Polyimide resin, negative photosensitive resin composition containing the same, and electronic device

Abstract

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

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, and more particularly, to a negative-type closed-loop polyimide resin having excellent solubility and no swelling during development, a negative-type photosensitive resin composition containing the same, and an electronic device.

[0002] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2022-0141533, filed with the Korean Intellectual Property Office on October 28, 2022, and Korean Patent Application No. 10-2023-0144299, filed with the Korean Intellectual Property Office on October 26, 2023, and all of the contents thereof are incorporated herein by reference.

Background Art

[0003] Photosensitive resins are typical functional polymer materials that have been put into practical use in the production of various precision electronics and information industry products, and are currently importantly used in the production of advanced technology industries, particularly semiconductors and displays. Generally, a photosensitive resin means a polymer compound in which a chemical change in the molecular structure occurs within a short time by light irradiation, and physical property changes such as solubility in a specific solvent, coloring, and curing occur. When using a photosensitive resin, fine and precise processing is possible, energy and raw materials can be significantly reduced compared to a thermal reaction process, and work can be carried out quickly and accurately in a small installation space. Therefore, it is widely used in various precision electronics and information industry fields such as the advanced printing field, semiconductor production, display production, and photocurable surface coating materials.

[0004] Such photosensitive resins are broadly classified into negative-type and positive-type. Negative-type photosensitive resins are of a type in which the irradiated portion becomes insoluble in the developer, and positive-type photosensitive resins are of a type in which the irradiated portion becomes soluble in the developer. The polymer used in the negative-type photosensitive resin is required to have a high solubility in the developer for the exposed portion and a low or no solubility in the developer for the unexposed portion after selective exposure. Such requirements are further required to enable the formation of extremely fine patterns in the field of precision electronics and information industries.

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a polyimide having a closed-ring structure that has no swelling phenomenon during the development process and excellent solubility, and a negative photosensitive resin composition containing the same when forming a pattern using a negative photosensitive composition.

[0006] Another object of the present invention is to provide an organic insulating film formed from the negative photosensitive resin composition or an electronic device including a photosensitive pattern.

Means for Solving the Problems

[0007] One embodiment of the present specification provides a polyimide resin including the structure of Chemical Formula 1 below. [Chemical Formula 1]

Chem.

Chem.

Chem.

[0008] Another embodiment of the present invention provides a negative-type photosensitive resin composition containing the above polyimide resin; photosensitizer; crosslinking agent; surfactant; and solvent.

[0009] Also, another embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed from the above negative-type photosensitive resin composition.

Advantages of the Invention

[0010] When forming a pattern using the negative-type photosensitive resin composition according to this specification, even during the development process after selective exposure, the polyimide resin does not swell and has excellent solubility. Also, an electronic device including an organic insulating film or a photosensitive pattern with excellent performance formed from the above negative-type photosensitive resin composition according to this specification can be provided.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Explanation of Reference Numerals

[0012] 1 ··· Silicon wafer (Si wafer) 2 ··· First photosensitive pattern (PID1) 3 ··· Pad 4 ··· Solder ball 5 ··· Second photosensitive pattern (PID2) 6 ··· Substrate 7 ··· First photosensitive pattern (RDL) 8 ··· Pad 9 ··· Second photosensitive pattern (PDL) 10 ··· OLED layer

Mode for Carrying Out the Invention

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

[0014] In this specification, when a certain part "includes" a certain component, it means that, unless otherwise specified, it does not exclude other components, but may further include other components.

[0015] One embodiment of the present invention provides a polyimide resin including the structure of Chemical Formula 1 below. [Chemical Formula 1]

Chem.

Chem.

[0016] The inventors have confirmed by experiments that a photosensitive resin containing a polyimide resin having the above specific structure can achieve high adhesion and adhesiveness to substrates used in semiconductor devices or display devices, such as metal substrates such as Au, Cu, Ni, Ti, and inorganic substrates such as SiO2 and SiNx, and has improved mechanical properties such as excellent heat resistance or chemical resistance, and can easily form ultra-fine patterns, thus completing the present invention.

[0017] In addition, the inventors have been able to ensure fine patterns and excellent physical properties by imparting acrylate (-COO-) to the polyimide resin containing the structure of the above Chemical Formula 1.

[0018] In particular, the negative photosensitive resin composition can omit the high-temperature imidization process by using a polyimide resin that enables a solution process at a low temperature without using a polyimide precursor that requires an indispensable high-temperature thermosetting process (imidization process).

