and the terminal group, the terminal group does not cause a ring-closing reaction with the main chain or the side chain bonded to the main chain even during development, and a swelling phenomenon does not occur during development.

[0073] Furthermore, the polyimide resin according to the exemplary embodiment of the present invention may additionally include an unreacted hydroxyl group (OH), carboxylic acid (COOH), thiol group, or sulfonic acid group at a terminal group, and such a group may provide excellent solubility.

[0074] According to an exemplary embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group.

[0075] According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other, and may be each independently selected from a tetravalent aromatic organic group, a tetravalent aliphatic organic group, and a tetravalent organic group in which an aromatic group and an aliphatic group are connected to each other.

[0076] According to an exemplary embodiment of the present specification, X1 and X2 are divalent hydrocarbons, or at least one carbon of the hydrocarbon is replaced by C(=O), SO2, NR', S or O, or at least one hydrogen of the hydrocarbon may be substituted by halogen or alkyl, and R' may be an unsubstituted or halogen-substituted alkyl; or an unsubstituted or halogen- or alkyl-substituted aryl.

[0077] According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other, and may be each independently selected from the following structures.

[0078]

[0079] In the structure,

[0080] represents a tetravalent organic group, and is a connecting portion to the carbonyl group (C(═O)) of Chemical Formula 1.

[0081] According to an exemplary embodiment of the present specification, X1 and X2 are

[0082] When the polyimide resin includes the above structure, mechanical properties of the polyimide resin are improved, and the penetration effect of a developer during development is increased, which is effective in forming an ultrafine pattern.

[0083] According to an exemplary embodiment of the present specification, Y may be selected from a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are connected to each other.

[0084] According to an exemplary embodiment of the present specification, Y is a divalent hydrocarbon, or at least one carbon of the hydrocarbon is replaced by C(=O), SO2, NR", S or O, or at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl group, and R" can be an alkyl group or an aryl group.

[0085] According to an exemplary embodiment of the present specification, Y may be selected from the following structures.

[0086]

[0087] In the structure, A is a divalent organic group, and It may be a connecting portion to N of Chemical Formula 1.

[0088] According to an exemplary embodiment of the present specification, It represents a minimum divalent to a maximum tetravalent organic group.

[0089] According to an exemplary embodiment of the present specification, A may be a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl.

[0090] According to an exemplary embodiment of the present specification, A can be a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl.

[0091] According to an exemplary embodiment of the present specification, A may be selected from the following structures.

[0092]

[0093] In the structure,

[0094] *for The connecting part of each phenol group.

[0095] According to an exemplary embodiment of the present specification, Y is Here, A is

[0096] According to an exemplary embodiment of the present specification, Z may be a direct bond or a divalent organic group of any one of the following structures.

[0097]

[0098] In the structure, B is a divalent organic group, and It may be a connecting portion to N of Chemical Formula 1.

[0099] According to an exemplary embodiment of the present specification, It represents a minimum divalent to a maximum tetravalent organic group.

[0100] According to an exemplary embodiment of the present specification, B may be a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl.

[0101] According to an exemplary embodiment of the present specification, B can be a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl.

[0102] According to an exemplary embodiment of the present specification, B may be selected from the following structures.

[0103]

[0104] In the structure, * is The connecting part of each phenyl group.

[0105] According to an exemplary embodiment of the present specification, Z is a direct bond.

[0106] The polyimide resin has a function of forming an ultrafine pattern by controlling the developability through inclusion of the above structure.

[0107] According to an exemplary embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0108] According to an exemplary embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0109] According to an exemplary embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0110] According to an exemplary embodiment of the present specification, R7 is hydrogen.

[0111] According to an exemplary embodiment of the present specification, n is a real number of 1 to 50, and m is 0.

[0112] According to an exemplary embodiment of the present specification, n is a real number of 1 to 50, and m is a real number of 1 to 50.

[0113] In the present specification, the aromatic (organic) group may be a C6 to C20 arylene group, and the aliphatic group may be a C1 to C20 alkylene group, or a C3 to C20 cycloalkylene group. Examples of the arylene group include a phenylene group and the like.

