Photosensitive resin precursor composition, photosensitive resin composition, insulating film, and semiconductor device

Abstract

The invention provides a photosensitive resin precursor composition, a photosensitive resin composition, an insulating film, and a semiconductor device.

Description

Technical Field

[0001] This specification relates to photosensitive resin precursor compositions, photosensitive resin compositions, insulating films, and semiconductor devices. Specifically, this specification relates to photosensitive resin precursor compositions for polymerizing polyimide resins, photosensitive resin compositions comprising polyimide resins, insulating films, and semiconductor devices. This application claims priority and benefit to Korean Patent Application No. 10-2023-0134202, filed on October 10, 2023, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Background Technology

[0002] Because the interlayer insulating film or surface protective film of semiconductor devices needs to have excellent mechanical properties and high heat resistance, polyimide-based adhesive resins with excellent physical properties are used.

[0003] As miniaturization technology expands its application in manufacturing processes (FAB), packaging technology is also undergoing significant changes in the process technology used to manufacture high-performance, thin, short, and small packages.

[0004] With the recent growth of the fan-out-wafer-level package (FO-WLP) market due to changes in semiconductor back-end process technology, there is a significant increase in demand for photosensitive polyimides (PIDs or PSPIs) for redistribution layers (RDLs) that can be cured at low temperatures and have excellent physical properties.

[0005] Although negative photosensitive polyimide (PID) has relatively superior mechanical properties, it is difficult to achieve high resolution. While positive photosensitive polyimide can achieve relatively high resolution, it is difficult to meet the required mechanical properties.

[0006] Furthermore, since harmful substances, such as highly toxic substances, are used in the photolithography process using photosensitive polyimide materials, especially during the development process, there are safety and environmental pollution issues.

[0007] Therefore, there is a need to develop technologies that can address safety and environmental pollution issues while providing photosensitive polyimide materials with excellent mechanical properties and the ability to achieve high resolution. Summary of the Invention

[0008] Technical issues

[0009] This invention aims to provide photosensitive resin precursor compositions for polymerizing polyimide resins, photosensitive resin compositions comprising polyimide resins, insulating films, and semiconductor devices.

[0010] However, the problems to be solved by the present invention are not limited to those described above, and those skilled in the art will clearly understand from the following description other problems not mentioned.

[0011] Technical solution

[0012] An exemplary embodiment of the present invention provides a photosensitive resin precursor composition comprising N,N-diethylformamide (DEF), wherein the photosensitive resin comprises a polyimide resin with an imidization rate of 90% or greater.

[0013] An exemplary embodiment of the present invention provides a photosensitive resin composition comprising a first organic solvent, wherein the photosensitive resin comprises a polyimide resin with an imidization rate of 90% or greater, and the first organic solvent comprises N,N-diethylformamide (DEF).

[0014] An exemplary embodiment of this specification provides an insulating film comprising a photosensitive resin composition or a cured product thereof.

[0015] One exemplary embodiment of this specification provides a semiconductor device that includes an insulating film.

[0016] Beneficial effects

[0017] The photosensitive resin precursor composition according to an exemplary embodiment of the present invention can improve safety and environmental pollution issues related to the polymerization process, while providing a photosensitive polyimide resin with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability.

[0018] The photosensitive resin composition according to an exemplary embodiment of the present invention can achieve an insulating film with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability, and improve safety and environmental pollution issues related to the preparation process.

[0019] In particular, the photosensitive resin composition according to an exemplary embodiment of the present invention exhibits excellent mechanical properties as a photosensitive material (e.g., high heat resistance, high elongation, low sensitivity, excellent adhesive strength, etc.) without modification by crosslinkable polymers, and therefore has excellent process compatibility and can achieve fine patterning.

[0020] Furthermore, since the insulating film according to an exemplary embodiment of the present invention comprises a photosensitive resin composition having high heat resistance, high elongation, low sensitivity and excellent adhesion, the semiconductor device using the insulating film has excellent reliability and the production efficiency of semiconductor packaging can be improved.

[0021] The effects of the present invention are not limited to those described above, and those skilled in the art will clearly understand from the description of this application any effects not mentioned. Detailed Implementation

[0022] Throughout this application, when a part “includes” a constituent element, unless otherwise specifically described, this does not mean the exclusion of other constituent elements, but rather that other constituent elements may be included.

[0023] Throughout this application, when a component is disposed "on" another component, this includes not only the case where one component is in contact with another component, but also the case where there is another component between the two components.

[0024] Throughout this application, the unit "parts by weight" may refer to the weight ratio between the components.

[0025] Throughout this application, “(meth)acrylate” is used to refer to both acrylates and methacrylates.

[0026] Throughout this application, the term “monomer” may mean the form in which a monomer is reacted to form a polymer, and more specifically, may mean the form in which the monomer that forms the backbone (e.g., main chain or side chain) of the monomer is reacted to form a polymer.

[0027] Throughout this application, the term "monomer unit" may refer to the form in which the monomer reacts in the polymer, and more specifically, may refer to the form in which the monomer undergoes a polymerization reaction to form the backbone (e.g., main chain or side chain) of the polymer.

[0028] In this specification, "polymer" means a compound consisting of repeating units (basic units). Polymers can be represented by macromolecules or compounds composed of macromolecules.

[0029] In this instruction manual, It can refer to a portion that is bonded to another substituent or bonding portion, or it can refer to a portion that is bonded to the main chain of the polymer of the present invention.

[0030] Examples of substituents will be described below in this specification, but are not limited thereto.

[0031] In this specification, the term "substituted or unsubstituted" means substituted with one or more of the following substituents: deuterium; halogen group; nitrile group; nitro group; hydroxyl group; -COOH group; alkoxy group; alkyl group; cycloalkyl group; alkenyl group; cycloalkenyl group; aryl group; heteroaryl group; and heterocyclic group containing one or more of O, N, or S atoms, or without substituents.

[0032] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0033] In this specification, the alkoxy group can be straight or branched, and there is no particular limitation on the number of carbon atoms, but it can be 1 to 30, specifically 1 to 20, and more specifically 1 to 10.

[0034] In this specification, the alkyl group can be straight-chain or branched, and its number of carbon atoms is not particularly limited, but is preferably from 1 to 60. In one exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. In another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. In yet another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0035] In this specification, the above description of alkyl groups is applied to alkylene groups, except that alkyl groups are divalent groups.

[0036] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and in one exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0037] In this specification, the alkenyl group can be linear or branched, and its carbon number is not particularly limited, but is preferably 2 to 60. In one exemplary embodiment, the alkyl group has 2 to 30 carbon atoms. In another exemplary embodiment, the alkyl group has 2 to 20 carbon atoms. In yet another exemplary embodiment, the alkyl group has 2 to 10 carbon atoms. Specific examples of alkenyl groups are preferably alkenyl groups in which an aryl group is substituted, for example... It includes, but is not limited to, styrene and styrene groups.

[0038] In this specification, the cycloalkenyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and in one exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Examples of cycloalkenyl groups are preferably cyclopentenyl and cyclohexenyl, but are not limited thereto.

[0039] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and can be monocyclic or polycyclic aryl. In one exemplary embodiment, the aryl group has 6 to 30 carbon atoms. In another exemplary embodiment, the aryl group has 6 to 20 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, etc. Examples of polycyclic aryl groups include naphthyl, anthraceneyl, indenyl, phenanthryl, pyrene, etc. Benzyl, phenylenetriene It includes, but is not limited to, methyl, fluorene, etc.

[0040] In this specification, the above description of aryl groups is applied to arylene groups, except that aryl groups are divalent groups.

[0041] In this specification, a heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom, and its number of carbon atoms is not particularly limited, but is 2 to 30, specifically 2 to 20. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazole, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] The heterocyclic group may include, but is not limited to, azole, benzimidazol, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, tetrahydropyran, etc. Preferably, the heterocyclic group is tetrahydropyran.

[0042] In this specification, the above description of heterocyclic groups can be applied to heteroaryl groups, except that heteroaryl groups are aromatic.

[0043] In this specification, the aromatic ring can be aryl or heteroaryl, and the above description applies to both aryl and heteroaryl rings. An aliphatic ring may refer to a ring that is not an aromatic ring.

[0044] In this specification, the "weight-average molecular weight" and "number-average molecular weight" of a compound can be calculated using the compound's molecular weight and molecular weight distribution. Specifically, a sample containing a 1% by weight concentration of the compound is prepared by placing tetrahydrofuran (THF) and the compound in a 1 ml glass vial. The standard sample (polystyrene) and the sample are filtered through a filter (0.45 μm pore size). The molecular weight and molecular weight distribution of the compound are then obtained by comparing the elution time of the sample with the calibration curve of the standard sample by injecting the sample into a GPC injector. In this case, an Infinity II 1260 (manufactured by Agilent Inc.) can be used as the measuring device, and the flow rate and column temperature can be set to 1.00 mL / min and 40.0 °C, respectively.

[0045] The invention will be described in more detail below.

[0046] [Photosensitive Resin Precursor Composition]

[0047] An exemplary embodiment of the present invention provides a photosensitive resin precursor composition comprising N,N-diethylformamide (DEF), wherein the photosensitive resin comprises a polyimide resin with an imidization rate of 90% or greater.

[0048] The photosensitive resin precursor composition according to an exemplary embodiment of the present invention can improve safety and environmental pollution issues related to the polymerization process, while providing a photosensitive polyimide resin with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability.

