Positive photosensitive resin composition and electronic device containing the same

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to a positive photosensitive resin composition and an electronic device including the same, more particularly to a positive photosensitive resin composition that has excellent solubility and does not swell during development, and an electronic device including the same.

[0002] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0182702, filed with the Korean Intellectual Property Office on December 23, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Photosensitive resins are representative functional polymer materials that have been put to practical use in the production of various precision electronics and information industry products, and are currently being used in the high-tech industry, particularly in the production of semiconductors and displays. Generally, photosensitive resins refer to polymer compounds whose molecular structure undergoes chemical changes in a short period of time when irradiated with light, resulting in changes in physical properties such as solubility in a specific solvent, coloration, and hardening. Photosensitive resins enable fine precision processing, significantly reduce energy and raw materials compared to thermal reaction processes, and enable rapid and accurate work in a small installation space. As a result, they are widely used in various precision electronics and information industry fields, including advanced printing, semiconductor production, display production, and photo-curable surface coating materials.

[0004] Such photosensitive resins are broadly divided into negative and positive types, with negative photosensitive resins being insoluble in the developer when exposed to light, and positive photosensitive resins being soluble in the developer when exposed to light.

[0005] Polymers used in positive photosensitive resins must have low or no solubility in the developer after selective exposure, while the unexposed parts must have high solubility in the developer. This requirement is even more prevalent in the precision electronics and information industries so that extremely fine patterns can be formed.

[0006] However, in the case of polyimide resin, although it has excellent basic insulating and physical properties that polymers have, there is a trade-off problem in that when it is improved into a photosensitive material with high resolution, the existing properties are significantly deteriorated. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a positive photosensitive resin composition containing a polyimide having a closed ring structure that is excellent in solubility and does not cause swelling development during development when a pattern is formed using the positive photosensitive composition.

[0008] Another object of the present invention is to provide an electronic device including an organic insulating film or a photosensitive pattern formed from the positive photosensitive resin composition. [Means for solving the problem]

[0009] One embodiment of the present specification provides a positive photosensitive resin composition comprising a polyimide resin represented by the following Chemical Formula 1; a heat curing agent containing an epoxy ring; and a development modifier represented by the following Chemical Formula 3. [Chemical formula 1] [ka] In the above Chemical Formula 1, [ka] means a moiety that is attached to another structure, X1 and X2 are the same or different and each independently represent a tetravalent organic group; Y is a trivalent or tetravalent organic group; R3 to R6 are the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group; m1, m2, k1, and k2 are the same or different, and each independently represents 0 or 1, and 1≦m1+m2+k1+k2≦2; Z is represented by the following chemical formula 2-1, the following chemical formula 2-2, or a bond thereof, When the sum of the molar ratios of Y and Z is 1, the sum of the molar ratios of Z is 0.05 or more and 0.3 or less, n is a real number between 1 and 50, m is a real number between 0 and 50, [Chemical formula 2-1] [ka] [Chemical formula 2-2] [ka] In the above Chemical Formula 2-1 and Chemical Formula 2-2, [ka] is a moiety linked to Chemical Formula 1; R7 and R8 are the same or different and each independently represent hydrogen; deuterium; a hydroxy group; an alkoxy group, or a carboxy group; t is a real number between 1 and 4, s is a real number between 1 and 5, [Chemical formula 3] [ka] In the above Chemical Formula 3, L1 and L2 are the same or different and each independently represent a divalent or tetravalent organic group; Q is CH; O; C=O; S; or N=N; The sum of o and p is a real number between 2 and 100.

[0010] Another embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed from the positive photosensitive resin composition. [Effects of the Invention]

[0011] When forming a pattern using the positive photosensitive resin composition according to the present invention, the developability of the exposed area is improved during selective exposure and development, thereby improving the resolution of the pattern, and flexibility can be improved during the thermal curing process by forming crosslinks between the polyimide main chain of Formula 1 and the carboxy group (—COOH) of the development modifier of Formula 3. This improves chemical resistance and mechanical properties and enables low-temperature curing.

