Polyimide resin and negative-type photosensitive resin composition containing the same

Abstract

To provide a negative-type closed-ring polyimide resin excellent in solubility without swelling during development, and a negative-type photosensitive resin composition including the same.SOLUTION: A polyimide resin includes a structure having the following chemical formula 11. X is a tetravalent organic group; Y is a divalent to hexavalent organic group; R3 to R6 are the same or different and are independently hydrogen or a C1-C10 organic group including a photopolymerizable unsaturated group; m1, m2, k1 and k2 are each 0 or 1; 0≤m1+m2+k1+k2≤2; R1 is -S-, -O-, -CO2- or -SO2-; * in the chemical formula 11 is a part connected to the main chain or terminal group of the polyimide resin; and n is an integer of 1 or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0085003, filed with the Korean Intellectual Property Office on July 20, 2018, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a photosensitive resin composition, and more particularly, to a negative-type ring-closed polyimide resin having excellent solubility and no swelling during development, and a negative-type photosensitive resin composition containing the same.

Background Art

[0003] A photosensitive resin is a typical functional polymer material that has been put into practical use in the production of various precision electronic and information industry products, and is importantly used in current advanced technology industries, particularly in the production of semiconductors and displays. Generally, a photosensitive resin refers to a polymer compound in which a chemical change in the molecular structure occurs within a short time by light irradiation, resulting in changes in physical properties such as solubility in a specific solvent, coloring, and curing. By using a photosensitive resin, fine precision processing is possible, and compared with a thermal reaction process, energy and raw materials can be greatly reduced, and work can be carried out quickly and accurately in a small installation space, and it is widely used in various precision electronic and information industry fields such as the advanced printing field, semiconductor production, display production, and photocurable surface coating materials.

[0004] Such photosensitive resins are roughly divided into negative-type and positive-type. The negative-type photosensitive resin is a type in which the irradiated portion becomes insoluble in the developer, and the positive-type photosensitive resin is a type in which the irradiated portion becomes soluble in the developer.

[0005] Polymers used in negative-type photosensitive resins are required to have high solubility in the developer in the exposed areas after selective exposure, while the unexposed areas must have low or no solubility in the developer. Such requirements are increasingly demanded in the precision electronics and information industries to enable the formation of extremely fine patterns. [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a negative-type photosensitive polyimide with a ring-closed structure that does not exhibit swelling during the development process and has excellent solubility when used in pattern formation, and a negative-type photosensitive resin composition containing the same.

[0007] Furthermore, the present invention provides an electronic element comprising an organic insulating film or a photosensitive pattern formed from the negative-type photosensitive resin composition. [Means for solving the problem]

[0008] One embodiment of the present invention provides a polyimide resin having the structure of the following chemical formula 1. [Chemical formula 1] [ka] In the aforementioned chemical formula 1, X is a tetravalent organic group, Y is a divalent to hexavalent organic group. R3 to R6 are C1-C10 organic groups that are identical or different from each other and each independently contain hydrogen; or a photopolymerizable unsaturated group, where m1, m2, k1, and k2 are each 0 or 1, and 0 ≤ m1 + m2 + k1 + k2 ≤ 2. L1 is a divalent organic group, which is an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group, and at least one carbon can be replaced by C(=O), SO2, NR, S, or O, R is an aryl group or an alkyl group, and L1 can be substituted by a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group, or an alkyl group. R1 is -S-, -O-, -CO2-, or -SO2-. R2 is represented by the following chemical formula 2. [Chemical formula 2] [ka] In the aforementioned chemical formula 2, R7 is hydrogen; or an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 10. In chemical formula 1, * represents a site that is linked to the main chain or end group of the polyimide resin, and in chemical formula 2, * represents a site that is linked to R1, and n is an integer of 1 or more.

[0009] Another embodiment of the present invention provides a negative-type photosensitive resin composition comprising the polyimide resin; a photocurable polyfunctional acrylic compound; and a photopolymerization initiator.

