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

Abstract

The present invention aims to provide a photosensitive resin precursor composition, a photosensitive resin composition, an insulating film, and a semiconductor device.

Description

[Technical Field]

[0001] This specification relates to a photosensitive resin precursor composition, a photosensitive resin composition, an insulating film, and a semiconductor device. Specifically, it relates to a photosensitive resin precursor composition for polyimide resin polymerization, a photosensitive resin composition containing a polyimide resin, an insulating film, and a semiconductor device. This application claims the benefit as of the filing date of Korean Patent Application No. 10-2023-0134202, filed with the Korean Intellectual Property Office on October 10, 2023, and all its contents are incorporated herein by reference. [Background technology]

[0002] Interlayer insulating films or surface protective films of semiconductor devices require excellent mechanical properties and high heat resistance, and polyimide-based binder resins with superior properties are used for these purposes.

[0003] With the expanding application of miniaturization technology in the FAB (Fabrication) process, significant changes are also occurring in packaging technology, with a focus on process technologies for manufacturing high-performance, thin, and compact packages.

[0004] In recent years, as fan-out wafer-level packaging (FO-WLP) technology has grown due to changes in semiconductor back-end processing technology, there has been a significant increase in demand for photosensitive polyimides (PID or PSPI) for redistribution (RDL) that are capable of low-temperature curing and possess excellent physical properties.

[0005] Negative-type photosensitive polyimides (PIDs) have relatively superior mechanical properties, but achieving high resolution is difficult. Positive-type photosensitive polyimides can achieve relatively high resolution, but satisfying mechanical property requirements is difficult.

[0006] Furthermore, lithography processes using photosensitive polyimide materials, particularly the developing process, involve the use of hazardous substances such as highly toxic materials, raising safety and environmental pollution concerns.

[0007] Therefore, there is a need for technological development that provides a photosensitive polyimide material with excellent mechanical properties and the ability to achieve high resolution, while also resolving safety and environmental pollution issues. [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a photosensitive resin precursor composition for polyimide resin polymerization, a photosensitive resin composition containing a polyimide resin, an insulating film, and a semiconductor device.

[0009] However, the problems that this invention aims to solve are not limited to those mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0010] One 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 more.

[0011] One 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 more, and the first organic solvent comprises N,N-diethylformamide (DEF).

[0012] One embodiment of this specification provides an insulating film comprising the photosensitive resin composition or a cured product thereof.

[0013] One embodiment of this specification provides a semiconductor device including the insulating film. [Effects of the Invention]

[0014] The photosensitive resin precursor composition according to an embodiment of the present invention can provide a photosensitive polyimide resin excellent in elongation, sensitivity, and / or adhesion to a substrate, having high reliability, and can improve safety problems and environmental pollution problems associated with the polymerization process.

[0015] The photosensitive resin composition according to an embodiment of the present invention can realize an insulating film excellent in elongation, sensitivity, and / or adhesion to a substrate, having high reliability, and can improve safety problems and environmental pollution problems associated with the manufacturing process.

[0016] In particular, the photosensitive resin composition according to an embodiment of the present invention exhibits excellent mechanical properties as a photosensitive material (e.g., high heat resistance, high elongation, low sensitivity, and excellent adhesive strength, etc.) without modifying the crosslinkable polymer, so it has excellent process compatibility and enables the development of fine patterns.

[0017] Also, since the insulating film according to an embodiment of the present invention contains the photosensitive resin composition having high heat resistance, high elongation, low sensitivity, and excellent adhesion, the reliability of the semiconductor device using the insulating film is excellent, and the semiconductor packaging production efficiency can be improved.

[0018] The effects of the present invention are not limited to the effects described above, and other effects not mentioned can be clearly understood by those skilled in the art from the specification of the present application.

Mode for Carrying Out the Invention

[0019] Throughout the specification of the present application, when a part "includes" a certain component, it means that, unless otherwise specified, it does not exclude other components, and may further include other components.

[0020] Throughout the specification of the present application, when a member is "on" another member, it includes not only the case where a member is in contact with another member, but also the case where there is another member between the two members.

[0021] Throughout the specification of this application, the unit "parts by weight" may mean the weight ratio between each component.

[0022] Throughout the specification of this application, "(meth)acrylate" is used to refer collectively to acrylate and methacrylate.

[0023] Throughout the specification of this application, the term "monomer" means the form of a monomer before it reacts to form a polymer, and more specifically, it may mean the form in which the monomer has a skeleton, such as a main chain or side chains, before undergoing a polymerization reaction.

[0024] Throughout the specification of this application, the term "monomer unit" means the form in which monomers have reacted in a polymer, and more specifically, the form in which the monomers undergo a polymerization reaction to form the backbone of the polymer, such as the main chain or side chains.

[0025] In this specification, "polymer" means a compound consisting of repeating units (basic units). The polymer may also be represented by a polymer or a compound consisting of a polymer.

[0026] In this specification,

[0027] [ka]

[0028] This refers to a site that bonds to another substituent or bond, and may refer to a site that bonds to the main chain of the polymer as specified herein.

[0029] Examples of substituents described herein are, but are not limited to, those listed below.

[0030] In this specification, the terms “substituted or unsubstituted” mean substituted with one or more substituents selected from the group consisting of deuterium; halogen groups; nitrile groups; nitro groups; hydroxyl groups; -COOH; alkoxy groups; alkyl groups; cycloalkyl groups; alkenyl groups; cycloalkenyl groups; aryl groups; heteroaryl groups; and heterocyclic groups containing one or more O, N, or S atoms, or having no substituents at all.

[0031] In this specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

[0032] In this specification, the alkoxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 30, more specifically 1 to 20, and more specifically 1 to 10.

[0033] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. In one embodiment, the alkyl group has 1 to 30 carbon atoms. In another embodiment, the alkyl group has 1 to 20 carbon atoms. In yet another embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and the like.

[0034] In this specification, the alkylene group is subject to the description of alkyl groups described above, except that the alkyl group is divalent.

[0035] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. In one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0036] In this specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. In one embodiment, the number of carbon atoms of the alkenyl group is 2 to 30. In another embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. In yet another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. Specific examples of the alkenyl group include, but are not limited to, alkenyl groups substituted with aryl groups such as stilbenyl and styrenyl.

[0037] In this specification, the cycloalkenyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. In one embodiment, the cycloalkenyl group has 3 to 30 carbon atoms. In another embodiment, the cycloalkenyl group has 3 to 20 carbon atoms. In yet another embodiment, the cycloalkenyl group has 3 to 6 carbon atoms. Examples of the cycloalkenyl group include, but are not limited to, a cyclopentenyl group and a cyclohexenyl group.

[0038] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. In one embodiment, the aryl group has 6 to 30 carbon atoms. In one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, and terphenyl groups. Examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, indenyl, phenantrenyl, pyrenyl, perilenyl, triphenyl, chrysenyl, and fluorenyl groups.

[0039] In this specification, the arylene group is described in the same way as the aryl group described above, except that the arylene group is divalent.

[0040] In this specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms. Examples of the heterocyclic group include, but are not limited to, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, an acridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuran group, a dibenzofuran group, a tetrahydropyran, and the like. Preferably, the heterocyclic group is a tetrahydropyran.

[0041] In this specification, the description of heterocyclic groups described above may apply to the heteroaryl group, except that it is aromatic.

[0042] In this specification, the aromatic ring may be an aryl group or a heteroaryl group, and the aryl group or heteroaryl group may be subject to the above description. The aliphatic ring may mean a ring other than the aromatic ring.

[0043] In this specification, the "weight-average molecular weight" and "number-average molecular weight" of a compound can be calculated using the molecular weight and molecular weight distribution of that compound. Specifically, a sample sample with a concentration of 1 wt% of the compound is prepared by placing tetrahydrofuran (THF) and the compound in a 1 ml glass bottle. After filtering the standard sample (polystyrene) and the sample sample through a filter (pore size 0.45 μm), the sample is injected into a GPC injector, and the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample sample with the calibration curve of the standard sample. In this case, an Infinity II 1260 (Agilient) can be used as the measuring instrument, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 °C.