[0012] In addition, an electronic device including an organic insulating film or a photosensitive pattern having excellent performance formed from the positive photosensitive resin composition according to the present specification can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] An example of an organic insulating film for semiconductor use containing a photosensitive resin composition according to one embodiment of the present invention is shown below. [Figure 2] 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 is shown below. [Figure 3] 1 is a photo of a photosensitive pattern using a photosensitive resin composition according to an embodiment of the present invention. [Figure 4] 1 is a photo of a photosensitive pattern using a photosensitive resin composition according to an embodiment of the present invention. [Explanation of symbols]

[0014] 1. Silicon wafer (Si wafer) 2. First photosensitive pattern (PID1) 3, 8 pads 4 Solder balls 5. Second Photosensitive Pattern (PID2) 6 Circuit Board 7. First photosensitive pattern (RDL) 9. Second Photosensitive Pattern (PDL) 10...OLED layer DETAILED DESCRIPTION OF THE INVENTION

[0015] In this specification, when a part is said to "comprise" a certain component, this does not mean that it may further include other components, unless specifically stated to the contrary, but rather that it does not exclude other components.

[0016] In this specification, when a compound has 1 to 10 carbon atoms, it may be expressed as C1 to C10, C1-C10, or C1 to C10.

[0017] In this specification, the aromatic (organic) group may be a C6 to C20 arylene group, and the aliphatic group may be a C1 to C20 alkylene group or a C3 to C20 cycloalkylene group. Examples of the arylene group include a phenylene group.

[0018] The halogen group may be F, Cl, Br, or I.

[0019] As used herein, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group including deuterium; halogen; hydroxyl; -COOH; alkyl; cycloalkyl; aryl; and heteroaryl.

[0020] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the number of carbon atoms in the alkyl group is 1 to 30. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

[0021] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and 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 another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0022] 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 another embodiment, the aryl group has 6 to 20 carbon atoms. When the aryl group is a monocyclic aryl group, it may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. When the aryl group is a polycyclic aryl group, it may be a naphthyl group, an anthracenyl group, an indenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.

[0023] In this specification, the heterocyclic group refers to 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, specifically 2 to 20. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, an acridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, and a dibenzofuranyl group, but are not limited to these.

[0024] In this specification, the heterocyclic group may be an aliphatic or aromatic ring group.

[0025] In this specification, the above explanation of the heterocyclic group is applicable to the heteroaryl group, except that the heteroaryl group is aromatic.

[0026] Hereinafter, a positive photosensitive resin composition according to a specific embodiment of the present invention and an electronic device including the same will be described in detail.

[0027] <Positive-type photosensitive resin composition> One embodiment of the present invention provides a positive photosensitive resin composition comprising a polyimide resin represented by the following Chemical Formula 1; a heat curing agent containing an epoxy ring; and a development modifier represented by the following Chemical Formula 3: [Chemical formula 1] [ka] In the above Chemical Formula 1, [ka] means a moiety that is attached to another structure, X1 and X2 are the same or different and each independently represent a tetravalent organic group; Y is a trivalent or tetravalent organic group; R3 to R6 are the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group; m1, m2, k1, and k2 are the same or different, and each independently represents 0 or 1, and 1≦m1+m2+k1+k2≦2; Z is represented by the following chemical formula 2-1, the following chemical formula 2-2, or a bond thereof: When the sum of the molar ratios of Y and Z is 1, the sum of the molar ratios of Z is 0.05 or more and 0.3 or less, n is a real number between 1 and 50, m is a real number between 0 and 50, [Chemical formula 2-1] [ka] [Chemical formula 2-2] [ka] In the above Chemical Formula 2-1 and Chemical Formula 2-2, [ka] is a moiety linked to Chemical Formula 1; R7 and R8 are the same or different and each independently represent hydrogen; deuterium; a hydroxy group; an alkoxy group, or a carboxy group; t is a real number between 1 and 4, s is a real number between 1 and 5, [Chemical formula 3] [ka] In the above Chemical Formula 3, L1 and L2 are the same or different and each independently represent a divalent or tetravalent organic group; Q is CH; O; C=O; S; or N=N; The sum of o and p is a real number between 2 and 100.