[0114] Examples of halogen groups include F, Cl, and the like.

[0115] In the present specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxyl group, -COOH, an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, or has no substituent.

[0116] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 30. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to yet another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc., but are not limited thereto.

[0117] In the present specification, an alkylene group means a divalent alkyl group, and the above description can be applied to the alkyl group.

[0118] In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to yet another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

[0119] In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 20. Examples of monocyclic aryl groups as aryl groups include phenyl, biphenyl, terphenyl, etc., but are not limited thereto. Examples of polycyclic aryl groups include naphthyl, anthracenyl, indenyl, phenanthrenyl, pyrenyl, phenylene, fluorenyl, etc., but are not limited thereto.

[0120] In the present specification, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is 2 to 30, specifically 2 to 20. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, triazine, acridinyl, pyridazinyl, quinolyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, dibenzofuranyl and the like, but are not limited thereto.

[0121] In the present specification, the heterocyclic group may be an aliphatic or aromatic ring group.

[0122] In the present specification, the above description about the heterocyclic group can be applied to the heteroaryl group, except that the heteroaryl group is aromatic.

[0123] The other end of the polyimide resin may also have the terminal represented by Chemical Formula 2, or may also have a diamine or dianhydride used during the preparation of the polyimide as a terminal group.

[0124] In an exemplary embodiment of the present specification, R3 to R6 are the same as or different from each other, and at least one of them is represented by Chemical Formula 2, and the rest are hydrogen, provided that the ratio of the structure represented by Chemical Formula 2 is 1 mol% or more relative to the total molar number of OH groups included in the polyimide resin.

[0125] Even in a development process after selective exposure during pattern formation using the negative photosensitive resin composition according to one exemplary embodiment, the polyimide resin has excellent solubility in a developer without swelling.

[0126] In an exemplary embodiment of the present specification, a ratio of the structure represented by Chemical Formula 2 is 10 mol % to 70 mol % with respect to the total moles of OH groups included in the polyimide resin.

[0127] When the ratio of the structure represented by Chemical Formula 2 is less than 10 mol% relative to the total molar number of OH groups contained in the polyimide resin, the number of OH groups protected by the protecting group is small, while the number of OH groups not protected by the protecting group is relatively large, so that the residual film rate may be reduced. In addition, when the ratio of the structure represented by Chemical Formula 2 is greater than 70 mol% relative to the total molar number of OH groups contained in the polyimide resin, the number of OH groups protected by the protecting group is large, while the number of OH groups not protected by the protecting group is relatively small, so that it may be difficult to realize ultra-fine patterns due to reduced solubility in alkaline aqueous solutions.

[0128] Preferably, the ratio of the structure represented by Chemical Formula 2 is 15 mol % to 45 mol % with respect to the total moles of OH groups included in the polyimide resin.

[0129] The polyimide resin falling within the above range may comprehensively improve physical properties such as developability, residual film rate, and sensitivity.

[0130] In an exemplary embodiment of the present specification, when m1+m2+k1+k2 is 1 or 2 and contains an OH or COOH group as in the above structure, the structure of Chemical Formula 2 exists not only at the end of the polyimide resin but also on its side chain, so that it is beneficial to improve the surface condition during the formation of the photosensitive film.

[0131] According to an exemplary embodiment of the present specification, as the input ratio of diamine in the polyimide resin of Chemical Formula 1, assuming that the sum of the molar ratios of Y and Z is 1, when Z is a divalent organic group, the sum of the molar ratios of Z may be 0.05≤Z≤0.3.

[0132] In an exemplary embodiment of the present specification, the polyimide resin may further include a structure represented by the following Chemical Formula 3 as a terminal group.

[0133] [Chemical formula 3]

[0134]

[0135] In chemical formula 3,

[0136] * is a part connected to Chemical Formula 1,

[0137] Re1 is hydrogen; or a substituted or unsubstituted alkyl group,

[0138] re1 is a real number from 0 to 4, and when re1 is 2 or more, Re1 are the same as or different from each other, and

[0139] Re is hydrogen; or a structure represented by Chemical Formula 2.