[0044] The present invention will be described in more detail below.

[0045] [Photosensitive resin precursor composition] One 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 more.

[0046] A photosensitive resin precursor composition according to one embodiment of the present invention can provide a highly reliable photosensitive polyimide resin with excellent elongation, sensitivity, and / or adhesion to a substrate, and can improve safety and environmental pollution problems associated with the polymerization process.

[0047] In one embodiment of the present invention, the photosensitive resin precursor composition may contain N,N-diethylformamide (DEF). The 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 play a role in facilitating 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 present invention can be maintained at a suitable level, and the polymerization of the polyimide resin contained in the photosensitive resin composition can be made easier.

[0048] Furthermore, the amount of polymerization solvents designated as hazardous substances, such as N-methyl-2-pyrrolidone (NMP) and cyclopentanone (CPO), can be reduced, thereby improving safety and environmental pollution issues associated with the polymerization process. In addition, by including the polyimide resin described later, it is particularly suitable for insulating film manufacturing processes and pattern formation methods that have excellent elongation, sensitivity, and / or adhesion to the substrate, and can realize patterns with excellent mechanical properties and high resolution on the insulating film.

[0049] In one embodiment of the present invention, the photosensitive resin may include a polyimide resin with an imidization rate of 90% or more. Specifically, the photosensitive resin precursor composition may be for polymerization of the photosensitive resin contained in the photosensitive resin composition, and the polymerized photosensitive resin may further contain a solvent and the like, and may be a photosensitive resin composition that hardens to form an insulating film.

[0050] In one embodiment of the present invention, the photosensitive resin precursor composition may be a polymerization precursor composition for the photosensitive resin, and the photosensitive resin may be a photosensitive polyimide resin. Specifically, the photosensitive resin may contain a polyimide resin, and the polyimide resin may have an imidization rate of 90% or more. More specifically, the imidization rate of the polyimide resin may be 90% or more, 92% or more, 94% or more, or 96% or more. This allows the manufactured insulating film to have excellent elongation, sensitivity, and / or adhesion to the substrate, and to have high reliability.

[0051] In one embodiment of the present invention, the photosensitive resin precursor composition may include a mixture of photosensitive polyimide resin precursors for photosensitive polyimide resin polymerization.

[0052] In one embodiment of the present invention, the photosensitive resin precursor composition may contain at least one first monomer represented by any one of the following chemical formulas 1-1-1 to 1-1-4.

[0053] [ka]

[0054] In the above chemical formulas 1-1-1 to 1-1-4, L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -SO2-; -CO-; or -OCO-. L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O-, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. n is an integer between 1 and 3, and if n is 2 or greater, L is either identical or different from each other. L13 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-. R1 to R6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and independently integers between 0 and 3. If r1 is 2 or greater, then R1 is either identical or different. If r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. r5 and r6 are either identical or different, and independently integers between 0 and 10. If r5 is 2 or greater, then R5 is either identical or different. If r6 is 2 or greater, then R6 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or the structure represented by the following chemical formula a.

[0055] [ka]

[0056] In the aforementioned chemical formula a,

[0057] [ka]

[0058] This refers to the portion connected to the aforementioned chemical formula 1-1-1 or chemical formula 1-1-2. R7 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

[0059] In one embodiment of the present invention, the photosensitive resin precursor composition may contain at least one first monomer represented by any one of the chemical formulas 1-1-1 to 1-1-4.

[0060] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-1 and the first monomer represented by chemical formula 1-1-2.

[0061] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-1 and the first monomer represented by chemical formula 1-1-3.

[0062] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-1 and the first monomer represented by chemical formula 1-1-4.

[0063] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-2 and the first monomer represented by chemical formula 1-1-3.

[0064] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-2 and the first monomer represented by chemical formula 1-1-4.

[0065] In one embodiment of the present invention, the photosensitive resin precursor composition may include the first monomer represented by chemical formula 1-1-3 and the first monomer represented by chemical formula 1-1-4.

[0066] In one embodiment of the present invention, the photosensitive resin precursor composition may contain the first monomer represented by the chemical formula 1-1-1.

[0067] In one embodiment of the present invention, the photosensitive resin precursor composition may contain the first monomer represented by the chemical formula 1-1-2.

[0068] In one embodiment of the present invention, the photosensitive resin precursor composition may contain the first monomer represented by the chemical formula 1-1-3.

[0069] In one embodiment of the present invention, the photosensitive resin precursor composition may contain the first monomer represented by the chemical formula 1-1-4.

[0070] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0071] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0072] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0073] In one embodiment of the present invention, L11 may be directly bonded; a halogen-substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -SO2-; -CO-; or -OCO-.

[0074] In one embodiment of the present invention, L12 is a directly bonded; substituted or unsubstituted alkylene group; substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n The group is -O-, where L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, and n is an integer from 1 to 3, and when n is 2 or greater, L may be the same or different from each other.

[0075] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0076] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0077] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0078] In one embodiment of the present invention, L12 is a directly bonded; substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -OCO-; or -O-(L) n -O- is also acceptable.

[0079] In one 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 arylene group having 6 to 12 carbon atoms.

[0080] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-.

[0081] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0082] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0083] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0084] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or -O-.

[0085] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0086] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0087] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0088] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0089] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C20 alkyl group.

[0090] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0091] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0092] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0093] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0094] In one embodiment of the present invention, Ra and Rb may be the same or different from each other, and each may independently be hydrogen; or a structure represented by the following chemical formula a.

[0095] [ka]

[0096] In one embodiment of the present invention, the chemical formula a may be any one of the following structures, and the value of q must satisfy an integer from 1 to 10, and is not limited to the following examples.

[0097] [ka]

[0098] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0099] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0100] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0101] In one embodiment of the present invention, at least one of Ra and Rb contains the structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be greater than 0 mol% and less than or equal to 100 mol% of the total content of the polyimide resin precursor mixture.

[0102] In one embodiment of the present invention, at least one of Ra and Rb contains the structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be 10 mol% to 100 mol%, 20 mol% to 100 mol%, 30 mol% to 100 mol%, 40 mol% to 100 mol%, 50 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 80 mol% to 100 mol%, 90 mol% to 100 mol%, or 100% based on the total content of the polyimide resin precursor mixture.

[0103] In one embodiment of the present invention, the content of the structure represented by chemical formula a relative to the total content of the polyimide resin precursor mixture can be confirmed by commercially available NMR. After the resin synthesis reaction is complete, the amount of OH before the reaction can be derived from the number of protons in the entire aromatic ring of the polyimide, and the content (mol%) of the structure represented by chemical formula a can be confirmed by the number of protons of chemical formula a (integration of the 6.41-5.83 ppm (3H) peak) relative to the amount of OH before the reaction.

[0104] In one embodiment of the present invention, the first monomer represented by any one of the chemical formulas 1-1-1 to 1-1-4 may be selected from any one of the following structural formulas.

[0105] [ka] [ka]

[0106] In the above structural formula, Ra and Rb have the same definitions as in chemical formulas 1-1-1 and 1-1-2.

[0107] In one embodiment of the present invention, the polyimide resin precursor mixture may further contain a third monomer as an end-capper. Specifically, the third monomer may form an end group of the polyimide resin.

[0108] In one embodiment of the present invention, the third monomer may be 5-norbornene-2,3-dicarboxylic anhydride (NDA).

[0109] In one embodiment of the present invention, the third monomer may be represented by the following chemical formula 1-E.

[0110] [ka]

[0111] In the aforementioned chemical formula 1-E, Re1 is hydrogen; or a substituted or unsubstituted alkyl group. re1 is an integer between 0 and 4, and if re1 is 2 or greater, then any Re1 values ​​greater than or equal to 2 are either identical or different from each other. Re is hydrogen; or the structure represented by the chemical formula a above.

[0112] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0113] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0114] In one embodiment of the present invention, Re1 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0115] In one embodiment of the present invention, Re may be hydrogen; or the structure represented by the chemical formula a.