[0019] The inventors have found that when using a structure in which a photopolymerizable unsaturated group is bonded to the side chain of a polyimide having a closed-ring structure as a conventional polyimide, the development that swells due to a decrease in solubility during development decreases. Further, when both a closed-ring polyimide and a monomer having a photopolymerizable polyfunctional group are used, since the polymer itself does not have a photopolymerizable group, high energy is generated during the curing process by exposure, making it difficult to form a precise pattern and increasing the process cost. Furthermore, after opening the anhydride closed-ring structure 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 type structure, but it has been found that the photopolymerizable group (R) desorbs during ring closure, resulting in unstable dimensional stability and gas generation.

Chemical formula

[0020] However, the polyimide resin according to the embodiment of the present invention described above contains a photopolymerizable unsaturated group (represented by Chemical formula 2) in a part of the main chain and terminal groups, so that the terminal groups do not undergo a ring closure reaction with the main chain or the side chain bonded thereto during development, and a swelling phenomenon does not occur during development.

[0021] Further, the polyimide resin according to the embodiment of the present invention may further 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. According to one embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group.

[0022] According to one embodiment of the present specification, X1 and X2 may be the same as or different from each other, and each independently may be selected from the group consisting of a tetravalent aromatic organic group, a tetravalent aliphatic organic group, and a tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0023] According to one embodiment of the present specification, X1 and X2 are divalent hydrocarbons, at least one carbon of the hydrocarbon is substituted with C(=O), SO2, NR', S, or O, or at least one hydrogen of the hydrocarbon may be substituted with a halogen or an alkyl group, and R' may be an alkyl group substituted or unsubstituted with a halogen group, or an aryl group substituted or unsubstituted with a halogen group or an alkyl group.

[0024] According to one embodiment of the present specification, the X1 and X2 may be the same as or different from each other, and each independently may be selected from the group consisting of the following structures.

Chemical formula

Chemical formula

[0025] According to one embodiment of the present specification, the X1 and X2 are

Chemical formula

[0026] When the polyimide resin contains the above structure, the mechanical properties of the polyimide resin are increased, and it is effective for forming an ultrafine pattern due to the increased penetration effect of the developing solution during development.

[0027] According to one embodiment of the present specification, the Y may be selected from the group consisting of a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0028] According to one embodiment of the present specification, Y is a divalent hydrocarbon, or at least one carbon of the hydrocarbon is substituted with C(=O), SO2, NR'', S, or O, or at least one hydrogen of the hydrocarbon may be substituted with a halogen or an alkyl group, and R'' may be an alkyl group or an aryl group.

[0029] According to one embodiment of the present specification, the Y may be selected from the group consisting of the following structures.

Chemical formula

Chemical formula

[0030] According to one embodiment of the present specification,

Chemical formula

[0031] According to one embodiment of the present specification, A is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is substituted with 0, S, C(=O), or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is substituted with a halogen or an alkyl group.

[0032] According to one embodiment of the present specification, A is a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is substituted with 0, S, C(=O), or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is substituted with a halogen or an alkyl group.

[0033] According to one embodiment of the present specification, A may be selected from the group consisting of the following structures.

Chemical formula

Chemical formula

[0034] According to one embodiment of the present specification, Y is

Chemical formula

Chemical formula

[0035] According to one embodiment of the present specification, Z may be a direct bond or any one of the following divalent organic groups

Chemical formula

Chemical formula

[0036] According to one embodiment of the present specification

Chemical formula

[0037] According to one embodiment of the present specification, B may be a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the said hydrocarbon is substituted with 0, S, C(=O), or SO2, or a divalent organic group in which at least one hydrogen of the said hydrocarbon is substituted with a halogen or an alkyl group

[0038] According to one embodiment of the present specification, B may be a divalent hydrocarbon, a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is substituted with 0, S, C(=O), or SO2, or a divalent organic group in which at least one hydrogen of the hydrocarbon is substituted with a halogen or an alkyl group.

[0039] According to one embodiment of the present specification, B may be selected from the group consisting of the following structures.

Chemical formula

Chemical formula

[0040] According to one embodiment of the present specification, Z is a direct bond.

[0041] By including the above structure in the polyimide resin, there is an effect of forming an ultrafine pattern by adjusting the developability.

[0042] According to one embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0043] According to one embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0044] According to one embodiment of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0045] According to one embodiment of the present specification, R7 is hydrogen.

[0046] According to one embodiment of the present specification, n is a real number from 1 to 50, and m is 0.