[0140] In an exemplary embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0141] In an exemplary embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0142] In an exemplary embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0143] In an exemplary embodiment of the present specification, Re1 is hydrogen.

[0144] In an exemplary embodiment of the present specification, Re is hydrogen.

[0145] In an exemplary embodiment of the present specification, Re is a structure represented by Chemical Formula 2.

[0146] According to an exemplary embodiment of the present specification, the polyimide resin has a weight average molecular weight of 5,000 g / mol to 200,000 g / mol.

[0147] When the weight average molecular weight is less than 5,000, it may be difficult to achieve desired coating characteristics and mechanical characteristics during application of the polyimide copolymer, and when the weight average molecular weight exceeds 200,000, solubility in a developer decreases, making it difficult to apply the polyimide copolymer as a photosensitive material.

[0148] The weight average molecular weight is one of average molecular weights in which the molecular weight is not uniform and the molecular weight of any one polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

[0149] The weight average molecular weight may be a value measured by gel permeation chromatography (ie, GPC).

[0150] For the polyimide resin, a type of polyimide (an example of the polyimide of Chemical Formula 1) can be prepared using a dianhydride compound and a diamine compound, as exemplified below. In addition, in order to prepare other types of polyimides, as materials constituting the polyimide and polymerization methods, those known in the art can be used.

[0151] [Reaction Scheme 1]

[0152]

[0153] In addition, in order to make the polyimide of Chemical Formula 1 have a terminal group, a compound having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group and a sulfonic acid group and having one anhydride group or one amine group can be used during the polymerization of the polyimide to prepare the polyimide having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group and a sulfonic acid group, and the terminal group of Chemical Formula 1 can be prepared by reacting an isocyanate-based compound with the polyimide. The following scheme involves introducing the side chain of Chemical Formula 2 into the main chain of Chemical Formula 1 by reacting an isocyanate-based compound with Chemical Formula 1.

[0154] [Reaction Scheme 2]

[0155]

[0156] Another exemplary embodiment of the present invention provides a negative photosensitive resin composition including: a polyimide resin; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

[0157] Examples of photosensitizers include a combination of a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds. By including a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds, active radicals generated in the light irradiation area promote radical polymerization of the ethylenically unsaturated bonds, so that a negative relief pattern in which the light irradiation area is insoluble can be obtained.

[0158] Based on 100 parts by weight of the entire polyimide resin, the content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight. When the content is 0.1 parts by weight or more, sufficient free radicals are generated by light irradiation, and the sensitivity is improved. In addition, when the content exceeds 20 parts by weight, due to the generation of too many free radicals, the unirradiated area is cured, making it difficult to form an ultra-fine pattern. Based on 100 parts by weight of the entire polyimide resin, the content of the compound having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by weight. When the content is 5 parts by weight or more, it is preferred because a cured resin film with high mechanical properties can be obtained by cross-linking. When the content is 50 parts by weight or less, it is preferred because the sensitivity is not impaired.

[0159] Furthermore, as the crosslinking agent, poly(ethylene glycol) diacrylate, dipentaerythritol hexaacrylate, or the like can be used.

[0160] According to an exemplary embodiment of the present specification, the cross-linking agent includes two or more types of structures represented by Chemical Formula 4 below.

[0161] [Chemical formula 4]

[0162]

[0163] In chemical formula 4,

[0164] R8 and R9 are hydrogen; or substituted or unsubstituted alkyl,

[0165] n' is an integer from 1 to 100, and

[0166] The acrylate group (—COO—) of Chemical Formula 4 is linked to the acrylate group of Chemical Formula 2.

[0167] According to an exemplary embodiment of the present specification, two or more types of structures represented by Chemical Formula 4 are included, and the cross-linking agent having the two types of structures may have different molecular weights.