[0116] In one embodiment of the present invention, Re has the structure represented by the chemical formula a. The details of the chemical formula a are as described above.

[0117] In one embodiment of the present invention, 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, based on 100 mol% of the first monomer. Specifically, the photosensitive resin precursor composition may contain two or more different first monomers, and may contain 25 mol% or more, or 30 mol% or more, of the first monomer represented by chemical formula 1-1-1, based on 100 mol% of the first monomer, or 35 mol% or less, or 30 mol% or less.

[0118] When the photosensitive resin precursor composition contains the first monomer represented by chemical formula 1-1-1 within the range described above, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, making it even more suitable for polymerization of the photosensitive resin according to the present invention.

[0119] In one embodiment of the present invention, the photosensitive resin precursor composition is represented by the chemical formula 1-1-3, with respect to 100 mol% of the first monomer, and L12 is -O-(L) n The first monomer, which is -O-, may contain 50 mol% or more. Here, L and n are as described above in chemical formula 1-1-3.

[0120] Specifically, the photosensitive resin precursor composition may contain two or more different first monomers, and may contain a first monomer represented by Chemical Formula 1-1-3, wherein L12 is -O-(L) n -O-. For example, the first monomer may be BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane).

[0121] More specifically, the photosensitive resin precursor composition may contain, based on 100 mol% of the first monomer, a first monomer represented by Chemical Formula 1-1-3, wherein L12 is -O-(L) n -O- in an amount of 55 mol% or more, 60 mol% or more, 65 mol% or more, or 70 mol% or more.

[0122] When the photosensitive resin precursor composition contains a first monomer represented by Chemical Formula 1-1-3, wherein L12 is -O-(L) n -O- in the above-described content, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, and it is more suitable for the polymerization of the photosensitive resin according to the present invention.

[0123] In one embodiment of the present invention, the polyimide resin precursor mixture may further contain a second monomer represented by any one of the following Chemical Formulas 1-2-1 to 1-2-4.

[0124]

Chemical formula

[0125] In the above Chemical Formulas 1-2-1 to 1-2-4, L21 to L23 are the same as or different from each other, and each independently is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')m-O, wherein L' and L'' are the same as or different from each other, and each independently is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being either identical or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is either identical or different from the others. If ra2 is 2 or greater, then Ra2 is either identical or different from the others. If ra3 is 2 or greater, then Ra3 is either identical or different from the others. If ra4 is 2 or greater, then Ra4 is either identical or different from the others. If ra5 is 2 or greater, then Ra5 is either identical or different from the others. If ra6 is 2 or greater, then Ra6 is either identical or different from the others. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

[0126] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0127] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0128] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0129] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0130] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0131] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0132] In one embodiment of the present invention, the second monomer represented by any one of the chemical formulas 1-2-1 to 1-2-4 may be selected from any one of the following chemical formulas.

[0133] [ka] [ka]

[0134] According to one embodiment of the present invention, the photosensitive resin precursor composition may contain 20 mol% or more of the second monomer represented by chemical formula 1-2-1, in which L21 is directly bonded, based on 100 mol% of the second monomer. Specifically, the photosensitive resin precursor composition may contain two or more different second monomers, and may also contain the second monomer represented by chemical formula 1-2-1, in which L21 is directly bonded. For example, the second monomer may be BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride).

[0135] More specifically, the photosensitive resin precursor composition may contain 20 mol% or more, or 25 mol% or more, of the second monomer represented by chemical formula 1-2-1, in which L21 is directly bonded, or 50 mol% or less, or 45 mol% or less, based on 100 mol% of the second monomer.

[0136] When the photosensitive resin precursor composition contains the second monomer represented by the chemical formula 1-2-1, in which L21 is a direct bond, in the aforementioned content, the solubility of the photosensitive resin precursor in N,N-diethylformamide (DEF) increases, making it even more suitable for polymerization of the photosensitive resin according to the present invention.

[0137] [Photosensitive resin composition] One embodiment of the present invention provides a photosensitive resin composition comprising a polyimide resin, the photosensitive resin composition comprising a polyimide resin described later.

[0138] A photosensitive resin composition according to one embodiment of the present invention is a photosensitive resin composition comprising a first organic solvent, wherein the photosensitive resin comprises a polyimide resin with an imidization rate of 90% or more, and the first organic solvent may also comprise N,N-diethylformamide (DEF).

[0139] In one embodiment of the present invention, the photosensitive resin composition may include a polyimide resin with an imidization rate of 90% or more. Specifically, the photosensitive resin composition may be a photosensitive polyimide resin composition, and the polyimide resin contained in the photosensitive resin composition may have an imidization rate of 90% or more. More specifically, the imidization rate of the polyimide resin may be 90% or more, 92% or more, 94% or more, or 96% or more. This allows the manufactured insulating film to have excellent elongation, sensitivity, and / or adhesion to the substrate, and to have high reliability.

[0140] In one embodiment of the present invention, the photosensitive resin composition comprises a first organic solvent, the first organic solvent may also comprise N,N-diethylformamide (DEF).

[0141] In one embodiment of the present 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 is within the range described above, it is more suitable for the manufacturing process of an insulating film containing polyimide resin, and the mechanical properties of the manufactured insulating film, such as elongation and dielectric constant, can be further improved, and an insulating film with excellent developability and capable of realizing patterns with high resolution can be provided.

[0142] In one embodiment of the present 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 flash point is within the range described above, it is more suitable for the manufacturing process of an insulating film containing polyimide resin, and the mechanical properties of the manufactured insulating film, such as elongation and dielectric constant, can be further improved.

[0143] In one embodiment of the present invention, the content of N,N-diethylformamide may be 50 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the first organic solvent. Specifically, the content of N,N-diethylformamide may 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 per 100 parts by weight of the first organic solvent, and may be 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 satisfies the above range, an insulating film with excellent elongation, sensitivity, and / or adhesion to the substrate and high reliability can be realized. Furthermore, the mechanical properties of the insulating film produced from the photosensitive resin composition can be further improved, an insulating film with excellent developability and capable of realizing patterns with high resolution can be provided, and safety issues and environmental pollution issues associated with the manufacturing process can be improved.

[0144] In one embodiment of the present invention, the first organic solvent may further comprise a polar organic solvent. Specifically, the first organic solvent may be a polar aprotic organic solvent. More specifically, the first organic solvent may further comprise any one selected from 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 further comprise propylene glycol monomethyl ether acetate (PGMEA). When the first organic solvent further comprises a polar organic solvent, the mechanical properties of the insulating film produced from the photosensitive resin composition can be further improved, providing an insulating film with excellent developability and capable of realizing patterns with high resolution.

[0145] In other words, the first organic solvent may be N,N-diethylformamide (DEF) alone, or a mixture of N,N-diethylformamide (DEF) and a polar organic solvent other than N,N-diethylformamide (DEF).

[0146] In one embodiment of the present invention, the photosensitive resin composition may further contain 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 upon exposure, and any ordinary photoradical initiator can be used without limitation. Preferably, an oxime ester-based photoradical initiator may be used, such as OXE-03, OXE-04, SPI-03, SPI-07, I367, etc., but is not limited to these.

[0147] In one embodiment of the present invention, the photosensitive resin composition may further contain a photoacid generator.

[0148] In one embodiment of the present invention, the photoacid generator is used to enable the photosensitive resin composition to act as a chemically amplified composition, and by effectively controlling the acid diffusion length, the resolution of the pattern can be improved. Any conventional photoacid generator can be used as the photoacid generator, and preferably, ionic photoacid generators, sulfonyl diazomethane-based, N-sulfonyl oxyimide-based, benzoin sulfonate-based, nitrobenzyl sulfonate-based, sulfone-based, glyoxime-based, and triazine-based agents may be used.

[0149] In one embodiment of the present invention, the photosensitive resin composition may further contain additives. Specifically, the additives may further contain one or more of the following: surfactants, antioxidants, sensitizers, and crosslinking agents.