[0028] The present inventors have confirmed through experiments that the terminal structure (Z) of the polyimide resin having the structure of Chemical Formula 1 and the carboxyl group (-COOH) of the development modifier of Chemical Formula 3 form a crosslinker, thereby improving flexibility, and as a result, not only are mechanical properties improved, but chemical resistance is also improved, and ultra-fine patterns can be easily formed. Based on this, the present invention has been completed.

[0029] In particular, the positive photosensitive resin composition does not use a polyimide precursor that requires a high-temperature thermal curing process (imidization process), but uses a polyimide resin that can be solution-processed at a low temperature, thereby replacing the high-temperature imidization process.

[0030] In one embodiment of the present invention, X1 and X2 may be the same or different and may each independently 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.

[0031] In one embodiment of the present invention, at least one of X1 and X2 may be a tetravalent aromatic organic group.

[0032] In one embodiment of the present invention, at least one of X1 and X2 may be a tetravalent aliphatic organic group.

[0033] In one embodiment of the present invention, at least one of X1 and X2 may be a tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0034] In one embodiment of the present invention, both X1 and X2 may be a tetravalent aromatic organic group.

[0035] In one embodiment of the present invention, both X1 and X2 may be tetravalent aliphatic organic groups.

[0036] In one embodiment of the present invention, both X1 and X2 may be a tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0037] In one embodiment of the present invention, X1 and X2 in Chemical Formula 1 may be the same or different and may each be independently selected from the group consisting of the following structures: [ka] In the above structure: [ka] may be a moiety that is linked to other structures (specifically, each carbonyl group) in Chemical Formula 1.

[0038] In one embodiment of the present invention, at least one of X1 and X2 may be selected from the group consisting of the following structures: [ka]

[0039] In one embodiment of the present invention, at least one of X1 and X2 may be selected from the group consisting of the following structures: [ka]

[0040] In one embodiment of the present invention, Y in Chemical Formula 1 may be selected from the group consisting of a trivalent or tetravalent aromatic organic group, a trivalent or tetravalent aliphatic organic group, and a trivalent or tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0041] In one embodiment of the present invention, Y may be a trivalent or tetravalent aromatic organic group.

[0042] In one embodiment of the present invention, Y may be a trivalent or tetravalent aliphatic organic group.

[0043] In one embodiment of the present invention, Y may be a trivalent or tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

[0044] In one embodiment of the present invention, Y may be selected from the group consisting of the following structures: [ka] In the above structure: A is a divalent organic group, [ka] may be a moiety that is linked to another structure in Chemical Formula 1 (specifically, N in Chemical Formula 1).

[0045] In some cases, any one of the -OH groups in the above structure may be replaced with -COOH.

[0046] In one embodiment of the present invention, Y may be any one of the following structures: [ka]

[0047] In one embodiment of the present invention, A may be selected from the group consisting of the following structures: [ka] In the above structure: * indicates other structures (specifically, [ka] This is the site that is linked to the respective phenol groups.

[0048] In one embodiment of the present invention, A may be any one of the following structures: [ka] [ka]

[0049] In one embodiment of the present invention, A may be of the following structure: [ka]

[0050] In one embodiment of the present invention, R3 to R6 in the above Chemical Formula 1 may be the same or different and may each independently represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms.

[0051] In one embodiment of the present invention, R3 to R6 may be the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms.

[0052] In one embodiment of the present invention, R3 to R6 may be the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0053] In one embodiment of the present invention, R3 to R6 may be the same or different and each independently represent a hydrogen atom or an unsubstituted alkyl group having 1 to 20 carbon atoms.

[0054] In one embodiment of the present invention, R3 to R6 may be the same or different and may each independently be hydrogen.

[0055] In one embodiment of the present invention, R7 and R8 in Chemical Formulas 2-1 and 2-2 are the same or different and each independently represent hydrogen; deuterium; a hydroxy group; an alkoxy group or a carboxy group, and at least one may be a hydroxy group or a carboxy group.