[0047] According to one embodiment of the present specification, n is a real number from 1 to 50, and m is a real number from 1 to 50.

[0048] In the present specification, the aromatic (organic) group may be an arylene group having 6 to 20 carbon atoms, and the aliphatic group may be an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms. Examples of the arylene group include a phenylene group.

[0049] In the present specification, examples of the halogen group include F, Cl, etc.

[0050] In the present specification, the term "substituted or unsubstituted" means that it is substituted with one or more substituents selected from the group consisting of deuterium; halogen group; hydroxyl group; -COOH; alkyl group; cycloalkyl group; aryl group; and heteroaryl group, or has no substituents.

[0051] In the present 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. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 30. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. Specific examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc.

[0052] In the present specification, the alkylene group means a divalent alkyl group, and the above-described explanation applies to the alkyl group.

[0053] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to still another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.

[0054] 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. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of the monocyclic aryl group include, but are not limited to, phenyl group, biphenyl group, terphenyl group, etc. Examples of the polycyclic aryl group include, but are not limited to, naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, etc.

[0055] 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, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridyl group, pyridazine group, quinolinyl group, isoquinolinyl group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuran group, etc.

[0056] In this specification, the heterocyclic group may be an aliphatic or aromatic ring group.

[0057] In this specification, unless the heteroaryl group is aromatic, the description regarding the heterocyclic group described above may be applicable.

[0058] The other terminals of the polyimide resin may also have the terminals of Chemical Formula 2, and may have a diamine or dianhydride used in the production of the polyimide as a terminal group.

[0059] In one embodiment of this specification, R3 to R6 are the same as or different from each other, at least one is represented by Chemical Formula 2, and the rest are hydrogen, provided that the structure represented by Chemical Formula 2 is 1 mol% or more based on the total number of moles of OH groups contained in the polyimide resin.

[0060] When forming a pattern using the negative-type photosensitive resin composition according to the above embodiment, even in the process of developing after selective exposure, the polyimide resin does not swell and has excellent solubility in the developer.

[0061] In one embodiment of this specification, the structure represented by Chemical Formula 2 is 10 mol% to 70 mol% based on the total number of moles of OH groups contained in the polyimide resin.

[0062] When the structure represented by Chemical Formula 2 is less than 10 mol% based on the total number of moles of OH groups contained in the polyimide resin, the number of OH groups protected by the protecting group is small, and relatively, the number of OH groups not protected by the protecting group is large, and the remaining film ratio may decrease. Further, when the structure represented by Chemical Formula 2 exceeds 70 mol% based on the total number of moles of OH groups contained in the polyimide resin, the number of OH groups protected by the protecting group is large, and relatively, the number of OH groups not protected by the protecting group is small, so the solubility in an alkaline aqueous solution decreases, and it may be difficult to realize an ultrafine pattern.

[0063] Preferably, the structure represented by Chemical Formula 2 is 15 mol% to 45 mol% based on the total number of moles of OH groups contained in the polyimide resin.

[0064] The polyimide resin belonging to the above range can comprehensively improve physical properties such as developability, residual film ratio, and sensitivity.

[0065] In one embodiment of the present specification, when m1 + m2 + k1 + k2 is 1 or 2 and contains an OH or COOH group as in the above structure, the structure of Chemical Formula 2 exists not only at the terminal but also in the side chain of the polyimide resin, which is advantageous for improving the surface state during the formation of the photosensitive film.

[0066] According to one embodiment of the present specification, assuming that the total molar ratio of Y and Z is 1 as the input ratio of the diamine in the polyimide resin of Chemical Formula 1, when Z is a divalent organic group, the molar ratio of Z may be 0.05 ≦ Z ≦ 0.3.

[0067] In one embodiment of the present specification, the polyimide resin may further contain a structure represented by the following Chemical Formula 3 as a terminal group. [Chemical Formula 3] [Chemical Structure] In Chemical Formula 3, * is the site linked to Chemical Formula 1, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is a real number from 0 to 4, and when re1 is 2 or more, Re1 may be the same as or different from each other, Re is hydrogen; or the structure represented by Chemical Formula 2.

[0068] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0069] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0070] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0071] In one embodiment of the present specification, Re1 is hydrogen.

[0072] In one embodiment of the present specification, Re is hydrogen.

[0073] In one embodiment of the present specification, Re has the structure represented by Chemical Formula 2 above.

[0074] According to one embodiment of the present specification, the weight average molecular weight of the polyimide resin is from 5,000 g / mol to 200,000 g / mol.