[0150] In one embodiment of the present invention, the photosensitive resin composition may contain any of the additives: a surfactant, an antioxidant, a sensitizer, and a crosslinking agent.

[0151] In one embodiment of the present invention, the surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, as a silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, manufactured by BYK-Chemie, 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. may be used as fluorine-based surfactants. DIC (DaiNippon Ink & F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F (manufactured by Chemicals) -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. may be used, but are not limited to these.

[0152] In one embodiment of the present invention, the antioxidant can play a role in improving the elongation characteristics of the cured film and its adhesion to metal materials. Furthermore, the antioxidant can suppress oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of the polyimide resin and suppress metal oxidation by providing rust prevention to metal materials. Specific examples of the antioxidant include, but are not limited to, the following compounds.

[0153] In one embodiment of the present invention, the sensitizer can improve the resolution of the pattern by effectively controlling the acid diffusion length. Specifically, the sensitizer, 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, bis(4-hydroxy-3-methylphenyl)-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. may be used, and preferably, an i-line sensitizer may be used.

[0154] In one embodiment of the present invention, the crosslinking agent is not particularly limited and can be used without restriction as long as it is applicable to the art. The crosslinking agent may mainly be a thermal crosslinking agent or a radical monomer. Examples of the crosslinking agent include, but are not limited to, compounds having at least two alkoxymethyl groups and / or methylol groups, and compounds having at least two epoxy groups and / or oxetanyl groups. By including the compounds exemplified above, a condensation reaction can occur with the resin of the present invention during firing after patterning to form a crosslinked structure, thereby improving the mechanical properties of the cured resin pattern, such as elongation. Furthermore, two or more types of crosslinking agents may be used in combination. This allows for a variety of designs.

[0155] In one embodiment of the present invention, preferred examples of compounds having at least two alkoxymethyl groups and / or methylol 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, and DMOM Examples include -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® 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.), which are available from various companies. Two or more of these may be included.

[0156] Furthermore, preferred examples of compounds having at least two epoxy groups and / or oxetanyl groups include, but are not limited to, bisphenol A type epoxy resin, bisphenol A type oxetanyl resin, bisphenol F type epoxy resin, bisphenol F type oxetanyl resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, EPICLON® 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, EPICLON Examples include EXA-4822 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin® BEO-60E (trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Corporation), and others, all of which are available from various companies. Two or more of these may be included.

[0157] Furthermore, as the crosslinking agent, 2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]propan-2-yl]phenoxy]methyl]oxirane, tetraethylene glycol dimethyl acrylate, and the like may be used.

[0158] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 10 parts by weight or more, per 100 parts by weight of the total polyimide resin, and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by weight or less, and more preferably 200 parts by weight or less.

[0159] In one embodiment of the present invention, in order to improve the resolution of the relief pattern, the photosensitive resin composition may further contain monomers having photopolymerizable unsaturated bonds. Preferred monomers are (meth)acrylic compounds that undergo radical polymerization reactions with a photopolymerization initiator, and are not particularly limited to the following, but include, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, mono or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, and 1,6-hexanediol. Examples of compounds include xanediol diacrylates and dimethacrylates, neopentyl glycol diacrylates and dimethacrylates, bisphenol A mono- or diacrylates and methacrylates, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylate and methacrylate, pentaerythritol di-, tri- or tetraacrylate and methacrylate, and ethylene oxide or propylene oxide adducts of these compounds.

[0160] The content of the monomer having the photopolymerizable unsaturated bond is preferably 1 to 50 parts by weight per 100 parts by weight of the total polyimide resin.

[0161] In one embodiment of the present invention, the photosensitive resin composition may further include, as a first organic solvent, a compound known in the art to which the present invention belongs to enable the formation of a photosensitive resin composition. Specifically, the first organic solvent may further include one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0162] The aforementioned ester compounds include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate) It may also be ethyl oxypropionate, alkyl esters of 2-oxypropionate (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-oxobutanoate, ethyl 2-oxobutanoate, etc.).

[0163] The ether compounds may include 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, and the like.

[0164] The ketone compounds may include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.

[0165] The aforementioned aromatic hydrocarbon compound may be toluene, xylene, anisole, limonene, or the like.

[0166] The aforementioned sulfoxide compounds may include dimethyl sulfoxide, among others.

[0167] In one embodiment of the present invention, the additive may further include, but is not limited to, an adhesion promoter, an antifoaming agent, a leveling agent, an antigelling agent, or a mixture thereof, and may further include additives well known in the industry depending on the application.

[0168] In one embodiment of the present invention, the photosensitive resin composition is 350 mJ / cm³ 2 It may have the following sensitivities.

[0169] In one embodiment of the present invention, the photosensitive resin composition is approximately 350 mJ / cm³ 2 Below, approximately 340mJ / cm 2 Below, approximately 330mJ / cm 2 Below, approximately 320mJ / cm 2 The following, or approximately 310 mJ / cm² 2The sensitivity may be as follows. The lower limit of sensitivity is not particularly limited, but is approximately 350 mJ / cm². 2 If the following values ​​are obtained, it can be determined that the photosensitive material has excellent physical properties (for example, easy development of fine patterns).

[0170] In one embodiment of the present invention, the photosensitive resin composition may contain 1 to 40 parts by weight of the photoacid generator; 5 to 50 parts by weight of the crosslinking agent; and 0.05 to 5 parts by weight of the surfactant, per 100 parts by weight of the polyimide resin.

[0171] In one embodiment of the present invention, the photosensitive resin composition may contain 50 to 500 parts by weight of the first organic solvent per 100 parts by weight of the polyimide resin.

[0172] When each of the above-mentioned components is included in the photosensitive resin composition in the aforementioned range of parts by weight, sensitivity and physical properties, as well as substrate adhesion, can be improved even with the use of a small amount of photoacid generator.

[0173] In one embodiment of the present invention, the photosensitive resin composition may be a negative-type photosensitive composition. Specifically, the photosensitive resin composition may be at least partially exposed, i.e., the exposed portion may undergo imidization of the precursor contained in the photosensitive resin composition, resulting in a decrease in its solubility in the aforementioned developer for photosensitive resin compositions, while the unexposed portion may be soluble in the aforementioned developer for photosensitive resin compositions. As a result, when the photosensitive resin composition is developed with the aforementioned developer for photosensitive resin compositions, the unexposed portion is dissolved and removed in the developer, while the exposed portion may remain because its solubility in the developer is insufficient. Examples of development methods include, but are not limited to, shower development, spray development, immersion development, and paddle development.

[0174] [Polyimide resin] In one 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.

[0175] [ka]

[0176] In the aforementioned chemical formulas 2-1-1 to 2-1-4,

[0177] [ka]

[0178] This refers to the part that is bonded to other substituents or repeating units. L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -SO2-; -CO-; or -OCO-. L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; -OCO-; or -O(L) n It is O-, The L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. n is an integer between 1 and 3, and if n is 2 or greater, L is either identical or different from each other. L13 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-. R1 to R6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and independently integers between 0 and 3. If r1 is 2 or greater, then R1 is either identical or different. If r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. r5 and r6 are either identical or different, and independently integers between 0 and 10. If r5 is 2 or greater, then R5 is either identical or different. If r6 is 2 or greater, then R6 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or the structure represented by the following chemical formula a.

[0179] [ka]

[0180] In the aforementioned chemical formula a,

[0181] [ka]

[0182] This refers to the portion connected to the aforementioned chemical formula 2-1-1 or chemical formula 2-1-2. R7 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

[0183] In one embodiment of the present invention, the polyimide resin may contain at least one structure represented by any one of the chemical formulas 2-1-1 to 2-1-4.

[0184] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-1 and the structure represented by chemical formula 2-1-2.

[0185] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-1 and the structure represented by chemical formula 2-1-3.

[0186] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-1 and the structure represented by chemical formula 2-1-4.

[0187] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-2 and the structure represented by chemical formula 2-1-3.

[0188] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-2 and the structure represented by chemical formula 2-1-4.

[0189] In one embodiment of the present invention, the polyimide resin may include the structure represented by chemical formula 2-1-3 and the structure represented by chemical formula 2-1-4.