[0010] Another embodiment of the present invention provides an electronic element comprising an organic insulating film or a photosensitive pattern formed from the negative-type photosensitive resin composition. [Effects of the Invention]

[0011] According to the embodiments described in this specification, when forming a pattern using a photosensitive resin composition, after selective exposure, the polyimide resin has excellent solubility without swelling during the development process. Also, according to the embodiments described in this specification, it shows high adhesion to the substrate used in a display device at a lower light amount than existing positive photosensitive polyimides, and can form an ultrafine pattern while having excellent mechanical physical properties. An electronic device including an organic insulating film or a photosensitive pattern formed from the photosensitive resin composition and the negative photosensitive resin composition can be provided.

Brief Description of the Drawings

[0012] [Figure 1] It shows the line pattern formed by Example 1. [Figure 2] It shows a photograph of the hole pattern formed by Example 1.

Modes for Carrying Out the Invention

[0013] Hereinafter, the polyimide resin, photosensitive resin composition, and electronic device according to specific implementation examples of the present invention will be described in detail.

[0014] One embodiment of the present invention provides a polyimide resin containing the unit of Chemical Formula 1 and the end group of Chemical Formula 2.

[0015] The inventors have confirmed through experiments that a photosensitive resin containing the polyimide resin of the specific structure can achieve high adhesion and adhesiveness to substrates used in semiconductor devices or display devices, such as metal substrates like Au, Cu, Ni, Ti, and inorganic substrates like SiO2, SiNx, has improved mechanical physical properties such as excellent heat resistance or chemical resistance, and can easily form an ultrafine pattern, and thus completed the invention.

[0016] In particular, the negative-type photosensitive resin composition can omit the high-temperature imidization step by using a polyimide resin that enables a solution process at a low temperature without using a polyimide precursor that requires a high-temperature thermosetting step (imidization step).

[0017] In addition, the present inventors have clarified that when using a structure in which a photopolymerizable unsaturated group is bonded to the side chain of a polyimide with a closed-ring structure as an existing polyimide, a phenomenon occurs in which the side chain swells or the solubility decreases due to ring closure during development. Also, when using both a closed-ring polyimide and a monomer having a photopolymerizable polyfunctional group, since the polymer itself does not have a photopolymerizable group, high energy is generated during the curing process by exposure, making precise patterning difficult and increasing the process cost. Furthermore, after opening the closed-ring structure of the acid anhydride of the closed-ring polyimide and attaching a photopolymerizable group (R) to the opened position, an attempt has been made to introduce a polyamic ester structure, but it has been clarified that during ring closure, the photopolymerizable group (R) detaches, resulting in unstable dimensional safety and gas generation problems.

Chemical formula

[0018] However, the polyimide resin according to the above-described embodiment of the present invention contains a structure of Chemical Formula 2 containing a photopolymerizable unsaturated group in the R2 portion among the terminal groups, so that the terminal group does not undergo a ring closure reaction with the main chain or the side chain bonded thereto during development, and thus no swelling phenomenon occurs during development.

[0019] The polyimide resin can contain an unreacted hydroxyl group (OH), carboxyl group (COOH), thiol group, or sulfonic acid group in the terminal group, and such groups can provide excellent solubility.

[0020] For example, the polyimide resin may contain 5-30% of R2 in the chemical formula 2 on an equivalent basis. For instance, if it contains an amine-terminated group, it may be present in 5-30% relative to the anhydride, and if it contains an anhydride-terminated group, it may be present in 5-30% relative to the amine.

[0021] According to one embodiment, in the chemical formula 1, X is not particularly limited as long as it is a tetravalent organic group, and may be, for example, a tetravalent aromatic organic group, a tetravalent aliphatic organic group, or a tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other, and at least one carbon can be replaced with C(=O), SO2, NR, S, or O, and R is an aryl group or an alkyl group. Specifically for X, there are the following structural formulas, etc. [ka]

[0022] In the above chemical formula 1, Y is a divalent to hexavalent organic group, which may be a divalent to hexavalent aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent organic group in which an aromatic group and an aliphatic group are linked to each other. At least one carbon can be replaced with C(=O), SO2, NR, S, or O, R is an aryl group or an alkyl group, and Y can be replaced with a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group, or an alkyl group. Specifically, [ka] The following are structural formulas, etc. [ka]

[0023] Among the aforementioned structural formulas, the example of Z includes the following structural formulas. [ka]

[0024] As described above, when m1+m2+k1+k2 is 1 or 2 and contains an OH or COOH group, the structure of chemical formula 2 is present not only at the ends of the polyimide resin but also in the side chains, which is advantageous for improving the surface condition when forming a photosensitive film.