[0056] In one embodiment of the present invention, R7 and R8 in the above chemical formulas 2-1 and 2-2 are the same or different and each independently represent hydrogen; deuterium; a hydroxyl group; or a carboxyl group, and at least one may be a hydroxyl group or a carboxyl group.

[0057] In one embodiment of the present invention, R7 and R8 are the same or different and each independently represent a hydrogen atom; a hydroxy group; or a carboxy group, and at least one of them may be a hydroxy group or a carboxy group.

[0058] In one embodiment of the present invention, Q in the above formula 3 may be CH2 or S.

[0059] In one embodiment of the present invention, Q in Formula 3 may be CH2.

[0060] The polyimide resin containing the above structure exhibits the effect of reducing the blocking of light with a wavelength of 365 nm by the polyimide resin during the exposure process, thereby achieving the effects of fine processing and increasing sensitivity.

[0061] In one embodiment of the present invention, the polyimide resin may further include a structure represented by the following chemical formula E as a terminal group. [Chemical formula E] [ka] In the above chemical formula E, * is a site connected to Chemical Formula 1; Re1 is hydrogen; or a substituted or unsubstituted alkyl group; re1 is a real number between 0 and 4. When re1 is 2 or more, Re1 may be the same or different. Re is hydrogen.

[0062] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms.

[0063] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms.

[0064] In one embodiment of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0065] In one embodiment herein, Re1 is hydrogen.

[0066] In one embodiment of the present invention, the polyimide resin may have a weight average molecular weight of 5,000 g / mol to 200,000 g / mol.

[0067] If the weight average molecular weight is less than 5,000, it may be difficult to achieve the desired coating properties and mechanical properties when applying the polyimide copolymer, and if it exceeds 200,000, it may be difficult to use it as a photosensitive material due to its low solubility in a developer.

[0068] The weight-average molecular weight is one of the average molecular weights in which the molecular weight of a polymeric substance is not uniform and is used as a standard, and is a value obtained by averaging the molecular weights of the component molecular species of a polymeric compound having a molecular weight distribution by weight fraction.

[0069] In this specification, the weight average molecular weight may be a value measured by gel permeation chromatography, i.e., GPC.

[0070] In one embodiment of the present invention, the thermal curing agent may contain two or more epoxy rings.

[0071] In one embodiment of the present specification, the thermal curing agent may contain additional functional groups such as aromatic rings, amine groups, and ether groups in addition to two or more epoxy rings.

[0072] In one embodiment of the present specification, the thermal curing agent may have the following structure, but is not limited thereto: [ka]

[0073] In one embodiment of the present invention, the composition may further comprise, but is not limited to, a photosensitizer; a surfactant; and a solvent.

[0074] The surfactant is a silicone surfactant or a fluorine surfactant. Specifically, the silicone surfactant is 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-3 31, 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. may also be used. As the fluorine-based surfactant, DIC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-47 0, 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. may be used, but are not limited to these.

[0075] The solvent may be any compound known in the art to which the present invention pertains that enables the formation of a photosensitive resin composition, without particular limitation. Non-limiting examples of the solvent include one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0076] Examples of the ester solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, epsilon-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, 3-ethoxypropionate, etc.)), and alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.). methyl 2-oxypropionate, ethyl 2-oxypropionate, 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.

[0077] 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.

[0078] The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, or the like.

[0079] The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, or the like.

[0080] The sulfoxide solvent may be dimethyl sulfoxide or the like.

[0081] The positive photosensitive resin composition may further include additives known in the art depending on its intended use, such as an adhesion promoter, a defoaming agent, a leveling agent, an anti-gel agent, or a mixture thereof.

[0082] The adhesion promoter may be a silane coupling agent having a functional group such as epoxy, carboxy, or isocyanate, and specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, or a mixture thereof. Such adhesion promoters may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polyimide resin.