[0049] In one exemplary embodiment of the invention, the photosensitive resin precursor composition may contain N,N-diethylformamide (DEF). N,N-diethylformamide (DEF) is a component that imparts solubility to the photosensitive resin precursor mixture contained in the photosensitive resin precursor composition and can be used to promote the polymerization of the photosensitive resin precursor mixture. By including N,N-diethylformamide (DEF) in the photosensitive resin precursor composition, the solubility of the photosensitive resin precursor mixture according to the invention can be maintained at an appropriate level, making it easier to polymerize the polyimide resin contained in the photosensitive resin composition.

[0050] Furthermore, safety and environmental pollution issues related to the polymerization process can be mitigated by reducing the use of polymerization solvents designated as hazardous substances (such as N-methyl-2-pyrrolidone (NMP) and cyclopentanone (CPO)). Additionally, by including the polyimide resin described below, the photosensitive resin precursor composition is particularly suitable for processes and methods of patterning insulating films with excellent elongation, sensitivity, and / or adhesion to substrates, as well as high reliability, and can achieve patterns with excellent mechanical properties and high resolution on the insulating film.

[0051] In one exemplary embodiment of the present invention, the photosensitive resin may comprise a polyimide resin with an imidization rate of 90% or greater. Specifically, the photosensitive resin precursor composition may be used for the polymerization of the photosensitive resin contained in the photosensitive resin composition, and the polymerized photosensitive resin may further comprise solvents, etc., and may be a photosensitive resin composition for curing to form an insulating film.

[0052] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may be a precursor composition for polymerizing a photosensitive resin, and the photosensitive resin may be a photosensitive polyimide resin. Specifically, the photosensitive resin may include a polyimide resin, and the imidization rate of the polyimide resin may be 90% or greater. More specifically, in the photosensitive resin composition, the imidization rate of the polyimide resin may be 90% or greater, 92% or greater, 94% or greater, or 96% or greater, and the insulating film to be prepared therefrom may have excellent elongation, sensitivity and / or adhesion to the substrate, and high reliability.

[0053] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a mixture of photosensitive polyimide resin precursors for polymerizing photosensitive polyimide resins.

[0054] In one exemplary embodiment of the invention, the photosensitive resin precursor composition may contain at least one first monomer represented by any of the following chemical formulas 1-1-1 to 1-1-4.

[0055] [Chemical Formula 1-1-1]

[0056]

[0057] [Chemical Formula 1-1-2]

[0058]

[0059] [Chemical Formula 1-1-3]

[0060]

[0061] [Chemical Formula 1-1-4]

[0062]

[0063] In chemical formulas 1-1-1 to 1-1-4,

[0064] L11 represents a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -SO2-; -CO-; or -OCO-.

[0065] L12 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-,

[0066] n is an integer from 1 to 3, and when n is 2 or greater, L is either the same or different from each other.

[0067] L13 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-.

[0068] R1 through R6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups.

[0069] r1 and r2 are either the same or different, and are each an independent integer from 0 to 3. Furthermore, when r1 is 2 or greater, r1 is either the same or different, and when r2 is 2 or greater, r2 is either the same or different.

[0070] r3 and r4 are either the same or different from each other, and are each an independent integer from 0 to 4. Furthermore, when r3 is 2 or greater, r3 is either the same or different from each other, and when r4 is 2 or greater, r4 is either the same or different from each other.

[0071] r5 and r6 are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when r5 is 2 or greater, r5 are either the same or different from each other, and when r6 is 2 or greater, r6 are either the same or different from each other.

[0072] Ra and Rb may be the same as or different from each other, and each is independently hydrogen; or a structure represented by the following chemical formula a,

[0073] [Chemical formula a]

[0074]

[0075] In chemical formula a,

[0076] This refers to the part connected to the chemical formula 1-1-1 or 1-1-2.

[0077] R7 is hydrogen; or a substituted or unsubstituted alkyl group, and

[0078] q is an integer from 1 to 10.

[0079] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may contain at least one first monomer represented by any one of chemical formulas 1-1-1 to 1-1-4.

[0080] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-1; and a first monomer represented by chemical formula 1-1-2.

[0081] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-1; and a first monomer represented by chemical formula 1-1-3.

[0082] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-1; and a first monomer represented by chemical formula 1-1-4.

[0083] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-2; and a first monomer represented by chemical formula 1-1-3.

[0084] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-2; and a first monomer represented by chemical formula 1-1-4.

[0085] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may comprise a first monomer represented by chemical formula 1-1-3; and a first monomer represented by chemical formula 1-1-4.

[0086] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may contain a first monomer represented by chemical formula 1-1-1.

[0087] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may contain a first monomer represented by chemical formula 1-1-2.

[0088] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may contain a first monomer represented by chemical formula 1-1-3.

[0089] In one exemplary embodiment of the present invention, the photosensitive resin precursor composition may contain a first monomer represented by chemical formula 1-1-4.

[0090] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0091] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0092] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0093] In one exemplary embodiment of the present invention, L11 can be a direct bond; an unsubstituted or halogenated alkylene group having 1 to 10 carbon atoms; -SO2-; -CO-; or -OCO-.

[0094] In one exemplary embodiment of the present invention, L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group, n is an integer from 1 to 3, and when n is 2 or greater, L can be the same or different from each other.

[0095] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0096] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0097] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0098] In one exemplary embodiment of the invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -OCO-; or -O-(L). n -O-.

[0099] In one exemplary embodiment of the present invention, L may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0100] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-.

[0101] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0102] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0103] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0104] In one exemplary embodiment of the invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or -O-.

[0105] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0106] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0107] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0108] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0109] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0110] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0111] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0112] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0113] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0114] In one exemplary embodiment of the invention, Ra and Rb may be the same as or different from each other, and may each be hydrogen independently; or a structure represented by the following chemical formula a.

[0115] [Chemical formula a]

[0116]

[0117] In one exemplary embodiment of the present invention, as an example, chemical formula a may include any of the following structures, and it is sufficient as long as q is an integer from 1 to 10, and chemical formula a is not limited to the following examples.

[0118]

[0119] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0120] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0121] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0122] In one exemplary embodiment of the invention, at least one of Ra and Rb includes a structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be greater than 0 mol% and 100 mol% or less relative to the total content of the polyimide resin precursor mixture.

[0123] In one exemplary embodiment of the invention, at least one of Ra and Rb includes a structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be 10 mol% or more and 100 mol% or less, 20 mol% or more and 100 mol% or less, 30 mol% or more and 100 mol% or less, 40 mol% or more and 100 mol% or less, 50 mol% or more and 100 mol% or less, 60 mol% or more and 100 mol% or less, 70 mol% or more and 100 mol% or less, 80 mol% or more and 100 mol% or less, 90 mol% or more and 100 mol% or less, or 100% relative to the total content of the polyimide resin precursor mixture.

[0124] In one exemplary embodiment of the invention, the content of the structure represented by chemical formula a relative to the total content of the polyimide resin precursor mixture can be determined by commercially available NMR, and after the resin synthesis reaction is completed, the content (mol%) of the structure represented by chemical formula a can be determined by: obtaining the amount of OH before the reaction from the number of protons in all the aromatic rings of the polyimide, to obtain the number of protons of chemical formula a relative to the amount of OH before the reaction (the integral of the (3H) peaks from 6.41 ppm to 5.83 ppm).

[0125] In one exemplary embodiment of the invention, the first monomer represented by any of the chemical formulas 1-1-1 to 1-1-4 may be selected from any of the following structural formulas.

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] In the structural formula, Ra and Rb are defined as described above in chemical formulas 1-1-1 and 1-1-2.

[0135] In one exemplary embodiment of the invention, the polyimide resin precursor mixture may further include a third monomer as a capping agent. Specifically, the third monomer may form end groups of the polyimide resin.

[0136] In one exemplary embodiment of the present invention, the third monomer may be 5-norbornene-2,3-dicarboxylic anhydride (NDA).

[0137] In one exemplary embodiment of the present invention, the third monomer may be represented by the following chemical formulas 1-E.

[0138] [Chemical Formula 1-E]

[0139]

[0140] In chemical formula 1-E,

[0141] Re1 is hydrogen; or a substituted or unsubstituted alkyl group.

[0142] re1 is an integer from 0 to 4, and when re1 is 2 or greater, two or more re1 values ​​are the same or different from each other.

[0143] Re represents hydrogen; or a structure represented by the chemical formula a.

[0144] In one exemplary embodiment of the invention, Re1 can be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0145] In one exemplary embodiment of the invention, Re1 can be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0146] In one exemplary embodiment of the invention, Re1 can be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0147] In one exemplary embodiment of the present invention, Re can be hydrogen; or a structure represented by chemical formula a.

[0148] In one exemplary embodiment of the present invention, Re is a structure represented by chemical formula a. The content of chemical formula a is as described above.

[0149] In one exemplary embodiment of the present invention, based on 100 mol% of the first monomer, the photosensitive resin precursor composition may contain 20 mol% or more and less than 40 mol% of the first monomer represented by chemical formula 1-1-1. Specifically, the photosensitive resin precursor composition may contain two or more different first monomers, and based on 100 mol% of the first monomer, the photosensitive resin precursor composition may contain 25 mol% or more or 30 mol% or more of the first monomer represented by chemical formula 1-1-1, and the photosensitive resin precursor composition may contain 35 mol% or less or 30 mol% or less of the first monomer represented by chemical formula 1-1-1.

