Polymer compound, photosensitive resin composition, insulating film, and electronic device comprising same

Abstract

Disclosed is a polymer compound providing excellent sensitivity, reliability of an electronic device, and adhesiveness. According to one aspect, provided is a polymer compound comprising at least one of repeating units represented by general formulas 1 and 2.

Description

Polymer compound, photosensitive resin composition, insulating film, and electronic device including the same

[0001] The present invention (Disclosure) relates to polymer compounds, and more specifically to polymer compounds, photosensitive resin compositions, insulating films, and electronic devices comprising the same.

[0002] Photosensitive resin compositions are representative functional polymer materials that have been commercialized in the production of various precision electronic products, and are currently utilized significantly in high-tech industries, particularly in the production of semiconductors and displays. Generally, a photosensitive resin composition refers to a composition in which chemical changes in the molecular structure occur within a short period upon light irradiation, resulting in changes in physical properties such as solubility in specific solvents, coloring, and curing.

[0003] The use of photosensitive resin compositions enables micro-precision machining, significantly reduces energy and raw materials compared to thermal reaction processes, and allows for rapid and accurate operation within a small installation space. Consequently, they are widely used in various precision electronics industries, such as advanced printing, semiconductor production, display manufacturing, and photocurable surface coating materials. These photosensitive resin compositions can be broadly classified into negative and positive types; negative-type compositions are those in which the irradiated area becomes insoluble in the developer, while positive-type compositions are those in which the irradiated area becomes solubilized in the developer.

[0004] According to one aspect, it provides a polymer compound with excellent sensitivity, adhesion, and reliability of electronic devices.

[0005] According to another aspect, it provides a polymer compound that does not generate residue within the insulating film.

[0006] According to another aspect, a photosensitive resin composition comprising the above-mentioned polymer compound is provided.

[0007] According to another aspect, the photosensitive resin composition provides a cured insulating film.

[0008] According to another aspect, an electronic device comprising the insulating film is provided.

[0009] The objects of the present invention are not limited to those mentioned above, and other unmentioned objects and advantages of the present invention may be understood from the following description and will be more clearly understood by the embodiments of the present invention. Furthermore, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof described in the specification.

[0010] According to a first aspect of the present invention, a polymer compound comprising at least one of the repeating units represented by the following general formulas 1 and 2 is provided.

[0011] [General Formula 1]

[0012]

[0013] [General Formula 2]

[0014]

[0015] In the above general formulas 1 and 2, R1 is each independently an identical or different tetravalent organic group, R2 is each independently an identical or different divalent organic group, X1 is each independently a hydrogen atom; or a structure represented by the following formula 1; and at least one of X1 is a structure represented by the following formula 1, and a is each independently an integer from 1 to 8.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1: X 11 and X 12 Each is independently directly bonded; a substituted or unsubstituted alkylene group at C1–C5; or a C5–C5 group substituted with a hydroxyl group.30 The cycloalkylene group of; and X 13 is a hydrogen atom; or a substituted or unsubstituted C1-C5 alkyl group, and in the above General Formula 2: X2 is each independently a hydrogen atom; or C1-C 20 It is a substituted or unsubstituted organic group.

[0019] According to a second aspect of the present invention, in the first aspect, the formula 1 may be a structure represented by the following formula 2.

[0020] [Chemical Formula 2]

[0021]

[0022] In the above chemical formula 2, X a is C5~C 30 It is a substituted or unsubstituted cycloalkylene group, n1 is an integer between 1 and 5 inclusive, and X 13 It is as defined in the first aspect above.

[0023] According to the third aspect of the present invention, according to the second aspect, the formula 2 is a structure represented by the following formula 2a.

[0024] [Chemical Formula 2a]

[0025]

[0026] R in the above chemical formula 2a 11 Each is independently a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; or a C2–C5 straight-chain or branched alkenyl group: and n1 and X 13 It is as defined in the second aspect above.

[0027] According to the fourth aspect of the present invention, in the first aspect, X in Formula 1 11 is a C1–C3 substituted or unsubstituted alkylene group, and X 12 It can be a direct combination.

[0028] According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the polymer compound is a compound produced by the reaction of a reactive compound comprising a diamine; an acid dianhydride; and at least one of an epoxy group and a hydroxyl group, and the content of the diamine having a hydroxyl group may be 50 mol% or more relative to 100 mol% of the total diamine.

[0029] According to the sixth aspect of the present invention, in any one of the first to fifth aspects, in general formulas 1 and 2, R1 is a structure derived from acid dianhydrides that are independently identical or different from each other, and R2-(OX1) a The structure may be produced by the reaction of a reactive compound comprising at least one of an epoxy group and a hydroxyl group with a moiety derived from each independently identical or different diamines.