[0190] In one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 2-1-1.

[0191] In one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 2-1-2.

[0192] In one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 2-1-3.

[0193] In one embodiment of the present invention, the polyimide resin may include the structure represented by the chemical formula 2-1-4.

[0194] The photosensitive resin composition containing the polyimide resin readily produces fine patterns and exhibits excellent resolution. Furthermore, the photosensitive resin composition according to this specification can provide a large quantity of photosensitive resin compositions with excellent sensitivity. Specifically, by including a DEF solvent, the photosensitive resin composition can provide excellent solubility and an environmentally friendly photosensitive resin composition.

[0195] According to one embodiment of the present invention, the photosensitive resin composition can have improved physical properties due to a fine pattern and a high crosslinking ratio by containing a suitable photoinitiator. In particular, a high crosslinking density can result in a high elongation ratio and a low dielectric constant.

[0196] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0197] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0198] In one embodiment of the present invention, L11 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0199] In one embodiment of the present invention, L11 may be directly bonded; a halogen-substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -SO2-; -CO-; or -OCO-.

[0200] In one embodiment of the present invention, L12 is a directly bonded; substituted or unsubstituted alkylene group; substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n The group is -O-, where L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, and n is an integer from 1 to 3, and when n is 2 or greater, L may be the same or different from each other.

[0201] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0202] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0203] In one embodiment of the present invention, L12 is a directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; -OCO-; or -O-(L) n -O- is also acceptable.

[0204] In one embodiment of the present invention, L12 is a directly bonded; substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; -OCO-; or -O-(L) n -O- is also acceptable.

[0205] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO2-; -CO-; or -OCO-.

[0206] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0207] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0208] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -O-; -SO2-; -CO-; or -OCO-.

[0209] In one embodiment of the present invention, L13 may be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or -O-.

[0210] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0211] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0212] In one embodiment of the present invention, R1 and R2 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0213] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0214] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C20 alkyl group.

[0215] In one embodiment of the present invention, R3 and R4 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0216] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0217] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0218] In one embodiment of the present invention, R5 and R6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted C1-C10 alkyl group.

[0219] In one embodiment of the present invention, Ra and Rb may be the same or different from each other, and each may independently be hydrogen; or a structure represented by the following chemical formula a.

[0220] [ka]

[0221] In one embodiment of the present invention, the chemical formula a may be any one of the following structures, and the value of q must satisfy an integer from 1 to 10, and is not limited to the following examples.

[0222] [ka]

[0223] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0224] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0225] In one embodiment of the present invention, R7 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0226] In one embodiment of the present invention, at least one of Ra and Rb contains 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 less than or equal to 100 mol% of the total content of the polyimide resin.

[0227] In one embodiment of the present invention, at least one of Ra and Rb contains the structure represented by chemical formula a, and the content of the structure represented by chemical formula a may be 10 mol% to 100 mol%, 20 mol% to 100 mol%, 30 mol% to 100 mol%, 40 mol% to 100 mol%, 50 mol% to 100 mol%, 60 mol% to 100 mol%, 70 mol% to 100 mol%, 80 mol% to 100 mol%, 90 mol% to 100 mol%, or 100% relative to the total content of the polyimide resin.

[0228] In one embodiment of the present invention, the content of the structure represented by chemical formula a relative to the total content of the polyimide resin can be confirmed by commercially available NMR. After the resin synthesis reaction is complete, the amount of OH before the reaction can be derived from the number of protons in the entire aromatic ring of the polyimide, and the content (mol%) of the structure represented by chemical formula a can be confirmed by the number of protons of chemical formula a (integration of the 6.41-5.83 ppm (3H) peak) relative to the amount of OH before the reaction.

[0229] In one embodiment of the present invention, the chemical formulas 2-1-1 to 2-1-4 may be represented by any one of the following structural formulas.

[0230] [ka] [ka]

[0231] In the above structural formula, Ra and Rb are defined in the same way as in chemical formulas 2-1-1 and 2-1-2.

[0232] [ka]

[0233] This can refer to a portion that bonds to other substituents or repeating units.

[0234] In one embodiment of the present invention, the polyimide resin may further include a structure represented by the following chemical formula 2-E-1 or the following chemical formula 2-E-2.

[0235] [ka]

[0236] In the aforementioned chemical formulas 2-E-1 and 2-E-2,

[0237] [ka]

[0238] This refers to the part that is bonded to other substituents or repeating units. Re2 is hydrogen; or a substituted or unsubstituted alkyl group. re2 is an integer between 0 and 4, and if re2 is 2 or greater, then any Re2 values ​​greater than or equal to 2 are either identical or different from each other. Re is hydrogen; or the structure represented by the chemical formula a above.

[0239] In one embodiment of the present invention, the structure represented by the chemical formula 2-E-1 or the chemical formula 2-E-2 may be an end group of the polyimide resin.

[0240] In one embodiment of the present invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0241] In one embodiment of the present invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0242] In one embodiment of the present invention, Re2 may be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0243] In one embodiment of the present invention, Re may be hydrogen; or a structure represented by the chemical formula a.

[0244] In one embodiment of the present invention, Re is a structure represented by the chemical formula a. The content regarding the chemical formula a is as described above.

[0245] In one embodiment of the present invention, the polyimide resin may further include any one of the structures represented by any one of the following chemical formulas 2-2-1 to chemical formula 2-2-4.

[0246]

Chemical formula

[0247] In the chemical formulas 2-2-1 to chemical formula 2-2-4,

[0248]

Chemical formula

[0249] means a part that binds to other substituents or repeating units, L21~L23 are either identical or different to each other, and each is independently directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')mO-. L' and L'' are identical or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being either identical or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is either identical or different from the others. If ra2 is 2 or greater, then Ra2 is either identical or different from the others. If ra3 is 2 or greater, then Ra3 is either identical or different from the others. If ra4 is 2 or greater, then Ra4 is either identical or different from the others. If ra5 is 2 or greater, then Ra5 is either identical or different from the others. If ra6 is 2 or greater, then Ra6 is either identical or different from the others. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

[0250] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; -SO2-; -CO-; or -OCO-.

[0251] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; -SO2-; -CO-; or -OCO-.

[0252] In one embodiment of the present invention, L21 to L23 may be the same or different from each other and independently be directly bonded; a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; -SO2-; -CO-; or -OCO-.

[0253] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0254] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0255] In one embodiment of the present invention, Ra1 to Ra6 may be the same or different from each other, and each may independently be hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0256] In one embodiment of the present invention, any one of the chemical formulas 2-2-1 to 2-2-4 may be derived from any one of the following chemical formulas.

[0257] [ka] [ka]

[0258] In one embodiment of the present invention, the weight average molecular weight of the polyimide resin may be from 3,000 g / mol to 70,000 g / mol. Specifically, the weight average molecular weight of the polyimide resin may 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 formed insulating film may be easily damaged or the adhesive force may decrease. Further, when the weight average molecular weight of the polyimide resin exceeds 70,000 g / mol, it is not preferable because the sensitivity may decrease and development may not occur, or residues (e.g., Scum) may remain.

[0259] According to one embodiment of the present invention, a film produced by coating, exposing, and drying the photosensitive resin composition to a thickness of 10 μm may have an elongation rate of 40% or more measured using a UTM (Universal Testing Machine) under the conditions of 25 °C and 5 cm / min. Specifically, a film produced by coating, exposing, and drying the photosensitive resin composition to a thickness of 10 μm may have an elongation rate of 20% or more and 80% or less measured using a UTM (Universal Testing Machine) under the conditions of 25 °C and 5 mm / min.

[0260] More specifically, the elongation rate may be 21% or more, 22% or more, 23% or more, 24% or more, or 25% or more, and may be 79% or less, 78% or less, 77% or less, 76% or less, or 75% or less. When the photosensitive resin composition has an elongation rate within the above-mentioned range under the above-mentioned measurement conditions, the insulating film containing the photosensitive resin composition or its cured product exhibits excellent chemical resistance and mechanical properties, and is preferably applicable to insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like.