[0075] When the weight average molecular weight is less than 5,000, it is difficult to achieve the desired coating properties and mechanical properties when applying the polyimide copolymer. When it exceeds 200,000, the solubility in the developer decreases, and it may be difficult to apply as a photosensitive material.

[0076] The weight average molecular weight is not a uniform molecular weight, but is one of the average molecular weights used as a reference for the molecular weight of a certain polymer substance. It is a value obtained by averaging the molecular weights of the component molecular species of a polymer compound with a molecular weight distribution by weight fraction.

[0077] The weight average molecular weight may be a value measured by gel permeation chromatography, i.e., GPC.

[0078] The polyimide resin can be used to produce one type of polyimide (an example of the polyimide of Chemical Formula 1) using a dianhydride compound and a diamine compound as shown in Reaction Formula 1 below. In addition, in order to produce other types of polyimides, materials and polymerization methods well-known in the art may be used. [Reaction Formula 1]

Chemical Formula

[0079] Also, in order to make the polyimide of Chemical Formula 1 have terminal groups, during the polyimide polymerization, a compound 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 is used, so that a polyimide having at least one group selected from a hydroxyl group, a carboxyl group, a thiol group, and a sulfonic acid group can be produced. By reacting this with an isocyanate-based compound, the terminal groups of Chemical Formula 1 can be produced. The following Reaction Formula 2 shows the reaction of an isocyanate-based compound with Chemical Formula 1 to introduce a side chain of Chemical Formula 2 into the main chain of Chemical Formula 1.

[0080] [Reaction Formula 2] [Chemical Formula]

[0081] Another embodiment of the present invention provides a negative photosensitive resin composition containing the polyimide resin; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

[0082] Examples of the photosensitizer include a combination of a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds. By containing a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds, the active radicals generated in the light-irradiated part cause radical polymerization of the ethylenically unsaturated bonds to proceed, and a negative relief pattern in which the light-irradiated part is insolubilized can be obtained.

[0083] The content of the photoinitiator is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total polyimide resin. When the content is 0.1 part by weight or more, sufficient radicals are generated by light irradiation, and the sensitivity is improved. When the content exceeds 20 parts by weight, the non-irradiated part is cured due to excessive radical generation, and it is difficult to form an ultrafine pattern. The content of the compound having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the total polyimide resin. When the content is 5 parts by weight or more, it is preferable because a resin cured film having high mechanical properties can be obtained by crosslinking. When the content is 50 parts by weight or less, it is preferable because the sensitivity is not damaged.

[0084] Further, as the crosslinking agent, Poly(ethylene glycol)diacrylate, Dipentaerythritol hexaacrylate, etc. may be used.

[0085] According to one embodiment of the present specification, the crosslinking agent contains two or more structures represented by the following Chemical Formula 4. [Chemical Formula 4]

Chemical Structure

[0086] According to one embodiment of the present specification, the structure represented by the Chemical Formula 4 includes two or more kinds, and the crosslinking agents having these two structures may have different molecular weights.

[0087] According to one embodiment of the present specification, R8 and R9 are the same as or different from each other, and each independently is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0088] According to one embodiment of the present specification, R8 and R9 are the same as or different from each other, and each independently is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0089] According to one embodiment of the present specification, R8 and R9 are the same as or different from each other, and each independently is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

[0090] With the above configuration, an ultrafine pattern, excellent mechanical properties, heat resistance characteristics, etc. can be ensured.

[0091] The content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, still more preferably 10 parts by weight or more, based on 100 parts by weight of the total polyimide resin, and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

[0092] The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, as the silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. manufactured by BYK-Chemie may be used. As the fluorine-based surfactant, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. manufactured by DIC (DaiNippon Ink & Chemicals) may be used, but are not limited thereto.

[0093] As the solvent, compounds known to enable the formation of a photosensitive resin composition in the technical field to which the present invention pertains can be applied without particular limitation. As non-limiting examples, the solvent may be one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0094] The ester solvents may be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionates (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.

[0095] The ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, or the like.

[0096] The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, or the like.

[0097] The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, or the like.

[0098] The sulfoxide solvent may be dimethyl sulfoxide or the like.

[0099] In addition, depending on its use, the negative photosensitive resin composition may further contain additives well-known in the art. For example, the negative photosensitive resin composition may further contain an adhesion promoter, an antifoaming agent, a leveling agent, a gelation inhibitor, or a mixture thereof.