[0030] According to the seventh aspect of the present invention, the acid anhydride in the sixth aspect may include at least one of the compounds represented by the following general formula 3.

[0031] [General Formula 3]

[0032]

[0033] In the above general formula 3, R 12 is an oxygen atom; a ketone group; a C1–C5 substituted or unsubstituted alkylene group; C6–C 30 A substituted or unsubstituted arylene group of; or -COO-R a -OOC-; and, here R a is a C1–C3 substituted or unsubstituted alkylene group, and R 13 Each is independently a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; or a C2–C5 substituted or unsubstituted alkenyl group, and n2 is 3.

[0034] According to the eighth aspect of the present invention, in the sixth or seventh aspect, the diamine may comprise at least one of the compounds represented by the following general formula 4.

[0035] [General Formula 4]

[0036]

[0037] In the above general formula 4, R 21 is an oxygen atom; or a C1–C5 substituted or unsubstituted alkylene group; and R 22 and R 23 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; -CF3; or is absent, or R 22 and R 23 They combine with each other to form a single ring or multiple rings, and R 21 In the case of this oxygen atom, R 22 and R 23 n3 and n4 are identical or distinct natural numbers satisfying n3+n4=4, and R 24 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; and C5–C 30 A substituted or unsubstituted cycloalkyl group of; or C6~C 30 A substituted or unsubstituted aryl group of; or, if n4 is 2 or greater, R 24 It combines with adjacent substituents to form a single ring or multiple rings.

[0038] According to the ninth aspect of the present invention, in the polymer compound, the degree of substitution of the structure represented by Formula 1 may be 50% or more.

[0039] According to the 10th aspect of the present invention, a photosensitive resin composition is provided, comprising: an alkali-soluble resin comprising a polymer compound according to any one of the 1st to 9th aspects; an initiator; and a coloring agent.

[0040] According to the 11th aspect of the present invention, in any one of the 1st to 10th aspects, the degree of imidization of the polymer compound may be 50% or more.

[0041] According to the 12th aspect of the present invention, in the 10th or 11th aspect, the content of the initiator may be 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin.

[0042] According to the 13th aspect of the present invention, in any one of the 10th to 12th aspects, the coloring agent may include a black pigment.

[0043] According to the 14th aspect of the present invention, a photosensitive resin composition comprising a solvent further comprising any one of the 10th to 13th aspects may be provided.

[0044] According to the 15th aspect of the present invention, an insulating film is provided in which a photosensitive resin composition according to any one of the 10th to 14th aspects is cured.

[0045] According to the 16th aspect of the present invention, an electronic device comprising an insulating film according to the 15th aspect is provided.

[0046] The means for solving the above problem are not all of the features of the present invention and may be combined with some embodiments of this specification. Various features of the present invention and the advantages and effects derived therefrom may be understood in more detail by referring to the specific description below.

[0047] According to one aspect, it is possible to achieve excellent sensitivity, reliability of electronic devices, and adhesion, as well as a residue-free effect.

[0048] According to another aspect, an insulating film applicable to a pixel define layer (PDL) and / or a column spacer can be implemented.

[0049] According to another aspect, highly reliable electronic devices can be implemented.

[0050] In addition to the effects described above, specific effects of the present invention are described together with the following explanation of specific details for implementing the invention. Furthermore, the effects of the present invention are not limited to those mentioned above and can be easily realized by means and combinations thereof described in the specification.

[0051] FIG. 1 shows an electronic device according to one embodiment of the present invention.

[0052] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0053] In this specification, the terms “comprise” and / or “comprising” specify the presence of the mentioned features, steps, numbers, actions, parts, elements, and / or groups thereof, and do not exclude the presence or addition of one or more other features, steps, numbers, actions, parts, elements, and / or groups thereof.

[0054] In this specification, expressions such as "first," "second," "(S1)," "(S2)," etc. may modify various components regardless of order and / or importance and do not limit such components. These expressions may be used to distinguish one component from another. For example, without departing from the scope of the present disclosure, the first component may be named the second component, and similarly, the second component may be renamed the first component.

[0055] In this specification, "at least one of a, b and c" is defined as comprising one or more selected from the group consisting of a, b and c.

[0056] Where various embodiments are described in this specification, each embodiment may be combined unless specifically stated otherwise. In this case, the effects of the present invention may be defined as including effects derived from each embodiment and effects resulting from the organic combination of each embodiment. For example, even if embodiments 1 and 2 are described independently in this specification, unless the context clearly indicates otherwise, embodiments 1 and 2 may be organically combined with each other, and the effects of the present invention may include effects resulting from the combination of embodiments 1 and 2.

[0057] In this specification, a range of numerical values ​​indicated by the term 'to' represents a range of numerical values ​​that includes the values ​​listed before and after the term as the lower and upper limits, respectively. For example, if 'a to b' is described in the specification, it may be understood that 'a to b' (a to b) is described.