[0025] In the above chemical formula 1, L1 is a divalent organic group, which is an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group, and at least one carbon can be replaced with C(=O), SO2, NR, S, or O, R is an aryl group or an alkyl group, and L1 can be replaced with a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group, or an alkyl group. Here, the aromatic group may be a C6-C20 arylene group, and the aliphatic group may be a C1-C20 alkylene group or a C3-C20 cycloalkylene group. The arylene group may be a phenylene group, etc. The halogen group may be F, etc.

[0026] According to one embodiment, L1 may be a phenylene group.

[0027] According to one embodiment, the structure of chemical formula 1 can be represented by the following chemical formula 11 or 12. [Chemical formula 11] [ka] [Chemical formula 12] [ka] In the chemical formulas 11 and 12 above, L2 is a divalent organic group, and the remaining substituents are as described above.

[0028] For example, L2 may be an alkylene or arylene, and more specifically, it may be an alkylene or phenylene from C1 to C12.

[0029] According to one embodiment, R1 is -S-, -O-, or -CO2-.

[0030] According to one embodiment, R1 is -S-.

[0031] According to one embodiment, R1 is -O-.

[0032] In one embodiment, R1 is -CO2-.

[0033] According to one embodiment, L2 is phenylene.

[0034] According to one embodiment, the polyimide resin may contain two or more units represented by chemical formula 1, and may further contain units other than those of chemical formula 1 as needed. However, it is preferable that the polyimide resin contains 50 mol% or more of the units of chemical formula 1.

[0035] The other end of the polyimide resin may also have the end of chemical formula 2, or it may have a diamine or dianhydride used in the production of the polyimide as an end group.

[0036] According to one embodiment, the polyimide resin may have a weight-average molecular weight of 1,000 to 500,000, preferably 5,000 to 200,000. If the weight-average molecular weight is less than 1,000, it may be difficult to achieve the desired coating properties and mechanical properties when applying the polyimide copolymer, and if it exceeds 500,000, the solubility in the developer may be low, making it difficult to apply as a photosensitive material. The weight-average molecular weight may be a value measured by gel permeation chromatography, i.e., GPC.

[0037] The polyimide resin can be produced using a dianhydride compound and a diamine compound, and the materials and polymerization methods constituting the polyimide can be those known in the art. However, in order to have the terminal group of chemical formula 1, a polyimide having at least one group selected from a hydroxyl group, a carboxyl group, a thiol group, and a sulfonic acid group, and having one anhydride group or one amine group, can be produced by using a compound during the polymerization of the polyimide, and the terminal group of chemical formula 1 can be produced by reacting it with an isocyanate compound.

[0038] Another embodiment of the present invention provides a negative-type photosensitive resin composition comprising a polyimide resin; a photocurable polyfunctional acrylic compound; and a photopolymerization initiator. The negative-type photosensitive resin composition may further contain a solvent. Optionally, the negative-type photosensitive resin composition may further contain an epoxy resin.

[0039] In the negative-type photosensitive resin composition of the above-mentioned example, the photocurable polyfunctional acrylic compound is a compound having at least two photocurable acrylic structures within its molecule, and specifically, it may include one or more acrylic compounds selected from the group consisting of acrylate compounds, polyester acrylate compounds, polyurethane acrylate compounds, epoxy acrylate compounds, and caprolactone-modified acrylate compounds.