[0168] According to an exemplary embodiment of the present specification, R8 and R9 are the same as or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0169] According to an exemplary embodiment of the present specification, R8 and R9 are the same as or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0170] According to an exemplary embodiment of the present specification, R8 and R9 are the same as or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0171] With the above configuration, ultrafine patterns, excellent mechanical properties, heat-resistant properties, and the like can be ensured.

[0172] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, even more preferably 10 parts by weight or more, based on 100 parts by weight of the entire polyimide resin, and from the viewpoint of maintaining mechanical properties such as elongation, the content of the crosslinking agent is preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

[0173] The surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, as the silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-336 manufactured by BYK-Chemie Co., Ltd. can be used. 41, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc., and as fluorine-based surfactants, DaiNippon Ink & Chemicals, Inc. (DIC) manufactured F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F- 484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc., but the surfactant is not limited to these.

[0174] As the solvent, compounds known to form a photosensitive resin composition in the art to which the present invention pertains may be used without particular limitation. As non-limiting examples, the solvent may be one or more compounds selected from esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0175] The ester solvent may be, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.) 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

[0176] The ether solvent can be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

[0177] The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone or the like.

[0178] The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, and the like.

[0179] The sulfoxide solvent may be dimethyl sulfoxide or the like.

[0180] In addition, the negative photosensitive resin composition may further include additives known in the art according to its use. For example, the negative photosensitive resin composition may further include an adhesion promoter, a defoaming agent, a leveling agent, an anti-gelling agent, a mixture thereof, and the like.

[0181] As the adhesion promoter, a silane coupling agent having a functional group such as epoxy, carboxyl or isocyanate may be used, and specific examples thereof include trimethoxysilylbenzoic acid, triethoxysilylbenzoic acid, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, a mixture thereof, etc. Such an adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

[0182] As the surfactant, any surfactant known to be usable in the photosensitive resin composition may be used without any particular limitation, but a fluorine-based surfactant or a silicone-based surfactant is preferably used. Such a surfactant may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyimide resin.

[0183] According to an exemplary embodiment of the present specification, the polyimide resin may include one kind or two or more kinds of polyimide resins.

[0184] According to an exemplary embodiment of the present specification, an electronic device may be an electronic device including an organic insulating film or a photosensitive pattern formed of the negative photosensitive resin composition.

[0185] The organic insulating film or photosensitive pattern contains a polyimide having a specific structure and an acrylic compound containing one or more photocurable acrylic functional groups, and therefore can have improved mechanical properties such as excellent heat resistance, insulation or chemical resistance while achieving high adhesion to a substrate used in a semiconductor device (for example, a metal substrate such as Au, Cu, Ni and Ti, or an inorganic substrate such as SiO2 and SiNx).

[0186] The electronic device may be any one of the following: a plasma display panel (PDP), a touch panel, a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), a thin film transistor-liquid crystal display (LCD-TFT), a cathode ray tube (CRT), and a semiconductor, but is not limited thereto.

[0187] Therefore, an electronic device including an organic insulating film or a photosensitive pattern formed of the negative photosensitive resin composition can achieve excellent properties such as high resolution and high sensitivity, and can exhibit not only excellent film properties and high mechanical properties, but also excellent heat-resistant properties, such as properties that the adhesion of the organic insulating film or the photosensitive pattern can be firmly maintained without any deterioration even when the electronic device is used for a long period of time or exposed to high temperature conditions for a long period of time.

[0188] Figure 1 An example of an organic insulating film for a semiconductor comprising a photosensitive resin composition according to an exemplary embodiment of the present invention is shown. Specifically, a silicon wafer 1 is coated with a positive photosensitive resin composition and then exposed to light to form a first photosensitive pattern (referred to as PID1) 2, and a pad 3 (e.g., a Cu pad) is provided in contact with the pattern, and a solder ball 4 is provided on the top upper portion of the pad. In order to fill the underfilled area formed in this case, a second photosensitive pattern (referred to as PID2) 5 is formed using a negative photosensitive resin composition according to an exemplary embodiment of the present invention. This PID25 can be used as an organic insulating film corresponding to the outermost layer of a semiconductor packaging material.