[0058] In the present specification, if multiple numerical values ​​are disclosed for the upper and lower limits of any numerical range, the numerical range disclosed in the present specification may be understood as a range of any numerical values ​​in which any one of the multiple lower limit values ​​and any one of the multiple upper limit values ​​are respectively the lower limit value and the upper limit value. For example, if a or greater, or b or greater; and c or less, or d or less is described, it may be understood as a or greater and c or less, a or greater and d or less, b or greater and c or less, or b or greater and d or less.

[0059] In this specification, terms such as “about” or “substantially” mean a reasonable amount of variation of a term modified so as not to significantly alter the final result. Such terms may be interpreted to include a deviation of at least ±5% or at least ±10% relative to the stated value, to the extent that the deviation does not alter or invalidate the meaning of the word.

[0060] In this specification, "substituted" means, unless otherwise defined below, that at least one hydrogen atom is a halogen atom, hydroxyl group, carboxyl group, nitro group, amine group, sulfide group, thiol group, alkoxy group, acetoxy group, nitrile group, aldehyde group, ether group, ester group, acetal group, ketone group, C1~C 30 alkyl group of, C2~C 30 alkenyl group of, C2~C 30 alkynyl group, C1~C 40 alkylsilyl group of, C5~C 40 arylsilyl group of, C3~C 30 cycloalkyl group of, C3~C 30 The notification of, C6~C 30 aryl groups, heterocyclic groups (e.g., C2~C 30 heterocycloalkyl group of, C3~C 30 It is defined as being replaced by any one selected from the group consisting of the heteroaryl group of, derivatives thereof, and combinations thereof. Here, each of the substituents may bond to each other when adjacent to one another to form a substituted or unsubstituted fusion ring or spiro structure.

[0061] In this specification, "fused ring" means a ring in which two or more rings are bonded by sharing two or more atoms, and may include, for example, a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

[0062] In this specification, "spiro structure" refers to a spiro union, where a spiro union means a connection formed by two rings sharing only one atom.

[0063] For example, the above alkyl group may be straight-chain or branched, and specifically, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, It may be 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc.

[0064] For example, the cycloalkyl group may be cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc.

[0065] For example, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited but may be 2 to 40. Specific examples include the alkenyl group being vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc.

[0066] For example, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and specifically, it may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc.

[0067] In this specification, "*" may indicate a point connected to another part within the molecule.

[0068] In this specification, "adjacent substituent" is defined as a substituent applied to another atom directly bonded to the atom on which the substituent is applied. Taking a benzene ring as an example, one substituent and another adjacent substituent may be in an ortho relationship with each other.

[0069] According to one aspect of the present invention, a polymer compound comprising at least one of the repeating units represented by the following general formulas 1 and 2 is provided.

[0070] [General Formula 1]

[0071]

[0072] [General Formula 2]

[0073]

[0074] In the above general formulas 1 and 2, R1 is each independently an identical or different tetravalent organic group, R2 is each independently an identical or different divalent organic group, X1 is each independently a hydrogen atom; or a structure represented by the following formula 1; and at least one of X1 is a structure represented by the following formula 1, and a is each independently an integer from 1 to 8.

[0075] [Chemical Formula 1]

[0076]

[0077] In the above chemical formula 1, X 11 and X 12 Each is independently directly bonded; a substituted or unsubstituted alkylene group at C1–C5; or a C5–C5 group substituted with a hydroxyl group. 30 The cycloalkylene group of; and X 13 It is a hydrogen atom; or a C1 to C5 substituted or unsubstituted alkyl group.

[0078] In the above general formula 2: X2 are each independently a hydrogen atom; or C1~C 20 It is a substituted or unsubstituted organic group.

[0079] According to one aspect of the present invention, by providing a polymer compound comprising at least one of the repeating units represented by general formulas 1 and 2, it is possible to achieve excellent sensitivity, reliability of electronic devices, and adhesion, and to achieve the effect of having no residue. Specifically, by introducing the structure represented by formula 1 into a diamine-derived structure of polyamic acid and / or polyimide, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is achieved, and the effect of having no residue in the insulating film is achieved.

[0080] The configuration of the present invention will be described in more detail below.

[0081] 1. Polymer compounds

[0082] The polymer compound according to the present invention comprises at least one of the repeating units represented by the following general formulas 1 and 2.

[0083] [General Formula 1]

[0084]

[0085] [General Formula 2]

[0086]

[0087] In this specification, an organic group is defined as a group comprising at least one carbon atom. For example, the number of carbon atoms in the organic group may be 1 or more and 60 or less. In some non-limiting examples, the number of carbon atoms in the organic group may be 1 or more, 10 or more, 20 or more, 30 or more, 40 or more, or 50 or more, and may be 10 or less, 20 or less, 30 or less, 40 or less, 50 or less, or 60 or less.