[0040] For example, the acrylate compounds include hydroxyl group-containing acrylate compounds such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate; and water-soluble acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate. The polyester acrylate compounds include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate. Furthermore, examples of polyurethane acrylate compounds include isocyanate-modified products of the hydroxyl group-containing acrylate compounds, examples of epoxy acrylate compounds include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or (meth)acrylic acid adducts of phenol novolac epoxy resins, and examples of caprolactone-modified acrylate compounds include caprolactone-modified ditrimethylolpropanetetraacrylate, ε-caprolactone-modified dipentaerythritol acrylate, or caprolactone-modified hydroxypivalate neopentyl glycol ester diacrylate.

[0041] Furthermore, in the negative-type photosensitive resin composition of the above-mentioned example, the epoxy resin can help to exhibit high adhesion and bonding to substrates used in semiconductor devices or display devices, and since the epoxy resin can undergo a low-temperature curing process, it also has the advantage of improving process efficiency.

[0042] Such epoxy resins may include, for example, one or more selected from the group consisting of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bromide bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin, and ε-caprolactone-modified epoxy resin, and preferably, liquid type N-glycidyl epoxy resin may be included.

[0043] Furthermore, in the negative-type photosensitive resin composition of the above-mentioned example, the photo-initiator can be any known to be commonly used in photosensitive resin compositions without any special restrictions, and the photo-initiator can be appropriately selected considering the wavelength of ultraviolet light used. Examples of such photo-initiators include acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, or mixtures thereof.

[0044] Specific examples of the aforementioned photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one. Acetophenone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; biimidazole compounds such as 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, or 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole;3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s Examples include triazine compounds such as [triazine-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazine, or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine; and oxime compounds such as CGI-242 and CGI-124 from Ciba Japan.

[0045] Furthermore, the negative-type photosensitive resin composition according to the above-mentioned example may contain 10 to 50 parts by weight of the photocurable polyfunctional acrylic compound and 0.1 to 10 parts by weight of the photopolymerization initiator per 100 parts by weight of the polyimide resin. The composition may further contain 10 to 100 parts by weight of epoxy resin per 100 parts by weight of the polyimide resin.

[0046] The negative-type photosensitive resin composition may further contain one or more curing accelerators selected from the group consisting of imidazole compounds, phosphine compounds, and tertiary amine compounds. The imidazole compound may be, for example, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 2-phenyl-4-methyl-5-hydroxymethylimidazole; the phosphine compound may be, for example, triphenylphosphine, diphenylphosphine, phenylphosphine, or tetraphenylphosphonium tetraphenylborate; and the tertiary amine compound may be, for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, or 4-methyl-N,N-dimethylbenzylamine. Such curing accelerators may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polyimide resin.

[0047] On the other hand, the negative-type photosensitive resin composition may further contain a solvent, an adhesion enhancer, a surfactant, an antifoaming agent, a leveling agent, a gelling inhibitor, or a mixture thereof.

[0048] In the solvent, any organic solvent known to be usable in the negative-type photosensitive resin composition can be used without special limitations, but preferably, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxypropionate, ethyl ethoxypropionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylporamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ -A solvent selected from butyrolactone (GBL), diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane can be used alone or in a mixture of two or more. The organic solvent can be included in an amount of 100 to 400 parts by weight per 100 parts by weight of the polyimide resin.

[0049] Furthermore, the adhesion enhancer may be a silane coupling agent having an active group such as epoxy, a carboxyl group, or an isocyanate. Specific examples of these include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, or mixtures thereof. Such an adhesion enhancer may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polyimide resin.

[0050] Furthermore, any surfactant known to be usable in photosensitive resin compositions can be used without special limitations, but it is preferable to use a fluorine-based surfactant or a silicone-based surfactant. Such a surfactant may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the polyimide resin.

[0051] On the other hand, according to another embodiment of the invention, an electronic element can be provided that includes an organic insulating film or a photosensitive pattern formed from the negative-type photosensitive resin composition of the above embodiment.

[0052] The organic insulating film or photosensitive pattern comprises a polyimide of a specific structure and an acrylic compound containing two or more photocurable acrylic active groups, and may have high adhesion to substrates used in semiconductor devices or display devices, such as metal substrates like Au, Cu, Ni, and Ti, or inorganic substrates like SiO2 and SiNx, while also possessing improved mechanical properties such as excellent heat resistance, insulation, or chemical resistance.