[0150] When the photosensitive resin precursor composition contains a first monomer represented by chemical formula 1-1-1 within the above range, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, making the photosensitive resin precursor composition more suitable for the polymerization of the photosensitive resin according to the present invention.

[0151] In one exemplary embodiment of the invention, based on 100 mol% of the first monomer, the photosensitive resin precursor composition may contain 50 mol% or more of the monomer represented by chemical formula 1-1-3, wherein L12 is -O-(L). n The first monomer of -O-. Here, L and n are as described above in chemical formula 1-1-3.

[0152] Specifically, the photosensitive resin precursor composition may contain two or more different first monomers, and may contain a monomer represented by chemical formula 1-1-3, wherein L12 is -O-(L). n The first monomer of the -O- group. For example, the first monomer can be 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP).

[0153] More specifically, based on 100 mol% of the first monomer, the photosensitive resin precursor composition may contain 55 mol% or more, 60 mol% or more, 65 mol% or more, or 70 mol% or more of the [representation] of chemical formula 1-1-3, wherein L12 is -O-(L). n The first monomer of -O-.

[0154] When the photosensitive resin precursor composition contains, in the above-mentioned amount, an ingredient represented by chemical formula 1-1-3, wherein L12 is -O-(L). n When the first monomer is -O-, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, making the photosensitive resin precursor composition more suitable for the polymerization of the photosensitive resin according to the present invention.

[0155] In one exemplary embodiment of the invention, the polyimide resin precursor mixture may further comprise a second monomer represented by any of the following chemical formulas 1-2-1 to 1-2-4.

[0156] [Chemical Formula 1-2-1]

[0157]

[0158] [Chemical Formula 1-2-2]

[0159]

[0160] [Chemical Formula 1-2-3]

[0161]

[0162] [Chemical Formula 1-2-4]

[0163]

[0164] In chemical formulas 1-2-1 to 1-2-4,

[0165] L21 to L23 may be the same as or different from each other, and each is an independent direct bond; substituted or unsubstituted alkylene groups; substituted or unsubstituted aryl groups; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-,

[0166] L' and L'' may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group.

[0167] m is an integer from 1 to 5, and when m is 2 or greater, L'' are either the same or different from each other.

[0168] Ra1 to Ra6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups.

[0169] Ra1 to Ra6 are either the same or different from each other, and are each an independent integer from 0 to 3. Ra1 is either the same or different from each other when Ra1 is 2 or greater; Ra2 is either the same or different from each other when Ra2 is 2 or greater; Ra3 is either the same or different from each other when Ra3 is 2 or greater; Ra4 is either the same or different from each other when Ra4 is 2 or greater; Ra5 is either the same or different from each other when Ra5 is 2 or greater; and Ra6 is either the same or different from each other when Ra6 is 2 or greater.

[0170] Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

[0171] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms; substituted or unsubstituted aryl groups having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0172] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms; substituted or unsubstituted aryl groups having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0173] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms; substituted or unsubstituted aryl groups having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0174] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0175] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0176] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0177] In one exemplary embodiment of the invention, the second monomer represented by any of the chemical formulas 1-2-1 to 1-2-4 may be selected from any of the following chemical formulas.

[0178]

[0179]

[0180]

[0181]

[0182]

[0183] According to an exemplary embodiment of the present invention, based on 100 mol% of the second monomer, the photosensitive resin precursor composition may contain 20 mol% or more of a second monomer represented by chemical formula 1-2-1, wherein L21 is a direct bond. Specifically, the photosensitive resin precursor composition may contain two or more different second monomers, and may contain a second monomer represented by chemical formula 1-2-1, wherein L21 is a direct bond. For example, the second monomer may be 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA).

[0184] More specifically, based on 100 mol% of the second monomer, the photosensitive resin precursor composition may contain 20 mol% or more, or 25 mol% or more, or 50 mol% or less, or 45 mol% or less of the second monomer represented by chemical formula 1-2-1, wherein L21 is a direct bond.

[0185] When the photosensitive resin precursor composition contains a second monomer represented by chemical formula 1-2-1 in the above-mentioned amount, wherein L21 is a direct bond, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, making the photosensitive resin precursor composition more suitable for the polymerization of the photosensitive resin according to the present invention.

[0186] [Photosensitive Resin Composition]

[0187] An exemplary embodiment of the present invention provides a photosensitive resin composition comprising polyimide resin as described below.

[0188] According to an exemplary embodiment of the present invention, the photosensitive resin composition may be a photosensitive resin composition comprising a first organic solvent, wherein the photosensitive resin comprises a polyimide resin with an imidization rate of 90% or greater, and the first organic solvent comprises N,N-diethylformamide (DEF).

[0189] In one exemplary embodiment of the present invention, the photosensitive resin composition may comprise a polyimide resin with an imidization rate of 90% or greater. Specifically, the photosensitive resin composition may be a photosensitive polyimide resin composition, and the imidization rate of the polyimide resin contained in the photosensitive resin composition may be 90% or greater. More specifically, in the photosensitive resin composition, the imidization rate of the polyimide resin may be 90% or greater, 92% or greater, 94% or greater, or 96% or greater, and the insulating film to be prepared therefrom may have excellent elongation, sensitivity and / or adhesion to the substrate, and high reliability.

[0190] In one exemplary embodiment of the present invention, the photosensitive resin composition comprises a first organic solvent, and the first organic solvent may include N,N-diethylformamide (DEF).

[0191] In one exemplary embodiment of the invention, the boiling point of the first organic solvent may be 160°C or higher and 200°C or lower. Specifically, the boiling point of the first organic solvent may be 165°C or higher, 170°C or higher, or 175°C or higher, and the boiling point of the first organic solvent may be 200°C or lower, 195°C or lower, 190°C or lower, or 185°C or lower. When the boiling point of the first organic solvent is within the above range, the photosensitive resin composition may be more suitable for the preparation process of an insulating film containing polyimide resin, thereby producing an insulating film with excellent mechanical properties such as elongation and dielectric constant, and providing an insulating film with high-resolution patterning due to excellent developability.

[0192] In one exemplary embodiment of the invention, the flash point of the first organic solvent may be 50°C or higher and 90°C or lower. Specifically, the flash point of the first organic solvent may be 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, and the flash point of the first organic solvent may be 85°C or lower, 80°C or lower, 75°C or lower, or 70°C or lower. When the boiling point of the first organic solvent is within the above range, the photosensitive resin composition may be more suitable for the preparation process of the insulating film containing polyimide resin, and the insulating film thus prepared may have excellent mechanical properties such as elongation and dielectric constant.

[0193] In one exemplary embodiment of the present invention, the content of N,N-diethylformamide based on 100 parts by weight of the first organic solvent can be 50 parts by weight or more and 100 parts by weight or less. Specifically, the content of N,N-diethylformamide based on 100 parts by weight of the first organic solvent can be 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more, or 70 parts by weight or more, and 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, or 80 parts by weight or less. When the content of N,N-diethylformamide meets the above ranges, an insulating film with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability can be achieved. Furthermore, the insulating film prepared from the photosensitive resin composition can have excellent mechanical properties and excellent developability, thereby improving safety and environmental pollution issues related to the preparation process, while providing an insulating film capable of achieving high-resolution patterns.

[0194] In one exemplary embodiment of the invention, the first organic solvent may further include a polar organic solvent. Specifically, the first organic solvent may be a polar aprotic organic solvent. More specifically, the first organic solvent may also include any of the following: propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), diethylene glycol methyl ethyl ether (MEDG), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxybutyl acetate (3-MBA), ethyl lactate (EL), and mixtures thereof. For example, the first organic solvent may also include propylene glycol monomethyl ether acetate (PGMEA). When the first organic solvent further includes a polar organic solvent, the insulating film prepared from the photosensitive resin composition can have excellent mechanical properties and excellent developability, and therefore, can provide an insulating film capable of achieving high-resolution patterns.

[0195] In other words, the first organic solvent can be a single solvent of N,N-diethylformamide (DEF) or a mixture of N,N-diethylformamide (DEF) and other polar organic solvents.

[0196] In one exemplary embodiment of the present invention, the photosensitive resin composition may further comprise a photoradical initiator. Specifically, the photoradical initiator is a substance that plays a role in initiating the crosslinking and / or curing reaction of the photosensitive resin when exposed to light. Any typical photoradical initiator can be used without limitation, and preferably, an oxime-based photoradical initiator can be used, such as OXE-03, OXE-04, SPI-03, SPI-07, I367, etc., but the photoradical initiator is not limited thereto.

[0197] In one exemplary embodiment of the present invention, the photosensitive resin composition may further comprise a photoacid generator.

[0198] In one exemplary embodiment of the present invention, the photoacid generator is used to allow the photosensitive resin composition to function as a chemically amplified composition, and to improve pattern resolution, etc., by effectively controlling the acid diffusion length. As the photoacid generator, any typical photoacid generator can be used without limitation, and preferably, ionic photoacid generators, sulfonyldiazomethane-based photoacid generators, N-sulfonyloxyimide-based photoacid generators, benzoin sulfonate / salt-based photoacid generators, nitrobenzyl sulfonate / salt-based photoacid generators, sulfone-based photoacid generators, oxime-based photoacid generators, triazine-based photoacid generators, etc., can be used.