[0100] As the adhesion promoter, a silane coupling agent having a functional group such as epoxy, carboxyl group, or isocyanate may be used. Specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, or a mixture thereof. Such an adhesion promoter may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

[0101] As the surfactant, any surfactant known to be usable in a photosensitive resin composition can be used without particular limitation, but a fluorine-based surfactant or a silicone-based surfactant is preferably used. Such a surfactant may be contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyimide resin.

[0102] According to one embodiment of the present specification, the polyimide resin may contain one or more polyimide resins.

[0103] Another embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition.

[0104] The organic insulating film or photosensitive pattern contains a polyimide with a specific structure and an acrylic compound containing one or more acrylic functional groups capable of photocuring, thereby achieving high adhesion to substrates used in semiconductor devices, such as metal substrates like Au, Cu, Ni, Ti, etc. and inorganic substrates like SiO2, SiNx, etc., and having improved mechanical properties such as excellent heat resistance, insulation properties, or chemical resistance.

[0105] The electronic device may be any one of a plasma display panel (PDP), a touch panel, a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), a thin film transistor liquid crystal display (LCD - TFT), a cathode ray tube (CRT), and a semiconductor, but is not limited thereto.

[0106] Therefore, an electronic device including an organic insulating film or a 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 realize excellent heat - resistant properties, for example, properties that can be firmly maintained without a decrease in the adhesion of the organic insulating film or photosensitive pattern even after long - term use or long - time exposure under high - temperature conditions.

[0107] FIG. 1 shows an example of an organic insulating film for a semiconductor including a photosensitive resin composition according to an embodiment of the present invention. Specifically, after coating a positive photosensitive resin composition on a silicon wafer 1 and then performing exposure, a first photosensitive pattern (referred to as PID1) 2 is formed, and a pad 3 (for example, a Cu pad) is provided in contact with this pattern, and a solder ball 4 is partially provided at the upper end of the pad. In order to fill the underfill region formed at this time, a second photosensitive pattern (referred to as PID2) 5 is formed using a negative photosensitive resin composition according to an embodiment of the present invention. This PID2 5 can be used as an organic insulating film corresponding to the outermost layer of the semiconductor package material.

[0108] FIG. 2 shows an example of an organic insulating film for an organic light-emitting device including a photosensitive resin composition according to an embodiment of the present invention. Specifically, in the OLED layer 10, a first photosensitive pattern (referred to as RDL (Redistributed layer)) 7 formed from a positive photosensitive resin composition is provided on a substrate 6 (for example, TFT glass or TFT plastic (here, TFT means a thin-film transistor)), and a pad 8 (for example, an Ag pad) is provided in contact with this pattern. At this time, in the OLED, in order to leave a portion where organic light-emitting substances enter, a second photosensitive pattern (referred to as PDL (Pixel define layer)) 9 is formed using a negative photosensitive resin composition according to an embodiment of the present invention. This PDL9 can be used as an organic insulating film of the organic light-emitting device.

[0109] FIGS. 3 and 4 are photographs of a photosensitive pattern according to an embodiment of the present invention. Specifically, FIG. 3 is a 15um square pattern with a thickness of 10um, and FIG. 4 is a 5um hole pattern with a thickness of 8um.

[0110] According to an embodiment of the present specification, the organic insulating film may include an interlayer insulating film and a surface protection film.

[0111] According to one embodiment of the present specification, the electronic device may further include a memory component.

[0112] The organic insulating film may include various insulating films of a semiconductor device, such as an interlayer insulating film, a surface protection film, a substrate electrode protection layer, a buffer coat film, or a passivation film. And the electronic device may include various components of a semiconductor device.

[0113] The interlayer insulating film and the surface protection film are not particularly limited, and those generally used in the art may be adopted.

[0114] The memory component is not particularly limited, and those generally used in the art may be adopted.

[0115] On the other hand, the organic insulating film or the photosensitive pattern may be formed by steps of coating the negative photosensitive resin composition on a support substrate and drying to form a resin film; exposing the resin film; developing the exposed resin film with a developer; and heat-treating the developed photosensitive resin film.

[0116] When using the negative photosensitive resin composition, a patterned photosensitive resin film can be easily formed on a substrate such as glass or a silicon wafer. At this time, as a method of coating the negative photosensitive resin composition, spin coating, bar coating, screen printing, etc. may be used.

[0117] As the support substrate that can be used in the formation process of the photosensitive resin film, any substrate known to be commonly used in the fields of electronic communication and semiconductors can be used without particular limitation. Specific examples thereof include a silicon wafer, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate.