[0053] Therefore, electronic elements including an organic insulating film or photosensitive pattern formed from the negative-type photosensitive resin composition can achieve excellent performance such as high resolution and high sensitivity, exhibit excellent film properties and high mechanical properties, and can also achieve excellent heat resistance, for example, the ability to maintain a firm bond without deterioration of adhesion of the organic insulating film or photosensitive pattern even after long-term use or long-term exposure to high-temperature conditions.

[0054] The organic insulating film may include various insulating films for semiconductor devices or display devices, such as interlayer insulating films, surface protective films, substrate electrode protective layer buffer coating films, or pessivation films. The electronic element may include various components for semiconductor devices or display devices.

[0055] On the other hand, the organic insulating film or photosensitive pattern can be formed by the steps of: applying the negative-type photosensitive resin composition onto a support substrate and drying it to form a resin film; exposing the resin film to light; developing the exposed resin film with a developer solution; and heat-treating the developed photosensitive resin film.

[0056] Using the aforementioned negative-type photosensitive resin composition, a patterned photosensitive resin film can be easily formed on a substrate such as glass or a silicone wafer. Methods for applying the negative-type photosensitive resin composition include spin coating, bar coating, and screen printing.

[0057] The support substrate that can be used in the process of forming the photosensitive resin film can be any substrate that is commonly used in the fields of electronic communications, semiconductors, or displays, without any special restrictions. Specific examples of such substrates include silicone wafers, glass substrates, metal substrates, ceramic substrates, and polymer substrates.

[0058] In the drying process after coating, a prebaked film can be formed by prebaking at 50°C to 150°C for 1 to 20 minutes to evaporate the solvent. If the drying temperature is too low, too much solvent will remain, resulting in film loss in unexposed areas during development and a low remaining film thickness. If the drying temperature is too high, the curing reaction may be accelerated, and unexposed areas may not be developed.

[0059] In the step of exposing the resin film, ultraviolet or visible light with a wavelength of 200-500 nm can be irradiated using a photomask on which the pattern to be processed is formed, and the exposure dose during irradiation is 10 mJ / cm². 3 From 4,000 mJ / cm² 3 This is preferable. The exposure time is not particularly limited and can be appropriately varied depending on the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure. Specifically, the exposure time can be varied within the range of 5 to 250 seconds.

[0060] In the photosensitive resin film formation step, an alkaline aqueous developer commonly known for use in semiconductor or display production can be used without any special limitations.

[0061] The present invention will be described in more detail by the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[0062] Synthesis Example 1 In a three-necked flask equipped with a stirrer, temperature control device, nitrogen gas injection device, Dean-Stark distillation apparatus, and condenser, 16.02 g (43.75 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (BisAPAF) was dissolved in 60 g of GBL (gammabutyroloactone) while passing nitrogen through it. Then, 10.58 g (34.12 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 3.67 g (19.25 mmol) of trimellitic anhydride were added to the solution, and the mixture was stirred for 4 hours. Subsequently, 20 g of toluene, 20 g of GBL, 0.84 g of acetic anhydride, and 2.12 g of aniline were added, the reaction temperature was raised to 160°C, and water was removed for 5 hours using a Dean-Stark distillation apparatus, after which the reaction was continued for 20 hours. After the reaction was complete, 104 g of SPI-1 was obtained. 100 g of the obtained SPI-1 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, the reaction temperature was raised to 60°C, and the mixture was stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.20 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-1. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylporumamide (DMF) solvent, and the weight-average molecular weight was 14,000.

[0063] Synthesis Example 2 Polyimide resin SPI-3 was prepared in the same manner as in Synthesis Example 1, except that 15.16 g (34.12 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was used instead of 4,4'-oxydiphthalic dianhydride (ODPA). 100 g of the obtained SPI-3 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that SPI-A-2 was obtained, in which an average of 0.21 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylpolamide (DMF) solvent, and the weight-average molecular weight was 16,000.