[0261] According to one embodiment of the present invention, a film manufactured to a thickness of 10 μm by coating, exposing, and drying the photosensitive resin composition may have a dielectric constant (Dk) of 3.35 or less and a dielectric loss (Df) of 0.03 or less. Specifically, a film manufactured to a thickness of 10 μm by coating, exposing, and drying the photosensitive resin composition may have a dielectric constant (Dk) of 2 or more and 3.35 or less, and a dielectric loss (Df) of 0.001 or more and 0.03 or less.

[0262] More specifically, the dielectric constant may be 2.05 or higher, 2.1 or higher, or 2.15 or higher, and may be 3.35 or lower, 3.3 or lower, or 3.25 or lower. Also, the dielectric loss may be 0.001 or higher, or 0.002 or higher, and may be 0.03 or lower, or 0.02 or lower.

[0263] When the photosensitive resin composition has a dielectric constant and dielectric loss within the range described above under the measurement conditions described above, the insulating film containing the photosensitive resin composition or its cured product exhibits excellent chemical resistance and mechanical properties, and is preferably applicable as an insulating film for semiconductor devices, an interlayer insulating film for redistribution layers, and the like.

[0264] [Insulated film] One embodiment of this specification provides an insulating film comprising the aforementioned photosensitive resin composition or a cured product thereof.

[0265] The insulating film may contain the photosensitive resin composition as is.

[0266] The insulating film may include a cured product of the photosensitive resin composition.

[0267] The insulating film exhibits excellent chemical resistance and mechanical properties, and is preferably applicable as an insulating film for semiconductor devices, an interlayer insulating film for redistribution layers, and the like. Furthermore, the insulating film is applicable to photoresists, etching resists, solder top resists, and the like.

[0268] The insulating film may include a support or a substrate.

[0269] The support or substrate is not particularly limited and may be one known in the art. Examples include electronic component substrates and substrates on which a predetermined wiring pattern is formed. Examples of substrates include metal substrates such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, and nickel, as well as glass substrates. Examples of materials for the wiring pattern include copper, solder, chromium, aluminum, nickel, and gold, but are not limited to these. Preferably, the support or substrate may be a silicon wafer.

[0270] In one embodiment of the present invention, the thickness of the insulating film may be 1 μm to 100 μm. When the thickness of the insulating film is within the specified range, an insulating film with excellent chemical resistance and mechanical properties, as intended by this specification, can be obtained. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0271] [Semiconductor device] One embodiment of the present invention provides a semiconductor device including the insulating film.

[0272] The semiconductor device may be manufactured to include, in addition to the insulating film, various components commonly used in the art.

[0273] The present invention will be described in detail below with reference to examples. However, the examples of the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples herein are provided to give a more complete explanation of the present invention to a person of average skill in the art. [Examples]

[0274] Examples Example 1 A polyimide resin precursor composition was prepared by sequentially adding 0.6 eq of 4,4'-oxydianiline (4,4'-ODA) and 0.4 eq of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Bis-APAF) and DEF (Diethyl formamide) as the first monomers to a 500 mL round-bottom flask, stirring while heating to 80°C until completely dissolved, then adding 0.5 eq of 4,4'-(hexafluoropropyridene)diphthalic anhydride (6FDA) and 0.5 eq of 4,4'-oxydiphthalic anhydride (ODPA) as the second monomers, and finally adding 0.13 eq of 5-norbornene-2,3-dicarboxylic anhydride (NDA) as the third monomer. Subsequently, under an N2 atmosphere, 10 g of toluene was added and the mixture was stirred at 80°C for 5 hours, and the temperature was increased. The photosensitive resin precursor composition was connected to a Dean-Stark and stirred at 150°C under reflux for 16 hours. After confirming the residual monomer and cyclization rate by NMR, the solution was cooled to room temperature when the imidization rate was 90% or higher, and the reaction was terminated to obtain a polymerization solution.

[0275] Subsequently, the obtained polymerization solution was diluted with THF, precipitated with MeOH, and then dried to obtain a solid photosensitive resin P1. At this time, the weight-average molecular weight of the photosensitive resin P1, measured using gel permeation chromatography (GPC), was 18,000 g / mol, and the glass transition temperature (Tg) of the photosensitive resin P1, measured using differential scanning calorimeter (DSC), was 245°C.

[0276] [ka]

[0277] In the aforementioned photosensitive resin P1, q is a value where the weight-average molecular weight of the photosensitive resin P1 is 18,000 g / mol. q is an integer between 5 and 40.

[0278] Examples 2 to 6 Photosensitive resins P2 to P6 were obtained in the same manner as in Example 1, except that the first and second monomers were used in the types and proportions (molar ratios) shown in Table 1 below.

[0279] Comparative Example 1 Photosensitive resin P1 was produced by polymerization in the same manner as in Example 1, except that PGMEA was used instead of DEF as the solvent.

[0280] Comparative Examples 2 to 6 Photosensitive resins P2 to P6 were produced in the same manner as in Comparative Example 1, except that the first and second monomers were used in the types and proportions (molar ratios) shown in Table 1 below. In this case, X indicates the case where the solubility in the solvent is low and polymerization is impossible.

[0281] [Table 1]

[0282] The monomers and compounds used in Table 1 are as follows: 4,4'-ODA: 4,4'-oxydianiline (Sigma-Aldrich) APP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane (tcichemical) Bis-APAF: 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Changzhou Sunlight Pharmaceutical Co.) ODPA: 4,4'-Oxydiphthalic anhydride (Shanghai Gu Chuang New Chemical Mat Co.) TMEG: Ethylene glycol bis(trimellitic anhydride) (RIKACID TMEG-100, New Japan Chemical Co., Ltd.) BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (Chinatech (Tianjin) Chemical) 6 FDA: 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (Chinatech (Tianjin) Chemical) DEF: N,N-Diethylformamide (DEZHOU DEHUA CHEMICAL) PGMEA; Propylene glycol monomethyl ether acetate (JAEWON Industries Co., Ltd.)

[0283] Synthesis Example 1 In the photosensitive resin P1 produced in Example 1, 0.016 eq of triethylamine and 0.1 eq of 2-acryloyloxyethyl isocyanate were added relative to the OH group of the polyimide. After setting up an oil bath, the mixture was reacted overnight at 60°C. The reaction was terminated when the 2H peak at 3.68 ppm of AOI (2-acryloyloxyethyl isocyanate) disappeared by NMR.

[0284] The total OH of the photosensitive resin P1 was calculated by comparing the total area of ​​the aromatic rings of the polymer that appeared at concentrations of 7 ppm or higher on NMR with the amount added. The substitution rate of AOI was confirmed by the area of ​​the peak (peak, 3H) that appeared around 6 ppm relative to the total OH. It was confirmed that the photosensitive resin was substituted with 10 mol% AOI. The weight-average molecular weight was confirmed to be 19,000 g / mol when the molecular weight was measured using gel permeation chromatography (GPC), and the glass transition temperature (Tg) measured by DSC of the solid precipitated with methanol was confirmed to be 260°C.

[0285] The structure of the polymer produced by the above synthesis example 1 is as follows.

[0286] [ka]

[0287] In the polymerization of the above synthesis example 1, q is a value where the weight-average molecular weight of the polymer is 19,000 g / mol, q is an integer between 5 and 40.

[0288] Manufacturing Example 1 - Production of a photosensitive resin composition Manufacturing Example 1-1 The photosensitive resin P1 produced in Example 1 was prepared. Then, a photosensitive resin composition was prepared by mixing 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, 0.2 parts by weight of BYK-307 (BYK-Chemie) as a surfactant and SIP6930 (Gelest) as an adhesion aid, with the remaining weight being a mixture of N,N-diethylformamide (DEF) and γ-butyrolactone (GBL) in a weight ratio of 90:10 as the first organic solvent.

[0289] Manufacturing Examples 1-2 to 1-7 The photosensitive resin compositions according to Production Examples 1-2 to 1-7 were produced in the same manner as in Production Example 1-1, except that they had the compositions shown in Table 2 below.