[0199] In one exemplary embodiment of the present invention, the photosensitive resin composition may further comprise additives. Specifically, the additives may further comprise one or more of surfactants, antioxidants, sensitizers, and crosslinking agents.

[0200] In one exemplary embodiment of the present invention, the photosensitive resin composition may include all of the surfactant, antioxidant, sensitizer and crosslinking agent as additives.

[0201] In one exemplary embodiment of the present invention, the surfactant is a silicon-based surfactant or a fluorine-based surfactant. Specifically, as a silicon-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, and BYK-325 manufactured by BYK-Chemie can be used. BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, 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, can be used from Dainippon Ink & Chemicals. (DIC), Inc. manufactures the 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, and F-4... 86, 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 surfactants are not limited to these.

[0202] In one exemplary embodiment of the present invention, antioxidants can play a role in improving the elongation properties of the cured film or its adhesion to metallic materials. Furthermore, antioxidants can inhibit the oxidative degradation of the aliphatic groups or phenolic hydroxyl groups of the polyimide resin, and can inhibit metal oxidation through their anti-corrosion effect on metallic materials. Specific examples of antioxidants include, but are not limited to, the following compounds.

[0203] In one exemplary embodiment of the present invention, the sensitizer can improve the resolution of the pattern, etc., by effectively controlling the acid diffusion length. Specifically, as sensitizers, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3-methylphenyl)-3,4-dihydroxyphenylmethane, and bis(4-hydroxy-3-methylphenyl)-3,4-dihydroxyphenylmethane can be used. 2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-4-hydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, etc., and preferably, a sensitizer for the i-line can be used.

[0204] In one exemplary embodiment of the invention, the crosslinking agent is not particularly limited and can be used without limitation, as long as the crosslinking agent is applicable in the art. Thermal crosslinking agents or free radical monomers can generally be used as crosslinking agents. Examples of crosslinking agents include compounds having at least two alkoxymethyl groups and / or hydroxymethyl groups, and compounds having at least two epoxy groups and / or oxetyl groups, but the crosslinking agent is not limited thereto. By including the compounds exemplified above, a condensation reaction can be induced with the resin of the invention during sintering after patterning to form a crosslinked structure, and the mechanical properties of the cured resin pattern, such as elongation, can be improved. Furthermore, two or more of the crosslinking agents can be used in combination, thereby allowing for a wide variety of designs.

[0205] In one exemplary embodiment of the invention, preferred examples of compounds having at least two alkoxymethyl and / or hydroxymethyl groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC- P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOMBPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), are available for purchase from the respective companies. Two or more of these may be included.

[0206] In addition, preferred examples of compounds having at least two epoxy groups and / or oxetyl groups include, but are not limited to, bisphenol A type epoxy resins, bisphenol A type oxetyl resins, bisphenol F type epoxy resins, bisphenol F type oxetyl resins, epoxy-containing organosilicones, such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl)siloxane. Specific examples include EPICLON (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, and EPICLON EXA-4822 (all trade names, manufactured by Dai Nippon Ink Kagaku KK), and RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by Shin-Nippon Rika). (KK manufactured), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Corporation), etc., which can be purchased from various companies. Two or more of these may be included.

[0207] In addition, 2-[[4-[2-[4-[1,1-bis[4-(ethylene oxide-2-ylmethoxy)phenyl]ethyl]phenyl]prop-2-yl]phenoxy]methyl]ethylene oxide, tetraethylene dimethacrylate, etc. can be used as crosslinking agents.

[0208] Based on 100 parts by weight of the whole polyimide resin, the content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, or even more preferably 10 parts by weight or more, and from the point of view of maintaining mechanical properties such as elongation, the content of the crosslinking agent is preferably 300 parts by weight or less, or more preferably 200 parts by weight or less.

[0209] In an exemplary embodiment of the present invention, to improve the resolution characteristics of the embossed pattern, the photosensitive resin composition may further comprise a monomer having photopolymerizable unsaturated bonds. As such monomers, (meth)acrylate compounds that undergo free radical polymerization via a photoinitiator are preferred, and in particular, examples include, but are not limited to, compounds such as monoacrylates or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; monoacrylates or diacrylates and methacrylates of propylene glycol or polyethylene glycol; monoacrylates, diacrylates or triacrylates and methacrylates of glycerol; cyclohexane diacrylates and cyclohexane dimethacrylates; and diacrylates and dimethacrylates of 1,4-butanediol. Diacrylates and dimethacrylates of 1,6-hexanediol; diacrylates and dimethacrylates of neopentyl glycol; monoacrylates or diacrylates and methacrylates of bisphenol A; trimethacrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane methacrylate; diacrylates or triacrylates and methacrylates of glycerol; diacrylates, triacrylates or tetraacrylates and methacrylates of pentaerythritol; and ethylene oxide or propylene oxide addition products of these compounds.

[0210] Based on 100 parts by weight of the whole polyimide resin, the content of monomers having photopolymerizable unsaturated bonds is preferably from 1 part by weight to 50 parts by weight.

[0211] In one exemplary embodiment of the present invention, the photosensitive resin composition may further comprise a compound known in the art to which this invention pertains that is capable of forming a photosensitive resin composition as a first organic solvent. Specifically, the first organic solvent may further comprise one or more compounds selected from the following: esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0212] The ester compounds can be 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 oxyacetic acid esters (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionic acid esters (e.g., methyl 3-oxypropionic acid, ethyl 3-oxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid)). Methyl ester, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxypropionate esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 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-oxobutyrate, ethyl 2-oxobutyrate, etc.

[0213] Ether compounds 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.

[0214] Ketone compounds can be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0215] Aromatic hydrocarbon compounds can include toluene, xylene, anisole, limonene, etc.

[0216] The sulfoxide compound can be dimethyl sulfoxide, etc.

[0217] In one exemplary embodiment of the present invention, the additive may also include adhesion promoters, defoamers, leveling agents, anti-gelling agents or mixtures thereof, but is not limited thereto, and may also include additives known in the art depending on the application.

[0218] In one exemplary embodiment of the present invention, the sensitivity of the photosensitive resin composition can be 350 mJ / cm. 2 Or smaller.

[0219] In one exemplary embodiment of the present invention, the sensitivity of the photosensitive resin composition can be approximately 350 mJ / cm.2 Or smaller, approximately 340 mJ / cm 2 Or smaller, approximately 330 mJ / cm 2 Or smaller, approximately 320 mJ / cm 2 Or smaller, or about 310 mJ / cm 2 Or even lower. There is no particular limitation on the lower limit of sensitivity, but it is approximately 350 mJ / cm². 2 At or below the minimum, it can be determined that the photosensitive resin composition has excellent physical properties as a photosensitive material (e.g., easy development to obtain fine patterns).

[0220] In one exemplary embodiment of the present invention, based on 100 parts by weight of polyimide resin, the photosensitive resin composition may contain 1 to 40 parts by weight of a photoacid generator; 5 to 50 parts by weight of a crosslinking agent; and 0.05 to 5 parts by weight of a surfactant.

[0221] In one exemplary embodiment of the invention, the photosensitive resin composition may contain 50 to 500 parts by weight of a first organic solvent relative to 100 parts by weight of polyimide resin.

[0222] When the components are included in the photosensitive resin composition within the above-mentioned weight range, even with the use of a small amount of photoacid generator, the sensitivity and physical properties can be improved, and the adhesion to the substrate can be improved.

[0223] In an exemplary embodiment of the present invention, the photosensitive resin composition may be a negative photosensitive composition. Specifically, in the photosensitive resin composition in which at least a portion is exposed to light, i.e., in the exposed portion, imidization of the precursor contained in the photosensitive resin composition is performed, and the solubility in the developer used for the photosensitive resin composition may decrease, while the unexposed portion may dissolve in the developer used for the photosensitive resin composition. Therefore, when the photosensitive resin composition is developed with the developer used for the photosensitive resin composition, the unexposed portion dissolves in the developer and is removed, while the exposed portion can be retained because it does not have sufficient solubility in the developer. As a developing method, for example, spray developing, immersion developing, paddle developing, etc., may be used, but the developing method is not limited to these.

[0224] [Polyimide resin]

[0225] In one exemplary embodiment of the present invention, the polyimide resin may be a polyimide resin comprising at least one of the structures represented by the following chemical formulas 2-1-1 to 2-1-4.

[0226] [Chemical Formula 2-1-1]

[0227]

[0228] [Chemical Formula 2-1-2]

[0229]

[0230] [Chemical Formula 2-1-3]

[0231]

[0232] [Chemical Formula 2-1-4]

[0233]

[0234] In chemical formulas 2-1-1 to 2-1-4,

[0235] This refers to the portion that is bonded to another substituent or repeating unit.

[0236] L11 represents a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -SO2-; -CO-; or -OCO-.

[0237] L12 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O(L) n O-,

[0238] L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group.

[0239] n is an integer from 1 to 3, and when n is 2 or greater, L is either the same or different from each other.

[0240] L13 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-.

[0241] R1 through R6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups.

[0242] r1 and r2 are either the same or different, and are each an independent integer from 0 to 3. Furthermore, when r1 is 2 or greater, r1 is either the same or different, and when r2 is 2 or greater, r2 is either the same or different.