[0064] Synthesis Example 3 Polyimide resin SPI-4 was prepared by the same method as in Synthesis Example 1, except that 10.04 g (34.12 mmol) of biphenyltetracarboxylic dianhydride (BPDA) was used instead of 4,4'-oxydiphthalic dianhydride (ODPA). 100 g of the obtained SPI-4 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that SPI-A-3 was obtained, in which an average of 0.25 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylpolamide (DMF) solvent, and the weight-average molecular weight was 15,000.

[0065] Synthesis Example 4 Polyimide resin SPI-2 was prepared in the same manner as in Synthesis Example 1, except that 3.69 g (19.25 mmol) of 1,2-cyclohexanedicaroxylic anhydride (CHA) was used instead of trimellitic anhydride. 100 g of the obtained SPI-2 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-4. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylporumamide (DMF) solvent, and the weight-average molecular weight was 13,000.

[0066] Synthesis Example 5 Polyimide resin SPI-5 was produced in the same manner as in Synthesis Example 1, except that 19.43 g (43.75 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was used instead of 4,4'-oxydiphthalic dianhydride (ODPA), 13.46 g (36.75 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) was used instead of 16.02 g (43.75 mmol), and 1.53 g (14.00 mmol) of 4-aminophenol was used instead of trimellitic anhydride. 100 g of the obtained SPI-5 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-5. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylporumamide (DMF) solvent, and the weight-average molecular weight was 12,000.

[0067] Synthesis Example 6 Polyimide resin SPI-6 was prepared in the same manner as in Synthesis Example 5, except that 1.75 g (14.00 mmol) of 4-aminobenzenthiol was used instead of 4-aminophenol. 100 g of the obtained SPI-6 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-6. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylpolamide (DMF) solvent, and the weight-average molecular weight was 13,000.

[0068] Synthesis Example 7 Polyimide resin SPI-7 was prepared in the same manner as in Synthesis Example 5, except that 2.63 g (14.00 mmol) of N-(4-aminophenyl)maleimide was used instead of 4-aminophenol. 100 g of the obtained SPI-7 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-7. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylporumamide (DMF) solvent, and the weight-average molecular weight was 13,000.

[0069] Synthesis Example 8 Polyimide resin SPI-8 was prepared in the same manner as in Synthesis Example 5, except that 1.64 g (14.00 mmol) of 4-ethylaniline was used instead of 4-aminophenol. 100 g of the obtained SPI-8 was slowly mixed with 3 g (21 mmol) of 2-acryloyloxyethyl isocyanate, and the reaction temperature was raised to 60°C and stirred for 12 hours. ¹H-NMR analysis revealed that an average of 0.23 equivalents per hydroxyl group (-OH) in the polyimide were substituted with AOI, yielding SPI-A-8. The molecular weight of this polyimide resin was measured by GPC (Gel Permeation Chromtography) under dimethylporumamide (DMF) solvent, and the weight-average molecular weight was 12,000.

[0070] Synthesis Example 9 One mole of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) was dissolved in 80 g of diethylformamide (DEF). To this, 1.1 mole of 4,4'-oxydiphthalic dianhydride (ODPA) was added, and the mixture was placed in 50 g of diethylformamide (DEF). Polymerization was carried out at 50°C for 24 hours to prepare a solution containing polyamic acid. To the prepared solution, 40 g of toluene was added, and the mixture was placed in a Dean-Stark distillation apparatus to remove water. The mixture was then refluxed at 180°C for 12 hours. The prepared polyimide solution was precipitated in methanol, dried, and then dissolved in 50 g of diethylformamide (DEF). 3 moles of 2-methacryloyloxyethyl isocyanate were added, followed by 30 g of diethylformamide (DEF). The mixture was reacted at room temperature for 24 hours, then precipitated in methanol and dried to obtain PI-M-1. The molecular weight was measured by GPC (Gel Permeation Chromtography) under dimethylformamide (DMF) solvent, and the weight-average molecular weight was 17,000.