[0083] The surfactant may be any surfactant known to be usable in photosensitive resin compositions without particular limitation, but a fluorine-based surfactant or a silicone-based surfactant is preferably used, and such surfactant may be contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the polyimide resin.

[0084] In one embodiment of the present invention, the photosensitizer may contain one or more diazonaphthoquinone structures.

[0085] When diazonaphthoquinone is used as the photosensitizer, the diazonaphthoquinone-structured photosensitizer in the non-exposed areas forms a hydrogen bond with the phenol in the bis-APAF diamine of the polyimide chain, inhibiting development in the developer. Meanwhile, in the exposed areas, the diazonaphthoquinone-structured photosensitizer is released in the form of N2, absorbs moisture around the area, and changes to -COOH. This -COOH allows the exposed areas to have a faster development speed in the developer than the non-exposed areas, further improving the developability of the exposed areas.

[0086] In one embodiment of the present invention, the polyimide resin may include one or more types of polyimide resins.

[0087] The polyimide resin described above can be prepared by using a dianhydride compound and a diamine compound to produce one type of polyimide (an example of the polyimide represented by Chemical Formula 1) as illustrated in the following reaction formula. To produce other types of polyimides, materials and polymerization methods known in the art may be used. [Reaction Scheme 1-a] [ka] [Reaction Scheme 1-b] [ka]

[0088] <Electronic elements> Another embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed from the above-mentioned positive photosensitive resin composition.

[0089] In one embodiment of the present invention, the organic insulating film includes an interlayer insulating film and a surface protection film, and the electronic device further includes a memory component.

[0090] 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, it is advantageous for improving the surface state during the formation of a photosensitive film.

[0091] The organic insulating film or photosensitive pattern includes a polyimide having a specific structure and an acrylic compound having one or more photocurable acrylic functional groups, and can achieve high adhesion to substrates used in semiconductor devices, for example, metal substrates such as Au, Cu, Ni, and Ti, and inorganic substrates such as SiO2 and SiNx, while also having improved mechanical properties such as excellent heat resistance, insulating properties, and chemical resistance.

[0092] 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.

[0093] Therefore, an electronic device including an organic insulating film or a photosensitive pattern formed from the positive photosensitive resin composition can realize excellent performance such as high resolution and high sensitivity, and can exhibit excellent film characteristics and high mechanical properties. In addition, the electronic device can realize excellent heat resistance characteristics, for example, the adhesiveness of the organic insulating film or the photosensitive pattern can be firmly maintained without being reduced even when used for a long period of time or exposed to high temperature conditions for a long period of time.

[0094] 1 shows an example of an organic insulating film for semiconductors containing a photosensitive resin composition according to one embodiment of the present invention. Specifically, a silicon wafer 1 is coated with a positive photosensitive resin composition according to one embodiment of the present invention and then exposed to light to form a first photosensitive pattern (referred to as PID1) 2, with a pad 3 (e.g., a Cu pad) provided in contact with this pattern and a solder ball 4 partially provided on the top end of the pad. This PID1 2 can be used as an organic insulating film corresponding to the outermost layer of a semiconductor packaging material.

[0095] FIG. 2 shows an example of an organic insulating film for an organic light-emitting device, which includes a photosensitive resin composition according to an embodiment of the present invention. Specifically, in the OLED layer 10, a first photosensitive pattern (redistributed layer (RDL)) 7 formed from a positive-tone photosensitive resin composition according to an embodiment of the present invention is provided on a substrate 6 (e.g., TFT glass or TFT plastic (here, TFT stands for thin film transistor)), and a pad 8 (e.g., an Ag pad) is provided in contact with this pattern. In this case, a second photosensitive pattern (pixel define layer (PDL)) 9 is formed using a negative-tone photosensitive resin composition according to an embodiment of the present invention to leave a portion of the OLED where an organic light-emitting material will be placed. This PDL 9 can be used as an organic insulating film for the organic light-emitting device.