[0243] r3 and r4 are either the same or different from each other, and are each an independent integer from 0 to 4. Furthermore, when r3 is 2 or greater, r3 is either the same or different from each other, and when r4 is 2 or greater, r4 is either the same or different from each other.

[0244] r5 and r6 are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when r5 is 2 or greater, r5 are either the same or different from each other, and when r6 is 2 or greater, r6 are either the same or different from each other.

[0245] Ra and Rb may be the same as or different from each other, and each is independently hydrogen; or a structure represented by the following chemical formula a,

[0246] [Chemical formula a]

[0247]

[0248] In chemical formula a,

[0249] This refers to the part connected to the chemical formula 2-1-1 or 2-1-2.

[0250] R7 is hydrogen; or a substituted or unsubstituted alkyl group, and

[0251] q is an integer from 1 to 10.

[0252] In one exemplary embodiment of the invention, the polyimide resin may comprise at least one structure represented by any one of chemical formulas 2-1-1 to 2-1-4.

[0253] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-1; and a structure represented by chemical formula 2-1-2.

[0254] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-1; and a structure represented by chemical formula 2-1-3.

[0255] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-1; and a structure represented by chemical formula 2-1-4.

[0256] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-2; and a structure represented by chemical formula 2-1-3.

[0257] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-2; and a structure represented by chemical formula 2-1-4.

[0258] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-3; and a structure represented by chemical formula 2-1-4.

[0259] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-1.

[0260] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-2.

[0261] In one exemplary embodiment of the invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-3.

[0262] In one exemplary embodiment of the present invention, the polyimide resin may comprise a structure represented by chemical formula 2-1-4.

[0263] Photosensitive resin compositions containing polyimide resins can easily achieve fine patterns and have excellent resolution. Furthermore, the photosensitive resin compositions according to this specification can provide a large number of photosensitive resin compositions with excellent sensitivity. Specifically, photosensitive resin compositions can be provided by containing DEF solvents to provide photosensitive resin compositions with excellent solubility and environmental friendliness.

[0264] According to an exemplary embodiment of the present invention, the photosensitive resin composition can have improved properties through fine patterning and a high crosslinking rate by including a suitable photoinitiator. In particular, the photosensitive resin composition can have high elongation and low dielectric constant due to its high crosslinking density.

[0265] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0266] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0267] In one exemplary embodiment of the present invention, L11 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0268] In one exemplary embodiment of the present invention, L11 can be a direct bond; an unsubstituted or halogenated alkylene group having 1 to 10 carbon atoms; -SO2-; -CO-; or -OCO-.

[0269] In one exemplary embodiment of the present invention, L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group, n is an integer from 1 to 3, and when n is 2 or greater, L can be the same or different from each other.

[0270] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0271] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0272] In one exemplary embodiment of the present invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-.

[0273] In one exemplary embodiment of the invention, L12 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -OCO-; or -O-(L). n -O-.

[0274] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-.

[0275] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0276] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0277] In one exemplary embodiment of the present invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0278] In one exemplary embodiment of the invention, L13 can be a direct bond; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or -O-.

[0279] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0280] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0281] In one exemplary embodiment of the invention, R1 and R2 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0282] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0283] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0284] In one exemplary embodiment of the invention, R3 and R4 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0285] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0286] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0287] In one exemplary embodiment of the invention, R5 and R6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0288] In one exemplary embodiment of the invention, Ra and Rb may be the same as or different from each other, and may each be hydrogen independently; or a structure represented by the following chemical formula a.

[0289] [Chemical formula a]

[0290]

[0291] In one exemplary embodiment of the present invention, as an example, chemical formula a may include any of the following structures, and it is sufficient as long as q is an integer from 1 to 10, and chemical formula a is not limited to the following examples.

[0292]

[0293] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0294] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0295] In one exemplary embodiment of the invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0296] In one exemplary embodiment of the invention, at least one of Ra and Rb includes a structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be greater than 0 mol% and 100 mol% or less relative to the total content of the polyimide resin.

[0297] In one exemplary embodiment of the present invention, at least one of Ra and Rb includes a structure represented by chemical formula a, and the content of the structure represented by chemical formula a relative to the total content of the polyimide resin can be 10 mol% or more and 100 mol% or less, 20 mol% or more and 100 mol% or less, 30 mol% or more and 100 mol% or less, 40 mol% or more and 100 mol% or less, 50 mol% or more and 100 mol% or less, 60 mol% or more and 100 mol% or less, 70 mol% or more and 100 mol% or less, 80 mol% or more and 100 mol% or less, 90 mol% or more and 100 mol% or less, or 100%.

[0298] In one exemplary embodiment of the invention, the content of the structure represented by chemical formula a relative to the total content of the polyimide resin can be determined by commercially available NMR, and the content (mol%) of the structure represented by chemical formula a after the resin synthesis reaction is completed can be determined by: obtaining the amount of OH before the reaction from the number of protons in all the aromatic rings of the polyimide, to obtain the number of protons of chemical formula a relative to the amount of OH before the reaction (the integral of the (3H) peaks from 6.41 ppm to 5.83 ppm).

[0299] In one exemplary embodiment of the present invention, chemical formulas 2-1-1 to 2-1-4 may be represented by any of the following structural formulas.

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308] In the structural formula, Ra and Rb are defined as in chemical formulas 2-1-1 and 2-1-2, and It can refer to additional substituents or portions that are bonded to the repeating unit.

[0309] In one exemplary embodiment of the invention, the polyimide resin may further comprise a structure represented by the following chemical formula 2-E-1 or the following chemical formula 2-E-2.

[0310] [Chemical formula 2-E-1]

[0311]

[0312] [Chemical formula 2-E-2]

[0313]

[0314] In chemical formulas 2-E-1 and 2-E-2,

[0315] This refers to the portion that is bonded to another substituent or repeating unit.

[0316] Re2 is hydrogen; or a substituted or unsubstituted alkyl group.

[0317] re2 is an integer from 0 to 4, and when re2 is 2 or greater, two or more re2 values ​​are the same or different from each other.

[0318] Re represents hydrogen; or a structure represented by the chemical formula a.

[0319] In one exemplary embodiment of the present invention, the structure represented by the chemical formula 2-E-1 or 2-E-2 can be an end group of a polyimide resin.

[0320] In one exemplary embodiment of the invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0321] In one exemplary embodiment of the invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0322] In one exemplary embodiment of the invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0323] In one exemplary embodiment of the present invention, Re can be hydrogen; or a structure represented by chemical formula a.

[0324] In one exemplary embodiment of the present invention, Re is a structure represented by chemical formula a. The content of chemical formula a is as described above.

[0325] In one exemplary embodiment of the invention, the polyimide resin may further comprise any of the structures represented by any of the following chemical formulas 2-2-1 to 2-2-4.

[0326] [Chemical Formula 2-2-1]

[0327]

[0328] [Chemical Formula 2-2-2]

[0329]

[0330] [Chemical Formula 2-2-3]

[0331]

[0332] [Chemical Formula 2-2-4]

[0333]

[0334] In chemical formulas 2-2-1 to 2-2-4,

[0335] This refers to the portion that is bonded to other substituents or repeating units.

[0336] L21 to L23 may be the same as or different from each other, and each is an independent direct bond; substituted or unsubstituted alkylene groups; substituted or unsubstituted aryl groups; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-,

[0337] L' and L'' may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group.

[0338] m is an integer from 1 to 5, and when m is 2 or greater, L'' are either the same or different from each other.

[0339] Ra1 to Ra6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups.

[0340] Ra1 to Ra6 are either the same or different from each other, and are each an independent integer from 0 to 3. Ra1 is either the same or different from each other when Ra1 is 2 or greater; Ra2 is either the same or different from each other when Ra2 is 2 or greater; Ra3 is either the same or different from each other when Ra3 is 2 or greater; Ra4 is either the same or different from each other when Ra4 is 2 or greater; Ra5 is either the same or different from each other when Ra5 is 2 or greater; and Ra6 is either the same or different from each other when Ra6 is 2 or greater.

[0341] Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

[0342] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms; substituted or unsubstituted aryl groups having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0343] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms; substituted or unsubstituted aryl groups having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0344] In one exemplary embodiment of the invention, L21 to L23 may be the same as or different from each other and may each be a direct bond independently; substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms; substituted or unsubstituted aryl groups having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0345] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

[0346] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0347] In one exemplary embodiment of the invention, Ra1 to Ra6 may be the same as or different from each other, and may each be hydrogen independently; or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0348] In one exemplary embodiment of the present invention, any of chemical formulas 2-2-1 to 2-2-4 may be derived from any of the following chemical formulas:

[0349]

[0350]

[0351]

[0352]

[0353]

[0354] In one exemplary embodiment of the invention, the weight-average molecular weight of the polyimide resin can be from 3,000 g / mol to 70,000 g / mol. Specifically, the weight-average molecular weight of the polyimide resin can be from 5,000 g / mol to 50,000 g / mol. When the weight-average molecular weight of the polyimide resin is less than 3,000 g / mol, the produced insulating film may be easily damaged or the adhesive strength may deteriorate. Furthermore, when the weight-average molecular weight of the polyimide resin exceeds 70,000 g / mol, the sensitivity decreases, and the polyimide resin may fail to develop or residues (e.g., scum) may remain, which is undesirable.