[0071] Example 1 10.0 g of the polyimide resin SPI-A-1 from Synthesis Example 1, 0.45 g of the photopolymerization initiator Irgacure369 (Ciba Specialty Chemical), and 2.0 g of the photocurable polyfunctional acrylic compound Kayarad DPHA (Nippon Kayaku) were dissolved in 20 g of the organic solvent MEDG (Diethyleneglycol methylethyl ether). Then, 0.05 g of DC-190 (Toray Dow Corning) was added and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting product was filtered through a filter with a pore size of 0.45 μm to produce a photosensitive resin composition.

[0072] Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-2 was used instead of the polyimide resin SPI-A-1.

[0073] Example 3 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-3 was used instead of the polyimide resin SPI-A-1.

[0074] Example 4 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-5 was used instead of the polyimide resin SPI-A-1.

[0075] Example 5 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-6 was used instead of the polyimide resin SPI-A-1.

[0076] Comparative Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-4 was used instead of the polyimide resin SPI-A-1.

[0077] Comparative Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-1 without the introduction of urethane acrylic active groups was used instead of the polyimide resin SPI-A-1 in Example 1.

[0078] Comparative Example 3 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-2 without the introduction of urethane acrylic active groups was used instead of the polyimide resin SPI-A-1.

[0079] Comparative Example 4 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-7 was used instead of the polyimide resin SPI-A-1.

[0080] Comparative Example 5 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of SPI-A-8 was used instead of the polyimide resin SPI-A-1.

[0081] Comparative Example 6 A photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 g of PI-M-1 was used instead of the polyimide resin SPI-A-1.

[0082] Experimental example: Photosensitivity experiment of photosensitive resin film The photosensitive resin compositions obtained in the above examples and comparative examples were applied to a 10 cm × 10 cm glass substrate using a spin coating method at 800 rpm to 1,200 rpm, and then dried at a temperature of 120°C for 2 minutes to obtain a substrate with a 5 μm thick photosensitive resin film. Then, using a mask on which a fine pattern was formed, exposure was performed at 40 mJ / cm² using a broadband aligner exposure apparatus. 3 The substrate was exposed to light with the specified energy. Subsequently, the exposed glass substrate was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 100 seconds, washed with ultrapure water, and then dried under nitrogen to form a pattern on the photosensitive resin film. The thickness of the exposed and remaining film was then measured using an alpha step.

[0083] The ability to create a fine hole pattern with a diameter of 3 μm or less in a photosensitive resin film was evaluated. The surface condition after coating and development was evaluated as "good" if there were no pinholes or cracks when observed with an optical microscope, and the surface uniformity measured using an AFM (Atomic Force Microscope) was 0.5 nm or less; otherwise, it was evaluated as "bad." Hole pattern formation was evaluated as "possible" if holes with a diameter of 3 μm or less were formed, and as "poor" if residual film remained or if the pattern was not formed due to incomplete development.

[0084] The measurement results are shown in Table 1 below. Figure 1 shows the line pattern formed by Example 1. Figure 2 is a photograph showing that a clear hole pattern with a diameter of 3 μm or less was formed by Example 1. [Table 1]