[0118] In the drying process after the coating, prebaking can be performed at 50°C to 150°C for 1 minute to 20 minutes to volatilize the solvent, thereby forming a prebaked film. When the drying temperature is excessively low, the amount of residual solvent becomes excessively large, and film loss also occurs in the exposed area during development, resulting in a low remaining film. When the drying temperature is excessively high, the curing reaction is promoted, and the unexposed area may not be developed.

[0119] In the step of exposing the resin film, ultraviolet light or visible light with a wavelength of 200 nm to 500 nm may be irradiated using a photomask on which the pattern to be processed is formed. The exposure dose during irradiation is 10 mJ / cm 2 ~4,000 mJ / cm 2 is preferable. The exposure time is not particularly limited and may be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the exposure dose. Specifically, the exposure time may be changed within the range of 1 second to 150 seconds.

[0120] In the step of forming the photosensitive resin film, an alkaline aqueous developer that is generally known to be usable in the production stage of semiconductors or displays can be used without particular limitation.

Examples

[0121] Hereinafter, examples will be given for a specific explanation of this specification. However, the examples according to this specification may be modified into various other forms, and it should not be construed that the scope of this specification is limited to the examples described below. The examples of this specification are provided to more fully explain this specification to those with average knowledge in the industry.

[0122] <Synthesis Example 1> 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (1 eq), 4,4'-oxydiphthalic anhydride (1.1 eq), and 3-aminophenol (0.13 eq) were dissolved in PMGEA under a nitrogen atmosphere. Then, toluene was added to the reaction mixture at 140 °C, and a Dean-Stark apparatus was connected. The reaction was carried out overnight at 150 °C. After the reaction, the toluene in the Dean-Stark apparatus was removed, and then PGMEA substitution was performed several times to remove the residual toluene. The reaction was terminated by confirming the residual monomers by NMR, and Polymer 1 was produced. When the molecular weight was measured using gel permeation chromatography (GPC), the weight-average molecular weight was 15,000 g / mol. The structure of Polymer 1 is as follows. [Polymer 1] [Chemical formula] In Polymer 1, q is a real number between 20 and 40, with the value such that the weight-average molecular weight of the polymer is 15,000 g / mol.

[0123] [Synthesis Example 2] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (1 eq), 4,4'-Oxydiphthalic diamine (0.25 eq), 4,4'-Oxydiphthalic anhydride (1.35 eq), and 3-Aminophenol (0.16 eq) were dissolved in PGMEA (Propylene glycol methyl ether acetate) under a N2 atmosphere. Then, toluene was added to the reactants at 150 °C, and a Dean-Stark apparatus was connected, followed by an overnight reaction at 180 °C. After the reaction, the toluene in the Dean-Stark apparatus was removed, and PGMEA substitution was performed several times to remove the residual toluene. The reaction was terminated by confirming the residual monomers by NMR, and Polymer 2 with the following structural formula was produced. When the molecular weight was measured using gel permeation chromatography (GPC), the weight-average molecular weight was confirmed to be 20,000 g / mol. The structure of Polymer 2 is as follows. [Polymer 2] [Chemical formula] In Polymer 2, p and q are real numbers where p ranges from 5 to 40 and q ranges from 2 to 15, with the weight-average molecular weight of the polymer having a value of 17,000 g / mol.

[0124] [Synthesis Example 3] To the Polymer 1 produced in Synthesis Example 1, 0.016 eq of triethylamine and 0.1 eq of 2-Acryloyloxyethyl isocyanate were added with respect to the OH of the polyimide. After setting up an oil bath, the reaction was carried out overnight at 80 °C. The reaction was terminated when the 2H peak at 4.25 ppm of AOI (2-Acryloyloxyethyl isocyanate) disappeared in the NMR.

[0125] The total OH of Polymer 1 was calculated by comparing the sum of the aromatic ring areas of the polymer that appeared at 7 ppm or higher in NMR with the input amount, and the substitution rate of AOI was confirmed by the area of the peak (peak, 3H) that appeared around 6 ppm with respect to the total OH. It was confirmed that the polymer was substituted with 10 mol% of AOI. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 18,000 g / mol. The structure of Polymer 3 is as follows. [Polymer 3] [Chemical formula] In the said Polymer 3, q is a real number of 20 to 40, taking the value where the weight average molecular weight of the polymer is 18,000 g / mol.