[0355] According to an exemplary embodiment of the present invention, when measured using a universal testing machine (UTM) at 25°C and 5 cm / min, the elongation of a 10 μm thick film prepared by applying, exposing, and drying the photosensitive resin composition can be 40% or greater. Specifically, when measured using a universal testing machine (UTM) at 25°C and 5 mm / min, the elongation of a 10 μm thick film prepared by applying, exposing, and drying the photosensitive resin composition can be 20% or greater and 80% or less.

[0356] More specifically, the elongation can be 21% or greater, 22% or greater, 23% or greater, 24% or greater, or 25% or greater, and 79% or less, 78% or less, 77% or less, 76% or less, or 75% or less. When the elongation of the photosensitive resin composition under the above measurement conditions is within the above range, the insulating film containing the photosensitive resin composition or its cured product exhibits excellent chemical resistance and mechanical properties, and is therefore preferably used as an insulating film for semiconductor devices, an interlayer insulating film for redistribution layers, etc.

[0357] According to an exemplary embodiment of the present invention, a 10 μm thick film prepared by applying, exposing, and drying a photosensitive resin composition can have a dielectric constant (Dk) of 3.35 or less and a dielectric loss (Df) of 0.03 or less. Specifically, a 10 μm thick film prepared by applying, exposing, and drying a photosensitive resin composition can have a dielectric constant (Dk) of 2 or greater and 3.35 or less and a dielectric loss (Df) of 0.001 or greater and 0.03 or less.

[0358] More specifically, the dielectric constant can be 2.05 or greater, 2.1 or greater, or 2.15 or greater, and 3.35 or less, 3.3 or less, or 3.25 or less. Furthermore, the dielectric loss can be 0.001 or greater, or 0.002 or greater, and 0.03 or less, or 0.02 or less.

[0359] When the photosensitive resin composition has an elongation within the range described above under the above measurement conditions, the insulating film containing the photosensitive resin composition or its cured product exhibits excellent chemical resistance and mechanical properties, and is therefore preferably used as an insulating film for semiconductor devices, an interlayer insulating film for redistribution layers, etc.

[0360] [Insulating film]

[0361] An exemplary embodiment of this specification provides an insulating film comprising the above-described photosensitive resin composition or its cured product.

[0362] The insulating film may contain a photosensitive resin composition as is.

[0363] The insulating film may contain a cured product of a photosensitive resin composition.

[0364] The insulating film exhibits excellent chemical resistance and mechanical properties, making it a preferred choice for applications such as insulating films in semiconductor devices and interlayer insulating films for redistribution layers. Furthermore, the insulating film can be used in photoresists, etch resists, and solder top resists.

[0365] The insulating film may include a support or a substrate.

[0366] There are no particular limitations on the support or substrate, and those known in the art can be used. For example, examples can be exemplified as substrates for electronic components or predetermined wiring patterns formed on substrates. Examples of substrates include metallic substrates such as silicon, silicon nitride, titanium, tantalum, palladium, tungsten titanate, copper, chromium, iron, aluminum, gold, and nickel, glass substrates, etc. Materials for wiring patterns can be, for example, copper, solder, chromium, aluminum, nickel, gold, etc., but are not limited to these materials. Preferably, the support or substrate can be a silicon wafer.

[0367] In one exemplary embodiment of the invention, the thickness of the insulating film can be from 1 μm to 100 μm. When the thickness range of the insulating film is met, an insulating film with excellent chemical resistance and mechanical properties as desired in this specification can be obtained. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0368] [Semiconductor Devices]

[0369] An exemplary embodiment of the present invention provides a semiconductor device including an insulating film.

[0370] In addition to the insulating film, semiconductor devices can be manufactured by further including various components commonly used in the art.

[0371] In the following description, the invention will be described in detail with reference to embodiments used to specifically describe the invention. However, embodiments of the invention can be modified in various different forms and should not be construed as limiting the scope of the invention to the embodiments described below. Embodiments are provided in this specification to describe the invention more completely to those skilled in the art.

[0372] Invention Embodiments

[0373] Example

[0374] Example 1

[0375] 0.6 equivalents of 4,4'-diphenylamine oxide (4,4'-ODA) and 0.4 equivalents of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (bis-APAF) as the first monomer, along with diethylformamide (DEF), were sequentially added to a 500-mL round-bottom flask. The mixture was stirred until completely dissolved while the temperature was raised to 80°C. Then, 0.5 equivalents of 4,4'-(hexafluoroisopropylidene)phthalic anhydride (6FDA) and 0.5 equivalents of 4,4'-oxybisphthalic anhydride (ODPA) as the second monomer, and 0.13 equivalents of 5-norbornene-2,3-dicarboxylic anhydride (NDA) as the third monomer were added to prepare a polyimide resin precursor composition. Subsequently, 10 g of toluene was added under a nitrogen atmosphere, and the resulting mixture was stirred at 80°C for 5 hours, followed by heating. After connecting the flask to the Dean-Stark apparatus and stirring and refluxing the photosensitive resin precursor composition at 150°C for 16 hours, the residual monomer and ring-closure ratio were determined by NMR, and the polymerization solution was obtained by cooling the solution to room temperature to terminate the reaction when the imidization ratio reached 90% or greater.

[0376] The obtained polymerization solution was then diluted with THF, precipitated with MeOH, and then dried to obtain solid photosensitive resin P1. In this case, the weight-average molecular weight of photosensitive resin P1, measured by gel permeation chromatography (GPC), was 18,000 g / mol, and the glass transition temperature (Tg) of photosensitive resin P1, measured by differential scanning calorimetry (DSC), was 245 °C.

[0377] [Photosensitive Resin P1]

[0378]

[0379] In photosensitive resin P1

[0380] q is the value when the weight-average molecular weight of photosensitive resin P1 is 18,000 g / mol, and

[0381] q is an integer between 5 and 40.

[0382] Examples 2 to 6

[0383] Photosensitive resins P2 to P6 were obtained in the same manner as in Example 1, except that the type and ratio (molar ratio) shown in Table 1 below used the first monomer and the second monomer.

[0384] Comparative Example 1

[0385] Photosensitive resin P1 was prepared by polymerization in the same manner as in Example 1, except that PGMEA was used as the solvent instead of DEF.

[0386] Comparative Examples 2 to 6

[0387] Photosensitive resins P2 to P6 were prepared in the same manner as in Comparative Example 1, except that the types and ratios (molar ratios) shown in Table 1 below were used for the first and second monomers. In this case, cases where the monomers could not polymerize due to their low solubility in the solvent are indicated by X.

[0388] [Table 1]

[0389]

[0390] The monomers and compounds used in Table 1 above are as follows.

[0391] 4,4'-ODA: 4,4'-diphenylamine oxide, Sigma-Aldrich Co., Ltd.

[0392] APP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane, TCI Chemical

[0393] Bis-APAF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, Changzhou Sunlight Pharmaceutical Co., Ltd.

[0394] ODPA: 4,4'-O-diphthalic anhydride, Shanghai Guchuang New Chemical Mat Company Limited

[0395] TMEG: Ethylene glycol bis(triphenyltriglyceridate), RIKACID TMEG-100, New Japan Chemical Co., Ltd.

[0396] BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride, Chinatech (Tianjin) Chemical Co., Ltd.

[0397] 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, Chinatech (Tianjin) Chemical Co., Ltd.

[0398] DEF: N,N-Diethylformamide, DEZHOU DEHUA CHEMICAL Co., Ltd.

[0399] PGMEA: Propylene glycol monomethyl ether acetate, Jaewon Industrial Co., Ltd.

[0400] Synthesis example 1

[0401] Relative to the OH group of polyimide, 0.016 equivalents of triethylamine and 0.1 equivalents of 2-acryloyloxyethyl isocyanate were added to the photosensitive resin P1 prepared in Example 1 above, and the mixture was placed in an oil bath and then reacted overnight at 60°C. The reaction was terminated when the 2H peak at 3.68 ppm of 2-acryloyloxyethyl isocyanate (AOI) disappeared using NMR.

[0402] The total OH groups of the photosensitive resin P1 were calculated by comparing the input amount with the total area of ​​the aromatic rings of the polymer appearing at 7 ppm or greater on NMR, and the substitution rate of the AOI was determined by the area of ​​the peak (peak, 3H) appearing at approximately 6 ppm compared to the total OH groups. The photosensitive resin was determined to be substituted with 10 mol% AOI. The weight-average molecular weight was determined to be 19,000 g / mol when the molecular weight was measured using gel permeation chromatography (GPC), and the glass transition temperature (Tg) was determined to be 260 °C when DSC was performed using a solid precipitated in methanol.

[0403] The structure of the polymer based on the above synthesis example 1 is as follows.

[0404] [Polymer of Synthetic Example 1]

[0405]

[0406] In the polymer of Synthetic Example 1,

[0407] q is the value when the polymer's weight-average molecular weight is 19,000 g / mol, and

[0408] q is an integer between 5 and 40.

[0409] Preparation Example 1 - Preparation of Photosensitive Resin Composition

[0410] Preparation Example 1-1

[0411] The photosensitive resin P1 prepared in Example 1 was prepared. In the following, based on 100 parts by weight of the photosensitive resin composition, 27 parts by weight of the photosensitive resin P1, 2 parts by weight of OXE-03 (BASF) as a photoradical initiator, 7 parts by weight of RP-1040 (Nippon Kayaku Co., Ltd.) as a crosslinking agent, and 0.2 parts by weight of BYK-307 (BYK-Chemie) as a surfactant and SIP6930 (Gelest Inc.) as an adhesive additive were contained in a first organic solvent in which N,N-diethylformamide (DEF) and γ-butyrolactone (GBL) were mixed in a weight ratio of 90:10 to prepare the photosensitive resin composition.