[0096] 3 and 4 are photographs of photosensitive patterns according to an embodiment of the present invention. Specifically, Fig. 4 shows a 15 μm square pattern with a thickness of 10 μm, and Fig. 3 shows a 5 μm hole pattern with a thickness of 8 μm.

[0097] The organic insulating film may include various insulating films of a semiconductor device, such as an interlayer insulating film, a surface protective film, a substrate electrode protective layer, a buffer coat film, or a passivation film, etc. The electric element may include various components of a semiconductor device.

[0098] The interlayer insulating film and surface protective film are not particularly limited, and those generally used in the relevant technical field can be adopted.

[0099] The memory component is not particularly limited, and any component commonly used in the art may be used.

[0100] Meanwhile, the organic insulating film or the photosensitive pattern may be formed through the steps of: applying the positive photosensitive resin composition on a supporting substrate and drying it 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.

[0101] The positive photosensitive resin composition can be used to easily form a patterned photosensitive resin film on a substrate such as glass, silicon wafer, etc. In this case, the positive photosensitive resin composition may be applied by spin coating, bar coating, screen printing, etc.

[0102] The support substrate used in the process of forming the photosensitive resin film is not particularly limited as long as it is known to be commonly used in the fields of electronics and communications or semiconductors, and specific examples thereof include a silicon wafer, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate.

[0103] During the drying process after coating, the coating is prebaked at 50°C to 150°C for about 1 to 20 minutes to evaporate the solvent, forming a prebaked film. If the drying temperature is too low, too much solvent remains, which can result in film loss even in the exposed areas during development, resulting in a low remaining film. If the drying temperature is too high, the curing reaction is accelerated, which can prevent the unexposed areas from being developed.

[0104] In the step of exposing the resin film, ultraviolet rays or visible light having a wavelength of 200 nm to 500 nm can be irradiated using a photomask having a pattern to be processed, and the exposure dose during irradiation is 10 mJ / cm. 2 ~4,000mJ / cm 2 The exposure time is also not particularly limited and may be appropriately changed depending on the exposure device used, the wavelength of the irradiating light, or the exposure dose, and specifically, the exposure time can be changed within the range of 1 to 150 seconds. In the step of forming the photosensitive resin film, an alkaline aqueous developer that is known to be commonly usable in the semiconductor or display manufacturing step may be used without any particular limitation. [Example]

[0105] Hereinafter, in order to specifically explain the present specification, a detailed description will be given using examples. However, the examples according to the present specification may be modified into various other forms, and the scope of the present specification should not be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to those skilled in the art.

[0106] Synthesis Example

[0107] <Synthesis Example 1> 1.2 eq of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1 eq of 4,4'-oxydiphthalic anhydride, and 1.2 eq of trimellitic anhydride were dissolved in PGMEA under a N2 atmosphere. Toluene was added to the reaction mixture at 140°C, and a Dean-Stark reactor was connected. The reaction was carried out overnight at 150°C. After the reaction, the toluene was removed using a Dean-Stark reactor, and the remaining toluene was removed by several PGMEA replacements. Residual monomer was confirmed by NMR, and the reaction was terminated to produce Polymer 1. The weight-average molecular weight was measured using gel permeation chromatography (GPC), and was found to be 15,000 g / mol. [Polymer 1] [ka]

[0108] In the polymer 1, n is a real number of 20 to 40, and is a value that allows the weight average molecular weight of the polymer to be 15,000 g / mol.

[0109] <Synthesis Example 2> 1 eq. of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.1 eq. of 4,4'-oxydiphthalic anhydride, and 0.13 eq. of 3-aminophenol were dissolved in PGMEA under a N2 atmosphere. Toluene was added to the reaction mixture at 140°C, and a Dean-Stark reactor was connected. The mixture was reacted overnight at 150°C. After the reaction, the toluene was removed using a Dean-Stark reactor, and the remaining toluene was removed by several PGMEA replacements. Residual monomer was confirmed by NMR, and the reaction was terminated to produce Polymer 2. The weight-average molecular weight was measured using gel permeation chromatography (GPC), and was found to be 15,000 g / mol. [Polymer 2] [ka]

[0110] In the polymer 1, n'' is a real number of 20 to 40, which indicates that the weight average molecular weight of the polymer is 15,000 g / mol.