[0189] Figure 2 An example of an organic insulating film for an organic light-emitting device comprising a photosensitive resin composition according to an exemplary embodiment of the present invention is shown. Specifically, in an OLED layer 10, a first photosensitive pattern (referred to as a redistributed layer (RDL)) 7 formed of a positive photosensitive resin composition is provided on a substrate 6 (e.g., TFT glass or TFT plastic (here, TFT means a thin film transistor)), and a pad 8 (e.g., an Ag pad) is provided in contact with the pattern. In this case, in order to leave a portion of the organic light-emitting material to enter the OLED, a second photosensitive pattern (referred to as a pixel define layer (PDL)) 9 is formed using a negative photosensitive resin composition according to an exemplary embodiment of the present invention. The PDL 9 can be used as an organic insulating film of an organic light-emitting device.

[0190] Figure 3 and Figure 4 is a photograph of a photosensitive pattern according to an exemplary embodiment of the present invention. Specifically, Figure 3 exhibits a 15 μm square pattern with a thickness of 10 μm, and Figure 4 A 5 μm hole pattern with a thickness of 8 μm was exhibited.

[0191] According to an exemplary embodiment of the present specification, the organic insulating film may include an interlayer insulating film and a surface protection film.

[0192] According to an exemplary embodiment of the present specification, the electronic device may further include a storage component.

[0193] The organic insulating film may include various insulating films of semiconductor devices, such as interlayer insulating films, surface protective films, substrate electrode protective layers, buffer coating films, passivation films, etc. In addition, the electronic device may include various components of the semiconductor device.

[0194] The interlayer insulating film and the surface protective film are not particularly limited, and those generally used in the art may be employed.

[0195] The storage component is not particularly limited, and those generally used in the art may be employed.

[0196] Meanwhile, an organic insulating film or a photosensitive pattern may be formed by: applying a negative photosensitive resin composition on a supporting substrate and drying the negative photosensitive resin composition to form a resin film; exposing the resin film to light; developing the exposed resin film with a developer; and heat-treating the developed photosensitive resin film.

[0197] Using the negative photosensitive resin composition, a patterned photosensitive resin film can be easily formed on a substrate such as glass or a silicon wafer, and in this case, as a method of applying the negative photosensitive resin composition, spin coating, bar coating, screen printing, etc. can be used.

[0198] A supporting substrate that can be used in the process of forming a photosensitive resin film can be used without any particular limitation as long as it is known to be commonly used in the electronic communication field or the semiconductor field, but specific examples thereof include silicon wafers, glass substrates, metal substrates, ceramic substrates, polymer substrates, etc.

[0199] In the drying process after application, a prebaked film may be formed by prebaking at 50° C. to 150° C. for about 1 minute to 20 minutes to evaporate the solvent. When the drying temperature is too low, the amount of residual solvent is so large that film loss may occur in the exposed area during development, resulting in a small residual film, while when the drying temperature is too high, the curing reaction is accelerated so that the unexposed area may not be developed.

[0200] In the exposure of the resin film, a photomask on which a pattern to be processed is formed may be used, so that the photomask is irradiated with UV or visible light having a wavelength of 200 nm to 500 nm, and the exposure amount during the irradiation is preferably 10 mJ / cm 2 Up to 4,000mJ / cm 2 The exposure time is also not particularly limited and may be appropriately changed depending on the exposure device used, the wavelength of the irradiated light, or the exposure amount, and specifically, the exposure time may be changed within the range of 1 second to 150 seconds.

[0201] In forming the photosensitive resin film, an alkaline aqueous developer generally known to be used in the production of semiconductors or displays may be used without any particular limitation.

[0202] Embodiments of the invention

[0203] Hereinafter, the present specification will be described in detail with reference to the embodiments for specifically describing the present specification. However, the embodiments according to the present specification can be modified in various forms and are not to be construed as limiting the scope of the present specification to the embodiments described below. The embodiments of the present specification are provided to more fully illustrate the present specification to those of ordinary skill in the art.