[0412] Preparation Examples 1-2 to 1-7

[0413] The photosensitive resin compositions according to Preparation Examples 1-2 to 1-7 were prepared in the same manner as in Preparation Example 1-1, except that those having the compositions shown in Table 2 below were used.

[0414] Refer to Preparation Examples 1-1 and 1-2

[0415] The photosensitive resin compositions according to the reference preparation examples 1-1 and 1-2 were prepared in the same manner as in preparation example 1-1, except that those having the compositions shown in Table 2 below were used.

[0416] [Table 2]

[0417]

[0418] The compounds used in Table 2 above are as follows.

[0419] A: OXE-03 (BASF)

[0420] B: RP-1040 (Nippon Kayaku Co., Ltd.)

[0421] C: BYK-307 (BYK-Chemie)

[0422] D: SIP-6930 (Gelest Inc.)

[0423] Preparation Example 2 - Preparation of Polyimide Film

[0424] Preparation Example 2-1

[0425] The photosensitive resin composition of Preparation Example 1-1 was cured under the following conditions to prepare a polyimide film of Preparation Example 2-1 with a thickness of 10 μm. Specifically, after spin coating, soft baking was performed, followed by exposure using an exposure device, development using a developing solution (cyclopentanone), and then post-baking.

[0426] Resist evaluation conditions: PrB 100℃ / 120 seconds, PB 200℃ / 2 hours, thickness 5 μm.

[0427] Exposure: 300 mJ / cm 2 Up to 900 mJ / cm 2 i-line stepper motor

[0428] Developing: 23°C, cyclopentanone, immersion, DI water rinse

[0429] Preparation Examples 2-2 to 2-7

[0430] The polyimide films of Preparation Examples 2-2 to 2-7 were prepared in the same manner as in Preparation Example 2-1, except that the photosensitive resin compositions of Preparation Examples 1-2 to 1-7 were used.

[0431] Refer to preparation examples 2-1 and 2-2

[0432] Polyimide films of reference preparation examples 2-1 and 2-2 were prepared in the same manner as in preparation example 2-1, except that the photosensitive resin compositions of reference preparation examples 1-1 and 1-2 were used.

[0433] In this case, based on the photosensitive resin compositions prepared according to Reference Preparation Examples 1-1 and 1-2, it was determined that the photosensitive resin composition was difficult to apply and cure uniformly because the solubility of the photosensitive resin was insufficient due to the low DEF content of the first organic solvent.

[0434] Therefore, the polyimide films prepared by the photosensitive resin compositions of Preparation Examples 1-1 and 1-2 are excluded from the following physical property evaluation because the polyimide films are not easily evaluated under the same conditions as the polyimide films of Preparation Examples 2-1 to 2-7.

[0435] Experimental Example

[0436] Experimental Example 1

[0437] Polyimide films prepared in Preparation Examples 2-1 to 2-7 were then prepared. Subsequently, the elongation of the polyimide films was measured at room temperature using a universal testing machine (UTM) at a speed of 5 mm / min, and evaluated under the following conditions. The evaluation results are shown in Table 3 below.

[0438] 40% or more

[0439] 20% or more but less than 40%

[0440] : 0 or greater and less than 20%

[0441] Experiment Example 2

[0442] Polyimide films prepared in Preparation Examples 2-1 to 2-7 were then prepared. Subsequently, polyimide films with a thickness of 10 μm were subjected to a split post dielectric resonator (SPDR) test (measurement frequency: 10 GHz) to evaluate the dielectric constant and dielectric loss, and the evaluation results are shown in Table 3 below.

[0443] [Table 3]

[0444]

[0445] Referring to Table 1, it was determined that in Examples 1 to 6, using DEF as a solvent, a highly reliable insulating film could be achieved, and the solubility of the first monomer and the second monomer, etc., was higher than in Comparative Examples 1 to 6, using PGMEA as a solvent. This facilitated the preparation of photosensitive resins, and compared to other solvents with high solubility for photosensitive resin precursors, such as NMP, Examples 1 to 6 improved safety and environmental pollution issues related to the preparation process of photosensitive resins. Furthermore, it was determined that when the composition of the photosensitive resin precursor composition was adjusted differently, the polymerization probability varied due to differences in solubility in the polymerization solvent. Specifically, polymers P1 and P4 were obtained in Comparative Examples 1 and 4, where PGMEA was used as a solvent. However, it was determined that the solubility of the photosensitive resin precursor was suitable in Examples 1 and 4, where DEF was used as a solvent, and therefore, safety and environmental pollution issues related to the preparation process of photosensitive resins could be further improved. In contrast, in Comparative Examples 1 and 4, where PGMEA was used as the polymerization solvent, trace amounts of PGMEA remained as impurities, as determined by NMR when the photosensitive resin composition was prepared by redissolving the photosensitive resin in DEF after precipitation. Furthermore, in batches containing large amounts of PGMEA as impurities, a change in the viscosity of the photosensitive resin composition was visually apparent, and the composition became cloudy after storage for a long period of 4 weeks or longer. Therefore, in Examples 1 to 6 where DEF was used as the polymerization solvent, excellent purity was observed because the polymerization solvent was the same as DEF, the main solvent used in the photosensitive resin composition, and excellent storage stability was also observed.

[0446] Furthermore, it was determined that in Comparative Examples 2 to 6, where DEF was not used as a solvent and PGMEA was used as a solvent, the monomers could not be polymerized due to insufficient solubility. However, in Examples 2 to 6, where DEF was used as a solvent, polymers P2, P3, P5, and P6 could be easily obtained due to sufficient solubility.

[0447] Meanwhile, referring to Tables 1 to 3, it was determined that the physical properties of the polyimide films prepared in Preparation Examples 2-1 to 2-7 varied with the type of photosensitive resin contained in the photosensitive resin composition.

[0448] Specifically, it was determined that the polyimide film of Preparation Example 2-2, prepared from the photosensitive resin composition according to Preparation Examples 1-2, contained the polymerizable photosensitive resin P2 of Example 2, which was used only in which DEF was used as a solvent. Therefore, the mechanical properties, such as elongation and dielectric constant, of the polyimide film of Preparation Example 2-2 were superior to those of the photosensitive resin composition of Preparation Example 1-1, which contained the polymerizable photosensitive resin P1 in both Example 1 and Comparative Example 1, or the photosensitive resin composition of Preparation Examples 1-7, in which photosensitive resin P1 and photosensitive resin P2 were mixed and used.

[0449] In particular, when the polyimide films containing the photosensitive resin P3 of Example 3 in Preparation Examples 2-3 were compared with the polyimide films containing the photosensitive resin P4 of Example 4 in Preparation Examples 2-4, it was determined that even when the same type of photosensitive resin precursors were mixed with different compositions, the polymerization ability was different due to the difference in solubility in the polymerization solvent, and the physical properties of the prepared polyimide films were different.

[0450] Specifically, compared with the photosensitive resin compositions of Examples 1-4 containing polymerizable photosensitive resin P4 in both Example 4 using DEF as a solvent and Comparative Example 4 using PGMEA as a solvent, the photosensitive resin compositions of Examples 1-3 containing polymerizable photosensitive resin P3 in Example 3 using DEF as a solvent have the excellent mechanical properties of the prepared polyimide film, such as elongation and dielectric constant.

[0451] Meanwhile, it was determined that, compared with the photosensitive resin composition according to Preparation Example 1-1 or the photosensitive resin composition according to Preparation Example 1-4, the polyimide film of Preparation Example 2-5 prepared from the photosensitive resin composition according to Preparation Example 1-5 and the polyimide film of Preparation Example 2-6 prepared from the photosensitive resin composition according to Preparation Example 1-6 have excellent mechanical properties such as elongation and dielectric constant of the prepared polyimide film by including photosensitive resin P5 or P6, which can be polymerized only in Example 5 or Example 6 using DEF as a solvent.

[0452] Meanwhile, referring to Preparation Examples 2-1 and 2-2, it was determined that when the DEF content in the first organic solvent of photosensitive resins P5 and P6 decreased, the viscosity of the photosensitive resin composition decreased, and the solubility of the photosensitive resin decreased.

[0453] That is, as in Preparation Examples 2-5 and 2-6 prepared from the photosensitive resin compositions according to Preparation Examples 1-5, it was determined that when the content of DEF in the first organic solvent was adjusted to a specific range or greater, the solubility of photosensitive resins P5 and P6 was sufficient, and thus a polyimide film with a more uniform thickness and surface could be prepared.

[0454] It can be seen that the photosensitive resin precursor composition according to an exemplary embodiment of the present invention contains DEF as a solvent, and therefore, it is easy to polymerize a photosensitive resin exhibiting high physical properties using a photosensitive resin precursor having a specific composition, and the desired physical properties of the photosensitive resin, such as high elongation and low dielectric constant, can be improved.

[0455] That is, it can be seen that the photosensitive resin precursor composition according to an exemplary embodiment of the present invention can improve safety and environmental pollution issues related to the polymerization process, while providing a photosensitive polyimide resin with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability.