[0111] Example

[0112] <Examples 1 to 8 and Comparative Examples 1 to 3> A positive photosensitive resin composition was prepared using the components listed in Table 1 below. Specifically, a photosensitive resin composition was prepared using the prepared polyimide resin and each component listed in Table 1 below. Table 1 below is based on 100 parts by weight of the resin composition containing Synthesis Example 1 or 2, a photosensitizer, a crosslinker, a surfactant, and a solvent.

[0113] [Table 1] A:TPA529 (Miwon) B: THA523 (Miwon) C: Poly(ethylene glycol) bis(carboxymethyl) ether (Mn600, Merck) D: Poly(ethylene glycol) bis(carboxymethyl) ether (Mn 250, Merck) E:VG3101L F: 4,4'-Methylenebis(N,N-diglycidylaniline) (Merck) G: BYK-307 (BYK-Chemie) H: Propylene glycol monomethyl ether acetate

[0114] Experimental example The photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated under the following process conditions, and the results are shown in Table 2. Specifically, the prepared photosensitive resin compositions were spin-coated onto Cu / Si wafers. After soft-baking at 120°C for 120 seconds, they were exposed to an appropriate exposure dose (i-line (365 nm)) and developed in a developer (2.38 wt% TMAH sol.). Post-baking was performed at 200°C for 1 hour to confirm pattern properties. Furthermore, to measure the cured film temperature and mechanical properties, each prepared photosensitive resin composition was coated onto a Si wafer, exposed to a front surface, soft-baked, and post-baked at 200°C for 1 hour. Resist evaluation conditions: PrB 120℃ / 120s, thickness 10μm Exposure: 600mJ / cm 2~900mJ / cm 2 i-line stepper Development: 23°C, 2.38 wt% (tetramethylammonium hydroxide) solution (TMAH (Tetramethylammonium hydroxide) solution), dipping, DI water rinse.

[0115] Pattern resolution The minimum size of the pattern of each photosensitive resin composition prepared at the same exposure dose and post-baked was measured using a scanning electron microscope (SEM).

[0116] [Adhesion to substrate] The cured film on the substrate thus prepared and exposed to the front side was cut with a blade into 10 rows x 10 columns of checkerboard patterns spaced 2 mm apart, and cellophane tape was attached and then peeled off. The number of checkerboard patterns that peeled off out of 100 was counted to evaluate the adhesion properties between the cured film and the substrate. ○: Peeled off into less than 15 pieces △: Peeled off into 15 or more but less than 30 pieces X: Peeled off in 30 or more pieces

[0117] [Measurement of glass transition temperature (Tg) and breaking elongation of cured film] The cured film was then peeled off from the substrate using a hydrogen fluoride solution to produce a cured film.The 10μm thick insulating film was dried in an oven and the Tg (glass transition temperature) and CTE (coefficient of thermal expansion) of the cured film were measured using a TMA (thermomechanical analysis) and the breaking elongation was measured using a UTM (universal testing machine) at room temperature and a speed of 5cm / min.

[0118] [Table 2]

[0119] As shown in Table 2, the polyimide resin according to the present specification and the photosensitive resin compositions of Examples 1 to 8 containing the same have high-resolution patterning characteristics, and the cured films have excellent adhesion to substrates. It was confirmed that the cured films of the produced photosensitive resin compositions have relatively high breaking elongation while maintaining good Tg (glass transition temperature) and CTE (coefficient of thermal expansion), ensuring excellent heat resistance and excellent mechanical properties, while also enabling the formation of fine patterns.