[0204] <Synthesis example 1>

[0205] After 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.1 equivalents of 4,4'-oxydiphthalic anhydride and 0.13 equivalents of 3-aminophenol were dissolved in PMGEA under N2 atmosphere, toluene was added to the reactants at 140°C, and the resulting mixture was connected to a Dean-Stark apparatus to react overnight at 150°C. After the reaction, toluene from the Dean-Stark apparatus was removed, and then PGMEA substitutions were performed several times to remove residual toluene. The residual monomers were determined by NMR to terminate the reaction, thereby preparing polymer 1. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight was 15,000 g / mol. The structure of polymer 1 is as follows.

[0206] [Polymer 1]

[0207]

[0208] In Polymer 1, q is a value where the weight average molecular weight of the polymer is 15,000 g / mol, and is a real number of 20 to 40.

[0209] <Synthesis example 2>

[0210] After 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.25 equivalents of 4,4'-oxydiphthalic acid diamine, 1.35 equivalents of 4,4'-oxydiphthalic anhydride and 0.16 equivalents of 3-aminophenol were dissolved in propylene glycol methyl ether acetate (PGMEA) under N2 atmosphere, toluene was added to the reactants at 150°C, and the resulting mixture was connected to a Dean-Stark apparatus to react overnight at 180°C. After the reaction, toluene from the Dean-Stark apparatus was removed, and then PGMEA substitutions were performed several times to remove residual toluene. The residual monomers were determined by NMR to terminate the reaction, thereby preparing a polymer 2 having the following structural formula. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight was determined to be 20,000 g / mol. The structure of polymer 2 is as follows.

[0211] [Polymer 2]

[0212]

[0213] In Polymer 2, p and q are values ​​where the weight average molecular weight of the polymer is 17,000 g / mol, p is a real number of 5 to 40, and q is a real number of 2 to 15.

[0214] <Synthesis example 3>

[0215] To the polymer 1 prepared in the above Synthesis Example 1, 0.016 equivalent of triethylamine and 0.1 equivalent of 2-acryloyloxyethyl isocyanate based on the OH of the polyimide were added, and an oil bath was placed, and then the reaction was carried out overnight at 80° C. The reaction was terminated when the 2H peak at 4.25 ppm of 2-acryloyloxyethyl isocyanate (AOI) disappeared by NMR.

[0216] The total OH of polymer 1 was calculated by comparing the input amount with the total area of ​​the aromatic ring of the polymer appearing at 7 ppm or more on NMR, and the substitution rate of AOI was determined by comparing the area of ​​the peak (peak, 3H) appearing at about 6 ppm with the total OH. The polymer was determined to be substituted with 10 mol% of AOI. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight was determined to be 18,000 g / mol. The structure of polymer 3 is as follows.

[0217] [Polymer 3]

[0218]

[0219] In the polymer of Synthesis Example 3, q ​​is a value in which the weight average molecular weight of the polymer is 18,000 g / mol, and q is a real number of 20 to 40.

[0220] <Synthesis example 4>

[0221] This procedure was carried out in the same manner as in Synthesis Example 3, except that polymer 2 prepared in Synthesis Example 2 was used instead of polymer 1. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight was determined to be 20,000 g / mol. The total OH of polymer 1 was calculated by comparing the input amount with the total area of ​​the aromatic rings of the polymer appearing at 7 ppm or more on NMR, and the substitution rate of AOI was determined by comparing the area of ​​the peak (peak, 3H) appearing at about 6 ppm with the total OH. It was determined that the polymer was substituted with 15 mol% AOI. The structure of polymer 4 is as follows.

[0222] [Polymer 4]

[0223]

[0224] In the polymer, p and q are values ​​where the weight average molecular weight of the polymer is 20,000 g / mol, p is a real number of 5 to 40, and q is a real number of 2 to 15.

[0225] <Examples 1 to 8 and Comparative Examples 1 to 3>

[0226] The photosensitive resin composition was prepared using the components described in the following Table 1. Specifically, a photosensitive resin composition including the prepared polyimide resin and the components shown in the following Table 1 was prepared. In the following table, 100 parts by weight of a resin composition including a polyimide resin (first and / or second polyimide resin), a photosensitizer, a crosslinking agent, a surfactant, and a solvent was used as a reference.