[0456] Meanwhile, referring to Preparation Examples 2-5, 2-6, 2-1, and 2-2, it was determined that photosensitive resins P5 and P6 can be polymerized using DEF as a solvent in Examples 5 and 6, and polyimide films with excellent physical properties can be prepared from them. Furthermore, when the content of DEF in the first organic solvent contained in the photosensitive resin composition is increased, the viscosity of the photosensitive resin composition and the sufficient solubility of the photosensitive resin can be ensured.

[0457] That is, in the process of preparing a photosensitive resin composition involving the precipitation and redissolution of a photosensitive resin using DEF as a solvent, it was determined that when the DEF content of the first organic solvent is within a certain range or greater, sufficient solubility of the photosensitive resin can be ensured, the photosensitive resin composition can be applied uniformly and it is easy to cure, and thus an insulating film with high heat resistance, high elongation, low sensitivity and excellent adhesion can be easily prepared.

[0458] It can be seen that the photosensitive resin composition according to an exemplary embodiment of the present invention can improve safety and environmental pollution issues related to the preparation process, while achieving an insulating film with excellent elongation, sensitivity and / or adhesion to the substrate and high reliability. The insulating film according to an exemplary embodiment of the present invention comprises a photosensitive resin composition with high heat resistance, high elongation, low sensitivity and excellent adhesion, and therefore the semiconductor device using the insulating film has excellent reliability, and the production efficiency of semiconductor packaging can be improved.

[0459] The foregoing detailed description illustrates and describes the invention by way of examples. Furthermore, the foregoing is merely illustrative of preferred embodiments of the invention, and as stated above, the invention can be used in various other combinations, modifications, and environments, and can be varied or modified within the scope of the inventive concept disclosed in this specification, the scope equivalent to the foregoing disclosure, and / or the skill or knowledge in the art. Therefore, the foregoing detailed description is not intended to limit the invention to the disclosed embodiments. Moreover, it should be understood that the appended claims also include other embodiments.

Claims

1. A photosensitive resin precursor composition comprising N,N-diethylformamide (DEF). The photosensitive resin mentioned herein comprises a polyimide resin with an imidization rate of 90% or greater.

2. The photosensitive resin precursor composition according to claim 1, wherein the photosensitive resin precursor composition comprises at least one first monomer represented by any one of the following chemical formulas 1-1-1 to 1-1-4: [Chemical Formula 1-1-1] ， [Chemical Formula 1-1-2] ， [Chemical Formula 1-1-3] ， [Chemical Formula 1-1-4] ， In chemical formulas 1-1-1 to 1-1-4, L11 represents a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -SO2-; -CO-; or -OCO-. L12 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group. n is an integer from 1 to 3, and when n is 2 or greater, L is either the same or different from each other. L13 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-. R1 through R6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups. r1 and r2 are either the same or different, and are each an independent integer from 0 to 3. Furthermore, when r1 is 2 or greater, r1 is either the same or different, and when r2 is 2 or greater, r2 is either the same or different. r3 and r4 are either the same or different from each other, and are each an independent integer from 0 to 4. Furthermore, when r3 is 2 or greater, r3 is either the same or different from each other, and when r4 is 2 or greater, r4 is either the same or different from each other. r5 and r6 are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when r5 is 2 or greater, r5 are either the same or different from each other, and when r6 is 2 or greater, r6 are either the same or different from each other. Ra and Rb may be the same as or different from each other, and each is independently hydrogen; or a structure represented by the following chemical formula a, [Chemical formula a] ， In chemical formula a, This refers to the part connected to the chemical formula 1-1-1 or 1-1-2. R7 is hydrogen; or a substituted or unsubstituted alkyl group, and q is an integer from 1 to 10.

3. The photosensitive resin precursor composition according to claim 2, wherein the photosensitive resin precursor composition further comprises a second monomer represented by any one of the following chemical formulas 1-2-1 to 1-2-4: [Chemical Formula 1-2-1] ， [Chemical Formula 1-2-2] ， [Chemical Formula 1-2-3] ， [Chemical Formula 1-2-4] ， In chemical formulas 1-2-1 to 1-2-4, L21 to L23 may be the same as or different from each other, and each is an independent direct bond; substituted or unsubstituted alkylene groups; substituted or unsubstituted aryl groups; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-, L' and L'' may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group. m is an integer from 1 to 5, and when m is 2 or greater, L'' are either the same or different from each other. Ra1 to Ra6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups. Ra1 to Ra6 are either the same or different from each other, and are each an independent integer from 0 to 3. Ra1 is either the same or different from each other when Ra1 is 2 or greater; Ra2 is either the same or different from each other when Ra2 is 2 or greater; Ra3 is either the same or different from each other when Ra3 is 2 or greater; Ra4 is either the same or different from each other when Ra4 is 2 or greater; Ra5 is either the same or different from each other when Ra5 is 2 or greater; and Ra6 is either the same or different from each other when Ra6 is 2 or greater. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

4. A photosensitive resin composition comprising a first organic solvent, The photosensitive resin comprises a polyimide resin with an imidization rate of 90% or greater, and The first organic solvent includes N,N-diethylformamide (DEF).

5. The photosensitive resin composition according to claim 4, wherein the content of N,N-diethylformamide is 50 parts by weight or more and 100 parts by weight or less, based on 100 parts by weight of the first organic solvent.

6. The photosensitive resin composition according to claim 4, wherein the first organic solvent further comprises any one of the following: propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), diethylene glycol methyl ethyl ether (MEDG), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), 3-methoxybutyl acetate (3-MBA), ethyl lactate (EL), and mixtures thereof.

7. The photosensitive resin composition according to claim 4, wherein the polyimide resin comprises at least any one of the structures represented by the following chemical formulas 2-1-1 to 2-1-4: [Chemical Formula 2-1-1] ， [Chemical Formula 2-1-2] ， [Chemical Formula 2-1-3] ， [Chemical Formula 2-1-4] ， In chemical formulas 2-1-1 to 2-1-4, This refers to the portion that is bonded to another substituent or repeating unit. L11 represents a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted aryl group; -SO2-; -CO-; or -OCO-. L12 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; -OCO-; or -O(L) n O-, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group. n is an integer from 1 to 3, and when n is 2 or greater, L is either the same or different from each other. L13 is a direct bond; substituted or unsubstituted alkylene group; substituted or unsubstituted aryl group; -O-; -SO2-; -CO-; or -OCO-. R1 through R6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups. r1 and r2 are either the same or different, and are each an independent integer from 0 to 3. Furthermore, when r1 is 2 or greater, r1 is either the same or different, and when r2 is 2 or greater, r2 is either the same or different. r3 and r4 are either the same or different from each other, and are each an independent integer from 0 to 4. Furthermore, when r3 is 2 or greater, r3 is either the same or different from each other, and when r4 is 2 or greater, r4 is either the same or different from each other. r5 and r6 are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when r5 is 2 or greater, r5 are either the same or different from each other, and when r6 is 2 or greater, r6 are either the same or different from each other. Ra and Rb may be the same as or different from each other, and each is independently hydrogen; or a structure represented by the following chemical formula a, [Chemical formula a] ， In chemical formula a, This refers to the part connected to the chemical formula 2-1-1 or 2-1-2. R7 is hydrogen; or a substituted or unsubstituted alkyl group, and q is an integer from 1 to 10.

8. The photosensitive resin composition according to claim 7, wherein the polyimide resin further comprises a structure represented by any one of the following chemical formulas 2-2-1 to 2-2-4: [Chemical Formula 2-2-1] ， [Chemical Formula 2-2-2] ， [Chemical Formula 2-2-3] ， [Chemical Formula 2-2-4] ， In chemical formulas 2-2-1 to 2-2-4, This refers to the portion that is bonded to another substituent or repeating unit. L21 to L23 may be the same as or different from each other, and each is an independent direct bond; substituted or unsubstituted alkylene groups; substituted or unsubstituted aryl groups; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-, L' and L'' may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted aryl group. m is an integer from 1 to 5, and when m is 2 or greater, L'' are either the same or different from each other. Ra1 to Ra6 may be the same as or different from each other, and each is independently hydrogen; or substituted or unsubstituted alkyl groups. Ra1 to Ra6 are either the same or different from each other, and are each an independent integer from 0 to 3. Ra1 is either the same or different from each other when Ra1 is 2 or greater; Ra2 is either the same or different from each other when Ra2 is 2 or greater; Ra3 is either the same or different from each other when Ra3 is 2 or greater; Ra4 is either the same or the same from each other when Ra4 is 2 or greater; Ra5 is either the same or different from each other when Ra5 is 2 or greater; and Ra6 is either the same or different from each other when Ra6 is 2 or greater. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

9. The photosensitive resin composition according to claim 4, wherein the photosensitive resin composition is a negative photosensitive composition.

10. The photosensitive resin composition according to claim 4, wherein the elongation of a 10 μm film prepared by applying, exposing, and drying the photosensitive resin composition is 40% or greater when measured using a universal testing machine (UTM) at 25°C and 5 mm / min.

11. The photosensitive resin composition according to claim 4, wherein the film with a thickness of 10 μm prepared by applying, exposing and drying the photosensitive resin composition has a dielectric constant (Dk) of 3.35 or less and a dielectric loss (Df) of 0.03 or less.

12. An insulating film comprising a photosensitive resin composition or a cured product thereof according to any one of claims 4 to 11.

13. A semiconductor device comprising the insulating film according to claim 12.

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