Claims

1. A positive photosensitive resin composition comprising a polyimide resin represented by the following Chemical Formula 1; a heat curing agent containing an epoxy ring; and a development modifier represented by the following Chemical Formula 3: [Chemical formula 1] 【Chemistry 1】 In the above Chemical Formula 1, 【Chemistry 2】 means a moiety that is attached to another structure, X1 and X2 are the same or different and each independently represent a tetravalent organic group; Y is a trivalent or tetravalent organic group; R ３ ~R ６ are the same or different and each independently represent hydrogen or a substituted or unsubstituted alkyl group; m １ , m ２ , k １ and k ２ are the same or different, and each independently represents 0 or 1, and 1≦m １ +m ２ +k １ +k ２ ≦2, Z is represented by the following chemical formula 2-1, the following chemical formula 2-2, or a bond thereof: When the sum of the molar ratios of Y and Z is 1, the sum of the molar ratios of Z is 0.05 or more and 0.3 or less; n is a real number from 1 to 50, m is a real number between 0 and 50, [Chemical formula 2-1] 【Transformation 3】 [Chemical formula 2-2] 【Chemistry 4】 In the above Chemical Formula 2-1 and Chemical Formula 2-2, 【Transformation 5】 is a moiety that is linked to Formula 1; R ７ and R ８ are the same or different and each independently represent hydrogen; deuterium; a hydroxy group; an alkoxy group, or a carboxy group; t is a real number between 1 and 4, s is a real number between 1 and 5, [Chemical formula 3] 【Transformation 6】 In the above Chemical Formula 3, L1 and L2 are the same or different and each independently represent a divalent or tetravalent organic group; Q is CH ２ O; C=O; S; or N=N, The sum of o and p is a real number between 2 and 100.

2. 2. The positive photosensitive resin composition according to claim 1, wherein X1 and X2 are the same or different and 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.

3. X1 and X2 are the same or different and are each independently selected from the group consisting of the following structures: 【Transformation 7】 In the above structure: 【Transformation 8】 is a moiety that is linked to another structure in Formula 1. The positive photosensitive resin composition according to claim 1,

4. 2. The positive photosensitive resin composition according to claim 1, wherein Y is selected from the group consisting of a trivalent or tetravalent aromatic organic group, a trivalent or tetravalent aliphatic organic group, and a trivalent or tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other.

5. Y is selected from the group consisting of the following structures: 【Chemistry 9】 In the above structure: A is a divalent organic group, 【Chemistry 10】 is a moiety that is linked to another structure in Formula 1. The positive photosensitive resin composition according to claim 1,

6. 6. The positive photosensitive resin composition according to claim 5, wherein A is selected from the group consisting of the following structures: 【Chemistry 11】 In the above structure: * indicates the site where the molecule is linked to another structure.

7. R ７ and R ８ and are the same or different and each independently represent hydrogen; deuterium; a hydroxy group; an alkoxy group, or a carboxy group, and at least one of them is a hydroxy group or a carboxy group.

8. The positive photosensitive resin composition according to claim 1, wherein the polyimide resin further comprises a structure represented by the following chemical formula E as an end group: [Chemical formula E] 【Chemistry 12】 In the above chemical formula E, * is a site connected to Chemical Formula 1; Re1 is hydrogen; or a substituted or unsubstituted alkyl group; re1 is a real number from 0 to 4, and when re1 is 2 or more, Re1 are the same or different from each other; Re is hydrogen.

9. 2. The positive photosensitive resin composition according to claim 1, wherein the polyimide resin has a weight average molecular weight of 5,000 g / mol to 200,000 g / mol.

10. The positive photosensitive resin composition according to claim 1 , wherein the heat curing agent contains two or more epoxy rings.

11. 2. The positive photosensitive resin composition according to claim 1, further comprising a photosensitizer; a surfactant; and a solvent.

12. The positive photosensitive resin composition according to claim 11, wherein the photosensitizer contains one or more diazonaphthoquinone structures.

13. The positive photosensitive resin composition according to claim 1 , wherein the polyimide resin comprises one or more polyimide resins.

14. An electronic device comprising an organic insulating film or a photosensitive pattern formed from the positive photosensitive resin composition according to any one of claims 1 to 13.

15. The electronic device according to claim 14 , wherein the organic insulating film includes an interlayer insulating film and a surface protection film, and the electronic device further includes a memory component.

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