[0126] [Synthesis Example 4] The procedure was the same as in Synthesis Example 3, except that Polymer 2 produced in Synthesis Example 2 was used instead of Polymer 1. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 20,000 g / mol. The total OH of Polymer 1 was calculated by comparing the sum of the aromatic ring areas of the polymer that appeared at 7 ppm or higher in NMR with the input amount, and the substitution rate of AOI was confirmed by the area of the peak (peak, 3H) that appeared around 6 ppm with respect to the total OH. It was confirmed that the polymer was substituted with 15 mol% of AOI. The structure of Polymer 4 is as follows. [Polymer 4] [Chemical formula] In the said Polymer 4, p and q are real numbers where p is 5 to 40 and q is 2 to 15, taking the value where the weight average molecular weight of the polymer is 20,000 g / mol.

[0127] [Examples 1 to 7 and Comparative Examples 1 to 3] A photosensitive resin composition was manufactured using the components described in Table 1 below. Specifically, a photosensitive resin composition containing the manufactured polyimide resin and each component described in Table 1 below was manufactured. Table 1 below is based on 100 parts by weight of a resin composition containing a polyimide resin (first and / or second polyimide resin), a photosensitizer, a crosslinking agent, a surfactant, and a solvent.

Table 1

[0128] <Experimental Example> The photosensitive resin compositions of the above Examples and Comparative Examples were evaluated under the following process conditions, and the results are shown in Table 2 below. Specifically, the manufactured photosensitive resin composition was spin-coated on a Cu / Si wafer. After soft baking at 120°C for 120 seconds (sec), after exposure at an appropriate exposure amount (i-line (365 nm)), a development process was performed with a developer (2.38 wt% TMAH sol.). Post-baking was performed at 200°C for 1 hour each to confirm the pattern property. Then, in order to measure the temperature and mechanical physical properties of the cured film, each manufactured photosensitive resin composition was further coated on a Si wafer, after full-surface exposure, soft baking was performed, and post-baking was performed at 200°C for 1 hour.

[0129] Resist evaluation conditions: PrB at 120°C for 120 s, thickness 10 μm exposure: 400 mJ / cm 2 ~500 mJ / cm 2 i-line stepper development: at 23°C, 2.38 wt% TMAH (Tetramethylammonium hydroxide) solution, Dipping, DI water rinse

[0130] [Pattern resolution] Samples of each photosensitive resin composition baked at the same exposure dose were post-baked and the minimum size of the pattern was measured by SEM (Scanning Electron Microscope).

[0131] [Adhesion to substrate] On the cured film exposed over the entire surface on the substrate manufactured above, a checkerboard of 10 rows × 10 columns was cut and inserted at intervals of 2 mm using a blade, pasted with cellophane tape and then peeled off. The number of peeled-off pieces out of a total of 100 checkerboards was counted to evaluate the adhesion characteristics between the cured film and the substrate. ○: Less than 15 peeled off △: 15 or more and less than 30 peeled off X: 30 or more peeled off

[0132] [Measurement of glass transition temperature (Tg) and elongation at break of cured film] After the cured film exposed over the entire surface on the substrate manufactured above was peeled off from the substrate with an aqueous hydrogen fluoride solution, a cured film was produced. The Tg (glass transition temperature) and CTE (thermal expansion coefficient) of the cured film were measured by TMA (Thermomechanical analysis) on an insulating film with a thickness of 10 μm dried in an oven, and the elongation at break was measured by UTM (Universal Testing Machine) at room temperature under the condition of a speed of 5 cm / min.

Table 2

[0133] As shown in the results of Table 2, the polyimide resin according to the present specification and the photosensitive resin composition containing the same have high-resolution pattern characteristics, and the cured film is excellent in adhesion to the substrate. The cured films using the photosensitive resin compositions of Examples 1 to 7 contain the unsaturated group of Chemical Formula 2 using the polymers of Synthesis Example 3 and / or 4, the total molar ratio of Y and Z is 1, and when Z is a divalent organic group, the molar ratio of Z satisfies the range of 0.05 ≦ Z ≦ 0.3, so that good Tg (glass transition temperature) and CTE (thermal expansion coefficient) are maintained, and since it has a relatively high elongation at break, it was confirmed that excellent heat resistance and excellent mechanical properties can be ensured, and fine pattern formation is possible. On the other hand, in Comparative Examples 1 to 3, since only the polymers of Synthesis Example 1 and / or 2 are used, they do not contain the unsaturated group of Chemical Formula 2, or the molar ratio of Z does not satisfy the above range, so the cured physical properties are very inferior to those of the Example group, the CTE is very low, or the elongation at break is low.