[0085] Comparative Example 1 had terminal groups of chemical formula 2 only on the side chains. While the surface condition was good, the realization of hole patterns with a diameter of 3 μm or less was poor. Comparative Examples 2 and 3 did not contain the structure of chemical formula 2 in either the side chains or terminals. During development, swelling occurred and solubility was low, resulting in poor surface conditions after development, as well as poor realization of hole patterns with a diameter of 3 μm or less. Comparative Examples 4 to 6 had terminal groups of chemical formula 2 on the side chains and photocurable groups at the terminals. While the surface condition was good, the realization of hole patterns with a diameter of 3 μm or less was poor. In particular, Comparative Example 6 could not be developed with the developer due to a lack of alkali-soluble groups after photocuring. On the other hand, Examples 1 to 5 not only had excellent surface conditions after coating and development, but also enabled the realization of hole patterns with a diameter of 3 μm or less. The following are examples of embodiments of the present invention. [Item 1] A polyimide resin containing the structure of the following chemical formula 1. [Chemical formula 1] [C1] JPEG0007838731000011.jpg36141 In chemical formula 1, X is a tetravalent organic group, Y is a divalent to hexavalent organic group. R3 to R6 are C1-C10 organic groups that are identical or different from each other and each independently contain hydrogen; or a photopolymerizable unsaturated group, where m1, m2, k1, and k2 are each 0 or 1, and 0 ≤ m1 + m2 + k1 + k2 ≤ 2. L1 is a divalent organic group, which is an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group, and at least one carbon can be replaced by C(=O), SO2, NR, S, or O, R is an aryl group or an alkyl group, and L1 can be substituted by a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group, or an alkyl group. R1 is -S-, -O-, -CO2-, or -SO2-. R2 is represented by the following chemical formula 2: [Chemical formula 2] [Case 2] JPEG0007838731000012.jpg55135 In chemical formula 2, R7 is hydrogen; or an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 10. In chemical formula 1, * represents a site that is linked to the main chain or end group of the polyimide resin, and in chemical formula 2, * represents a site that is linked to R1, and n is an integer of 1 or more. [Item 2] The polyimide resin described in item 1, wherein chemical formula 1 is represented by chemical formula 11 or 12 below. [Chemical formula 11] [C3] JPEG0007838731000013.jpg34139[Chemical formula 12] [C4] In chemical formulas 11 and 12, L2 is a divalent organic group, and the remaining substituents are as described above. [Item 3] R1 is -S-, -O-, or -CO2-, a polyimide resin as described in item 1 or 2. [Item 4] L2 is phenylene, a polyimide resin as described in item 2. [Item 5] The polyimide resin is a polyimide resin according to any one of items 1 to 4, having a weight-average molecular weight of 1,000 to 500,000. [Item 6] A negative-type photosensitive resin composition comprising a polyimide resin according to any one of items 1 to 5; a photocurable polyfunctional acrylic compound; and a photopolymerization initiator. [Item 7] A negative-type photosensitive resin composition according to item 6, further comprising an organic solvent. [Item 8] A negative-type photosensitive resin composition according to item 6 or 7, comprising 100 parts by weight of polyimide resin, 10 to 50 parts by weight of a photocurable polyfunctional acrylic compound, and 0.1 to 10 parts by weight of a photopolymerization initiator. [Item 9] An electronic element comprising an organic insulating film or photosensitive pattern formed from a negative-type photosensitive resin composition as described in any one of items 6 to 8.

Claims

1. A polyimide resin containing the structure of the following chemical formula 11. [Chemical formula 11] 【Transformation 3】 In the aforementioned chemical formula 11, X is a tetravalent organic group, Y is a divalent to hexavalent organic group. R ３ to R ６ are the same as or different from each other, and each independently is hydrogen; or a C1-C10 organic group containing a photopolymerizable unsaturated group, and m １ m ２ k １ and k ２ are each 0 or 1, and 0 ≦ m １ + m ２ + k １ + k ２ ≦ 2, R １ It is a single bond, R ２ It is represented by the following chemical formula 2, [Chemical formula 2] 【Chemistry 2】 In the aforementioned chemical formula 2, R ７ is hydrogen; or an alkyl group having 1 to 4 carbon atoms, and p is an integer from 1 to 10. In the above chemical formula 11, * represents a part that is linked to the main chain or end group of the polyimide resin, and in the chemical formula 2, * represents R １ This is the part that is connected to the next element, and n is an integer greater than or equal to 1.

2. The polyimide resin according to claim 1, wherein the polyimide resin has a weight-average molecular weight of 1,000 to 500,000.

3. A negative-type photosensitive resin composition comprising a polyimide resin according to any one of claims 1 and 2; a photocurable polyfunctional acrylic compound; and a photopolymerization initiator.

4. The negative-type photosensitive resin composition according to claim 3, further comprising an organic solvent.

5. The negative-type photosensitive resin composition according to claim 3 or 4, wherein the photocurable polyfunctional acrylic compound is contained in an amount of 10 to 50 parts by weight and the photopolymerization initiator is contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polyimide resin.

6. An electronic element comprising an organic insulating film or photosensitive pattern formed from the negative-type photosensitive resin composition according to any one of claims 3 to 5.

Images