[0227] [Table 1]

[0228]

[0229]

[0230] A:OXE-01(BASF)

[0231] B: OXE-03 (BASF)

[0232] C: Poly(ethylene glycol) (200) diacrylate (Miramer M282, Miwon)

[0233] D: Poly(ethylene glycol) (600) diacrylate (Miramer M286, Miwon)

[0234] E: BYK-307 (BYK-Chemie Co.,Ltd.)

[0235] F: Propylene glycol monomethyl ether acetate

[0236] <Experimental example>

[0237] Under the following process conditions, the photosensitive resin compositions of the embodiments and comparative examples were evaluated, and the results are shown in Table 2 below. Specifically, the prepared photosensitive resin composition was applied to a Cu / Si wafer by spin coating. After soft baking for 120 seconds at 120°C, the wafer was exposed to light with a suitable exposure amount (i line (365nm)), and then a developer (2.38 wt % TMAH solution) was used to carry out a developing process. The pattern characteristics were determined by post-baking for 1 hour at 200°C each time. In addition, in order to additionally measure the temperature and mechanical properties of the cured film, the Si wafer was additionally coated with each prepared photosensitive resin composition, the entire surface was exposed to light, then soft baked, and post-baked for 1 hour at 200°C.

[0238] Resist evaluation conditions: PrB 120°C / 120 seconds, thickness 10 μm

[0239] Exposure: 400mJ / cm 2 Up to 500mJ / cm 2 i-line stepper

[0240] Development: 23°C, 2.38 wt% tetramethylammonium hydroxide (TMAH) solution, immersion, DI water rinse

[0241] [Pattern resolution]

[0242] For samples obtained by post-baking each of the prepared photosensitive resin compositions using the same exposure amount, the minimum size of a pattern was measured using a scanning electron microscope (SEM).

[0243] [Adhesion to substrate]

[0244] A scraper was used to cut and align 10 rows × 10 columns of squares at 2 mm intervals on the cured film completely exposed to light on the previously manufactured substrate, and the adhesive properties between the cured film and the substrate were evaluated by attaching the squares with a transparent tape and detaching the transparent tape to count the number of peeled pieces in a total of 100 squares.

[0245] ○: Less than 15 pieces were peeled off

[0246] △: 15 or more and less than 30 removed

[0247] X: Strip 30 or more

[0248] [Measurement of glass transition temperature (Tg) and elongation at break of cured film]

[0249] The cured film was prepared by peeling off the cured film which had been completely exposed to light on the previously prepared substrate from the substrate using an aqueous solution of hydrogen fluoride. For the insulating film having a thickness of 10 μm dried in an oven, the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the cured film were measured by thermomechanical analysis (TMA), and the elongation at break was measured using a universal testing machine (UTM) at room temperature at a speed of 5 cm / min.

[0250] [Table 2]

[0251]

[0252] As shown in the results of Table 2 above, the polyimide resin and the photosensitive resin composition containing the same according to the present specification have high-resolution pattern characteristics, and the cured film has excellent adhesion to the substrate. Since the cured film of the photosensitive resin composition using Examples 1 to 7 uses the polymer of Synthesis Example 3 and / or 4 and contains the unsaturated group of Chemical Formula 2, and when the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, by making the molar ratio of Z satisfy the range of 0.05≤Z≤0.3, while maintaining a good glass transition temperature (Tg) and thermal expansion coefficient (CTE) with a relatively high elongation at break, it can be determined that excellent heat resistance and excellent mechanical properties can be ensured, and fine patterns can be formed at the same time. In contrast, in Comparative Examples 1 to 3, only the polymer of Synthesis Example 1 and / or 2 is used, so that since the unsaturated group of Chemical Formula 2 is not included or the molar ratio of Z does not satisfy the above range, the curing physical properties are very poor compared to the Example group, the CTE is very low, and the elongation at break is low.