Claims

1. A polyimide resin containing the structure of the following Chemical Formula 1: [Chemical Formula 1] 【Chemical Formula 1】 In the above Chemical Formula 1, 【Chemical Formula 2】 means a part bonded to other substituents or repeating units, X1 and X2 are the same as or different from each other, and are each independently a tetravalent organic group, Y is a divalent to tetravalent organic group, R ３ ~R ６ are the same as or different from each other, and are each independently hydrogen; or represented by the following Chemical Formula 2, provided that the structure represented by the following Chemical Formula 2 is 1 mol% or more based on the total number of moles of -OH contained in the polyimide resin, m1, m2, k1, and k2 are each 0 or 1, and 1 ≦ m1 + m2 + k1 + k2 ≦ 2, Z is a direct bond or a divalent organic group, The total molar ratio of Y and Z is 1. When Z is a divalent organic group, the molar ratio of Z is 0.05 ≦ Z ≦ 0.3, n is a real number from 1 to 50, m is a real number from 0 to 50, [Chemical Formula 2] 【Chemical Formula 3】 In the above Chemical Formula 2, * is the site linked to the above Chemical Formula 1, R7 is hydrogen; or a substituted or unsubstituted alkyl group, p is an integer from 1 to 10.

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

3. X1 and X2 are the same as or different from each other, and each independently is selected from the group consisting of the following structures, the polyimide resin according to claim 1: [Chemical Formula 4] In the above structure, [Chemical Formula 5] is the linking site with the carbonyl group (C(=O)) of the above Chemical Formula 1.

4. Y is selected from the group consisting of a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other, the polyimide resin according to claim 1.

5. Y is selected from the group consisting of the following structures, the polyimide resin according to claim 1: [Chemical Formula 6] In the above structure, A is a divalent organic group, [Chemical Formula 7] is the linking site with N of the above Chemical Formula 1.

6. A is a divalent hydrocarbon or a divalent organic group in which at least one carbon of the hydrocarbon is substituted with 0, S, C(=O), or SO ２ The polyimide resin according to claim 5.

7. A is selected from the group consisting of the following structures, the polyimide resin according to claim 5: [Chemical Formula 8] In the above structure, * is the [Chemical Formula 9] linking site to each phenolic group of.

8. Z is a direct bond or a divalent organic group of any one of the following structures, the polyimide resin according to claim 1: [Chemical Formula 10] In the above structure, B is a divalent organic group, [Chemical Formula 11] is a polyimide resin, which is the linking site with N in the above Chemical Formula 1.

9. B is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is substituted by 0, S, C(=O), or SO ２ and is a divalent organic group in which at least one hydrogen of the hydrocarbon is substituted by a halogen or an alkyl group. The polyimide resin according to Claim 8.

10. B is selected from the group consisting of the following structures. The polyimide resin according to Claim 8: [Chemical Formula 12] In the above structure, * is [Chemical Formula 13] is the linking site to each phenyl group of

11. The polyimide resin further includes a structure represented by the following Chemical Formula 3 as a terminal group. The polyimide resin according to Claim 1: [Chemical Formula 3] [Chemical Formula 14] In the above Chemical Formula 3, * is the site linked to the above Chemical Formula 1, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is a real number from 0 to 4. When re1 is 2 or more, Re1 may be the same as or different from each other, Re is hydrogen; or a structure represented by the above Chemical Formula 2.

12. The structure represented by the above Chemical Formula 2 is 10 mol% to 70 mol% based on the total number of moles of OH groups contained in the polyimide resin. The polyimide resin according to Claim 1.

13. The polyimide resin according to claim 1, wherein the weight average molecular weight is from 5,000 g / mol to 200,000 g / mol.

14. A negative photosensitive resin composition comprising the polyimide resin according to any one of claims 1 to 13; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

15. The negative photosensitive resin composition according to claim 14, wherein the crosslinking agent contains two or more structures represented by the following chemical formula 4: [Chemical formula 4] 【Chemical formula 15】 In the chemical formula 4, R8 and R9 are the same as or different from each other, and each independently is hydrogen; or a substituted or unsubstituted alkyl group, n' is an integer from 1 to 100, The acrylate group (—COO—) of the chemical formula 4 is linked to the acrylate group of the chemical formula 2 during exposure.

16. The negative photosensitive resin composition according to claim 14, wherein the polyimide resin contains one or more polyimide resins.

17. An electronic device comprising an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition according to claim 14.

18. The electronic device according to claim 17, wherein the organic insulating film includes an interlayer insulating film and a surface protection film.

19. The electronic device according to claim 17, wherein the electronic device further includes a memory component.

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