[0290] Reference Manufacturing Example 1-1 and Reference Manufacturing Example 1-2 The photosensitive resin compositions according to Reference Production Example 1-1 and Reference Production Example 1-2 were produced in the same manner as in Production Example 1-1, except that they had the compositions shown in Table 2 below.

[0291] [Table 2]

[0292] The compounds used in Table 2 are as follows: A: OXE-03 (BASF) B: RP-1040 (Nippon Kayaku Co., Ltd.) C:BYK-307 (BYK Corporation) D: SIP-6930 (Gelest Corporation)

[0293] Manufacturing Example 2 - Manufacturing of Polyimide Film Manufacturing Example 2-1 The photosensitive resin composition of Production Example 1-1 was cured under the following conditions to produce a polyimide film of Production Example 2-1 with a thickness of 10 μm. Specifically, after spin coating, soft baking was performed, followed by exposure using an exposure unit, development with cyclopentanone, and then post-baking.

[0294] Resist evaluation conditions: PrB 100℃ / 120s, PB 200℃ / 2hr, thickness 5μm. Exposure: 300-900 mJ / cm² 2 i-line stepper, Development: 23°C, Cyclopentanone, Dipping, DI water rinse

[0295] Manufacturing Examples 2-2 to 2-7 The polyimide films of Production Examples 2-2 to 2-7 were produced in the same manner as in Production Example 2-1, except that the photosensitive resin compositions of Production Examples 1-2 to 1-7 were used.

[0296] Reference manufacturing examples 2-1 and 2-2 The polyimide films of Reference Production Example 2-1 and Reference Production Example 2-2 were produced in the same manner as in Production Example 2-1, except that the photosensitive resin compositions of Reference Production Example 1-1 and Reference Production Example 1-2 were used.

[0297] In this case, it was confirmed that in the case of the photosensitive resin compositions according to Reference Production Examples 1-1 and 1-2, the DEF content of the first organic solvent was low, and the solubility of the photosensitive resin was insufficient, making it difficult to uniformly coat and cure the photosensitive resin composition.

[0298] Consequently, the polyimide films produced from the photosensitive resin compositions according to Reference Production Examples 1-1 and 1-2 were excluded from the physical property evaluation described later, as they were not easily evaluated under the same conditions as the polyimide films according to Production Examples 2-1 to 2-7.

[0299] Experimental example Experimental Example 1 Polyimide films were prepared using manufacturing examples 2-1 to 2-7. The elongation of these polyimide films was then measured using a UTM (Universal Testing Machine) at room temperature at a speed of 5 mm / min. The results were evaluated under the following conditions, and the evaluation results are shown in Table 3 below.

[0300] ◎: 40% or more ○: 20% or more and less than 40% △: 0% or more and less than 20%

[0301] Experimental Example 2 Polyimide films manufactured according to Manufacturing Examples 2-1 to 2-7 were prepared. Subsequently, the dielectric constant and dielectric loss of the 10 μm thick polyimide film were evaluated by SPDR (Split post dielectric resonators) testing (measurement frequency: 10 GHz), and the evaluation results are shown in Table 3 below.

[0302] [Table 3]

[0303] Referring to Table 1, in Examples 1 to 6, where DEF was used as the solvent, a highly reliable insulating film could be realized. Furthermore, compared to Comparative Examples 1 to 6, where PGMEA was used as the solvent, the solubility of the first and second monomers was higher, making the production of the photosensitive resin easier. Compared to other solvents with high solubility of photosensitive resin precursors such as NMP, it was confirmed that safety and environmental pollution issues associated with the production of the photosensitive resin could be improved. It was also confirmed that when the composition of the photosensitive resin precursor composition was adjusted to be different, the ability to polymerize differed depending on the difference in solubility in the polymerization solvent. Specifically, polymers P1 and P4 were obtained in Comparative Examples 1 and 4, where PGMEA was used as the solvent, but in Examples 1 and 4, where DEF was used as the solvent, the solubility of the photosensitive resin precursor was suitable, and it was confirmed that safety and environmental pollution issues associated with the production of the photosensitive resin 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 after precipitation of the photosensitive resin and were redissolved in DEF to produce the photosensitive resin composition. This was confirmed by NMR. Furthermore, in lots with a high amount of PGMEA present as an impurity, the viscosity of the photosensitive resin composition changed, and turbidity was observed with the naked eye during long-term storage of 4 weeks or more. Thus, in Examples 1 to 6, where DEF is the polymerization solvent, it is clear that the purity is superior and storage stability is even better because it is the same as DEF, the main solvent used in the photosensitive resin composition.

[0304] Furthermore, in Comparative Examples 2 to 6, which did not contain DEF as a solvent and used PGMEA as the solvent, the solubility was insufficient and polymerization was impossible. However, in Examples 2 to 6, which used DEF as the solvent, the solubility was sufficient, and it was confirmed that polymers P2, P3, P5, and P6 could be easily obtained.

[0305] On the other hand, referring to Tables 1 to 3, it was confirmed that the physical properties of the polyimide films produced in Production Examples 2-1 to 2-7 differed depending on the type of photosensitive resin contained in the photosensitive resin composition.

[0306] Specifically, the polyimide film of Production Example 2-2, produced from the photosensitive resin composition of Production Example 1-2, contains a photosensitive resin P2 that can only be polymerized in Example 2 using DEF as a solvent. This resulted in superior mechanical properties such as elongation and dielectric constant of the produced polyimide film compared to the photosensitive resin composition of Production Example 1-1, which contains a photosensitive resin P1 that can be polymerized in both Example 1 and Comparative Example 1, or the photosensitive resin composition of Production Example 1-7, which uses a mixture of photosensitive resin P1 and photosensitive resin P2.

[0307] In particular, when comparing the polyimide film of Production Example 2-3 containing the photosensitive resin P3 according to Example 3 with the polyimide film of Production Example 2-4 containing the photosensitive resin P4 according to Example 4, it was confirmed that even when the same type of photosensitive resin precursor is mixed in different compositions, the ability to polymerize differs due to differences in solubility in the polymerization solvent, resulting in different physical properties of the produced polyimide films.

[0308] Specifically, the photosensitive resin compositions of Production Examples 1-3, which include photosensitive resin P3 that can only be polymerized in Example 3 using DEF as a solvent, were found to exhibit superior mechanical properties such as elongation and dielectric constant of the produced polyimide film compared to the photosensitive resin compositions of Production Examples 1-4, which include photosensitive resin P4 that can be polymerized in both Example 4 using DEF as a solvent and Comparative Example 4 using PGMEA as a solvent.

[0309] On the other hand, the polyimide film of Production Example 2-5, produced from the photosensitive resin composition of Production Example 1-5, and the polyimide film of Production Example 2-6, produced from the photosensitive resin composition of Production Example 1-6, contain photosensitive resin P5 or P6, which can only be polymerized in Example 5 or Example 6 using DEF as a solvent. As a result, it was confirmed that the resulting polyimide films exhibit superior mechanical properties such as elongation and dielectric constant compared to the photosensitive resin composition of Production Example 1-1 or Production Example 1-4.

[0310] On the other hand, referring to Reference Production Examples 2-1 and 2-2, it was confirmed that when the DEF content of the first organic solvent decreases, the viscosity of the photosensitive resin composition decreases and the solubility of the photosensitive resin decreases.

[0311] In other words, similar to Production Example 2-5, which is produced from the photosensitive resin composition of Production Example 1-5, and Production Example 2-6, which is produced from the photosensitive resin composition of Production Example 1-6, it was confirmed that when the DEF content of the first organic solvent is adjusted to a certain range or higher, the solubility of the photosensitive resins P5 and P6 is sufficient, and a polyimide film with more uniform thickness and surface can be produced.

[0312] This demonstrates that, by including DEF as a solvent, the photosensitive resin precursor composition according to one embodiment of the present invention facilitates the polymerization of a photosensitive resin exhibiting high physical properties using a photosensitive resin precursor having a specific composition, thereby improving physical properties required for photosensitive resins, such as high elongation and low dielectric constant.