Claims

1. A polyimide resin comprising the structure of the following chemical formula 1: [Chemical formula 1] in, In Chemical Formula 1, -* means a portion bonded to another substituent or a repeating unit, X1 and X2 are the same as or different from each other and are each independently a tetravalent organic group, Y is a divalent to tetravalent organic group, R3 to R6 are the same as or different from each other and are each independently hydrogen; or represented by the following Chemical Formula 2, provided that the ratio of the structure represented by the following Chemical Formula 2 is 1 mol% or more relative to the total molar number of -OH contained in the polyimide resin, m1, m2, k1 and k2 are each 0 or 1, and 1≤m1+m2+k1+k2≤2, Z is a direct bond or a divalent organic group, When the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05≤Z≤0.3, n is a real number from 1 to 50, and m is a real number from 0 to 50, [Chemical formula 2] Wherein, in Chemical Formula 2, * is a part connected to Chemical Formula 1, R7 is hydrogen; or substituted or unsubstituted alkyl, and p is an integer from 1 to 10.

2. The polyimide resin according to claim 1, wherein X1 and X2 are the same as or different from each other and are each independently selected from a tetravalent aromatic organic group, a tetravalent aliphatic organic group, and a tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

3. The polyimide resin according to claim 1, wherein X1 and X2 are the same as or different from each other and are each independently selected from the following structures: In the structure, It is a connecting portion to the carbonyl group (C(═O)) of Chemical Formula 1. 4 . The polyimide resin according to claim 1 , wherein Y is selected from a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

5. The polyimide resin according to claim 1, wherein Y is selected from the following structures: In the structure, A is a divalent organic group, and It is a connecting part with N of Chemical Formula 1.

6. The polyimide resin according to claim 5, wherein A is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2.

7. The polyimide resin according to claim 5, wherein A is selected from the following structures: In the structure, *for The connecting part of each phenol group.

8. The polyimide resin according to claim 1, wherein Z is a direct bond or any divalent organic group in the following structures: In the structure, B is a divalent organic group, and It is a connecting part with N of Chemical Formula 1.

9. The polyimide resin according to claim 8, wherein B is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or an alkyl.

10. The polyimide resin according to claim 8, wherein B is selected from the following structures: In the structure, *for The connecting part of each phenyl group.

11. The polyimide resin according to claim 1, further comprising a structure represented by the following Chemical Formula 3 as an end group: [Chemical formula 3] in, In chemical formula 3, * is a part connected to Chemical Formula 1, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is a real number from 0 to 4, and when re1 is 2 or more, Re1 are the same as or different from each other, and Re is hydrogen; or a structure represented by Chemical Formula 2. 12 . The polyimide resin according to claim 1 , wherein a ratio of the structure represented by Chemical Formula 2 is 10 mol % to 70 mol % with respect to the total moles of OH groups included in the polyimide resin. 13 . The polyimide resin according to claim 1 , wherein the polyimide resin has a weight average molecular weight of 5,000 g / mol to 200,000 g / mol. 14 . A negative photosensitive resin composition, comprising: the polyimide resin according to claim 1 ; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

15. The negative photosensitive resin composition according to claim 14, wherein the crosslinking agent comprises two or more types of structures represented by the following Chemical Formula 4: [Chemical formula 4] In chemical formula 4, R8 and R9 are the same as or different from each other and are each independently hydrogen; or substituted or unsubstituted alkyl, n' is an integer from 1 to 100, and The acrylate group (—COO—) of Chemical Formula 4 is connected to the acrylate group of Chemical Formula 2 during exposure. 16 . The negative photosensitive resin composition according to claim 14 , wherein the polyimide resin comprises one or two or more polyimide resins. 17 . An electronic device comprising an organic insulating film or a photosensitive pattern formed of the negative photosensitive resin composition according to claim 14 . 18 . The electronic device according to claim 17 , wherein the organic insulating film includes an interlayer insulating film and a surface protection film.

19. The electronic device of claim 17, further comprising a storage component.

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