[0313] In other words, a photosensitive resin precursor composition according to one embodiment of the present invention can provide a highly reliable photosensitive polyimide resin with excellent elongation, sensitivity, and / or adhesion to a substrate, and can improve safety and environmental pollution issues associated with the polymerization process.

[0314] On the other hand, referring to Production Examples 2-5, 2-6, Reference Production Example 2-1, and Reference Production Example 2-2, it was confirmed that photosensitive resins P5 and P6 could be polymerized from Examples 5 and 6 using DEF as the solvent, thereby enabling the production of polyimide films with excellent physical properties, and that sufficient viscosity of the photosensitive resin composition and solubility of the photosensitive resin could be ensured when the DEF content of the first organic solvent contained in the photosensitive resin composition increased.

[0315] In other words, in the manufacturing process of a photosensitive resin composition involving precipitation and redissolution of a photosensitive resin using DEF as a solvent, it was confirmed that when the DEF content of the first organic solvent is above a certain range, sufficient solubility of the photosensitive resin can be ensured, uniform coating and curing of the photosensitive resin composition are easy, and the production of an insulating film with high heat resistance, high elongation, low sensitivity, and excellent adhesion is easy.

[0316] This demonstrates that a photosensitive resin composition according to one embodiment of the present invention can realize an insulating film with excellent elongation, sensitivity, and / or adhesion to a substrate, and has high reliability, while also improving safety and environmental pollution issues associated with the manufacturing process. Furthermore, since the insulating film according to one embodiment of the present invention contains the photosensitive resin composition having high heat resistance, high elongation, low sensitivity, and excellent adhesion, it is possible to achieve excellent reliability in semiconductor devices using the insulating film and improve semiconductor packaging production efficiency.

[0317] The above detailed description is illustrative and illustrative of the present invention. Furthermore, the foregoing is merely an illustration of preferred embodiments of the present invention, and as stated above, the present invention can be used in a variety of other combinations, modifications, and environments, and can be modified or altered within the scope of the concept of the invention disclosed herein, the scope equivalent to the foregoing disclosure, and / or within the scope of the art or knowledge of the art. Accordingly, the above detailed description of the invention is not intended to limit the present invention to the disclosed embodiments. Furthermore, the appended claims should be construed to include other embodiments as well.

Claims

1. A photosensitive resin precursor composition comprising N,N-diethylformamide (DEF), The aforementioned photosensitive resin is a photosensitive resin precursor composition comprising a polyimide resin with an imidization rate of 90% or more.

2. The photosensitive resin precursor composition according to claim 1, comprising at least one first monomer represented by any one of the following chemical formulas 1-1-1 to 1-1-4: 【Chemistry 1】 In the aforementioned chemical formulas 1-1-1 to 1-1-4, L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; or -SO ２ -; -CO-; or -OCO-, L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO ２ -; -CO-; -OCO-; or -O-(L) ｎ -O-, The L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. n is an integer from 1 to 3, and if n is 2 or greater, L is either the same or different from each other. L13 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO ２ -; -CO-; or -OCO-, R1 to R6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and each is an integer between 0 and 3, and if r1 is 2 or greater, then R1 is either identical or different, and if r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. r5 and r6 are either identical or different, and each is an integer between 0 and 10, and if r5 is 2 or greater, then R5 is either identical or different, and if r6 is 2 or greater, then R6 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or a structure represented by the following chemical formula a. 【Chemistry 2】 In the aforementioned chemical formula a, 【Transformation 3】 This refers to the portion connected to the aforementioned chemical formula 1-1-1 or chemical formula 1-1-2, R7 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

3. The photosensitive resin precursor composition according to claim 2, further comprising a second monomer represented by any one of the following chemical formulas 1-2-1 to 1-2-4: 【Chemistry 4】 In the aforementioned chemical formulas 1-2-1 to 1-2-4, L21 to L23 are either identical or different from each other, and each is independently directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')m-O-. L' and L'' are identical or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being the same or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is the same or different from the others; if ra2 is 2 or greater, then Ra2 is the same or different from the others; if ra3 is 2 or greater, then Ra3 is the same or different from the others; if ra4 is 2 or greater, then Ra4 is the same or different from the others; if ra5 is 2 or greater, then Ra5 is the same or different from the others; if ra6 is 2 or greater, then Ra6 is the same or different from the others. Cy refers to a substituted or unsubstituted aliphatic or aromatic ring.

4. A photosensitive resin composition comprising a first organic solvent, The aforementioned photosensitive resin includes a polyimide resin with an imidization rate of 90% or more. The first organic solvent is a photosensitive resin composition containing 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 per 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 selected from 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 aforementioned polyimide resin is The photosensitive resin composition according to claim 4, comprising at least one of the structures represented by the following chemical formulas 2-1-1 to 2-1-4: 【Transformation 5】 In the aforementioned chemical formulas 2-1-1 to 2-1-4, 【Transformation 6】 This refers to the part that is bonded to other substituents or repeating units. L11 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; or -SO ２ -; -CO-; or -OCO-, L12 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO ２ -; -CO-; -OCO-; or -O(L) ｎ It is O-, The L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. n is an integer from 1 to 3, and if n is 2 or greater, L is either the same or different from each other. L13 is a direct bond; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -SO ２ -; -CO-; or -OCO-, R1 to R6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. r1 and r2 are either identical or different, and each is an integer between 0 and 3, and if r1 is 2 or greater, then R1 is either identical or different, and if r2 is 2 or greater, then R2 is either identical or different. r3 and r4 are either identical or different, and each is an integer between 0 and 4, and if r3 is 2 or greater, then R3 is either identical or different, and if r4 is 2 or greater, then R4 is either identical or different. r5 and r6 are either identical or different, and each is an integer between 0 and 10, and if r5 is 2 or greater, then R5 is either identical or different, and if r6 is 2 or greater, then R6 is either identical or different. Ra and Rb are either identical or different from each other, and independently represent hydrogen; or a structure represented by the following chemical formula a. 【Transformation 7】 In the aforementioned chemical formula a, 【Transformation 8】 This refers to the portion connected to the aforementioned chemical formula 2-1-1 or chemical formula 2-1-2. R7 is hydrogen; or a substituted or unsubstituted alkyl group. q is an integer between 1 and 10.

8. The aforementioned polyimide resin is The photosensitive resin composition according to claim 7, further comprising a structure represented by any one of the following chemical formulas 2-2-1 to 2-2-4: 【Chemistry 9】 In the aforementioned chemical formulas 2-2-1 to 2-2-4, 【Chemistry 10】 This refers to the part that is bonded to other substituents or repeating units. L21 to L23 are either identical or different from each other, and each is independently directly bonded; a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group; -O-; -CO-; -S-; -COO-L'-OCO-; -O-(L'')m-O-. L' and L'' are identical or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group. m is an integer from 1 to 5, and if m is 2 or greater, L'' are either identical or different from each other. Ra1 to Ra6 are either identical or different from each other, and each is independently a hydrogen atom; or a substituted or unsubstituted alkyl group. ra1 to ra6 are integers from 0 to 3, each being the same or different from the others, and each being independent. If ra1 is 2 or greater, then Ra1 is the same or different from the others; if ra2 is 2 or greater, then Ra2 is the same or different from the others; if ra3 is 2 or greater, then Ra3 is the same or different from the others; if ra4 is 2 or greater, then Ra4 is the same or different from the others; if ra5 is 2 or greater, then Ra5 is the same or different from the others; if ra6 is 2 or greater, then Ra6 is the same or different from the others. 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-type photosensitive composition.

10. The photosensitive resin composition according to claim 4, wherein a film prepared by coating, exposing, and drying the photosensitive resin composition to a thickness of 10 μm has an elongation of 40% or more, as measured using a UTM (Universal Testing Machine) at 25°C and 5 mm / min.

11. The photosensitive resin composition according to claim 4, wherein a film produced to a thickness of 10 μm by coating, 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 described in claim 12.

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