[0088] Specifically, in the above general formulas 1 and 2: R1 is each independently an identical or different tetravalent organic group, and R2 is each independently an identical or different divalent organic group.

[0089] Specifically, X1 is each independently a hydrogen atom; or a structure represented by the following Chemical Formula 1; and at least one of X1 is a structure represented by the following Chemical Formula 1. At this time, by introducing a structure represented by the following Chemical Formula 1 into at least one of X1, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is realized, and a residue-free effect can be realized.

[0090] Specifically, a can be an integer of 1 to 8 independently, or 1, 2, 3, 4, 5, 6, 7, or 8. For example, a can be determined according to the number of hydroxyl groups bonded to the diamine compound to form R2. As an example, one or more hydroxyl groups of the diamine compound can be converted to -OX1 groups through a predetermined reaction.

[0091] [Chemical Formula 1]

[0092]

[0093] Specifically, in the above chemical formula 1, X 11 and X 12 Each is independently directly bonded; a substituted or unsubstituted alkylene group at C1–C5; or a C5–C5 group substituted with a hydroxyl group. 30 It is a cycloalkylene group.

[0094] Specifically, X 13 is a hydrogen atom; or a C1-C5 substituted or unsubstituted alkyl group. For example, the above X 13 It can be a hydrogen atom or a methyl group.

[0095] In the above chemical formula 1, * is the point where it is bonded to the oxygen atom of OX1.

[0096] Specifically, in the above general formula 2, X2 is each independently a hydrogen atom; or C1~C 20 It is a substituted or unsubstituted organic group. For example, in the above general formula 2, X2 can be a hydrogen atom.

[0097] In some examples, the polymer compound may be a random copolymer containing repeating units represented by general formulas 1 and 2.

[0098] In some embodiments of the present invention, the above chemical formula 1 may be a structure represented by the following chemical formula 2. In some embodiments of the present invention, by including the above chemical formula 1 in a structure represented by the following chemical formula 2, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is realized, and a residue-free effect can be realized.

[0099] [Chemical Formula 2]

[0100]

[0101] In the above chemical formula 2, X a is C5~C 30 It is a substituted or unsubstituted cycloalkylene group, and n1 is an integer between 1 and 5 inclusive. Here, X a The -OH group bonded to may be a substituent bonded to a cycloalkylene group that is a divalent linker. For example, the above X a The number of carbon atoms in the cycloalkylene group can be 5 or 6.

[0102] For example, X 13 is a hydrogen atom; or a C1–C5 substituted or unsubstituted alkyl group. In some examples, the above X 13 It can be a hydrogen atom or a methyl group.

[0103] In some embodiments of the present invention, n1 in Formula 2 may be 1, 2, 3, 4, or 5, and specifically may be 1 or 2. Here, n1 may be a factor that simultaneously affects the solubility of the photosensitive resin composition in a solvent and the solubility of the polymer compound in a developer. In some embodiments of the present invention, by adjusting n1 to the above numerical range, the solubility of the photosensitive resin composition in a solvent and the solubility of the polymer compound in a developer, which are in a trade-off relationship, can be simultaneously increased. Accordingly, sensitivity performance can be further improved.

[0104] In some examples, X of the above chemical formula 2 a The -OH group bonded to can be a substituent bonded to an atom adjacent to the ring atom of Xa directly connected to *. Such X a The -OH group bonded to it can be formed by the ring-opening reaction of a compound having an epoxy structure (e.g., ECMMA).

[0105] In some embodiments of the present invention, X of Formula 2 a The hydroxyl groups bonded to it can increase sensitivity by increasing affinity with water-soluble developers, and can improve the mechanical durability of the insulating film by forming hydrogen bonds between polymer compounds.

[0106] In some embodiments of the present invention, the above formula 2 may be a structure represented by the following formula 2a. In some embodiments of the present invention, by including the structure represented by the following formula 2a, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is realized, and an effect of having no residue in the insulating film can be realized.

[0107] [Chemical Formula 2a]

[0108]

[0109] Specifically, R in the above chemical formula 2a 11Each is independently a hydrogen atom; a C1-C5 straight-chain or branched alkyl group; or a C2-C5 straight-chain or branched alkenyl group.

[0110] X in the above chemical formula 2a 13 is a hydrogen atom; or a C1-C5 substituted or unsubstituted alkyl group. Specifically, in the above formula 2a, X 13 It can be a hydrogen atom or a methyl group.

[0111] In some embodiments of the present invention, n1 in Formula 2a may be 1, 2, 3, 4, or 5, and specifically may be 1 or 2. Here, n1 may be a factor that simultaneously affects the solubility of the photosensitive resin composition in a solvent and the solubility of the polymer compound in a developer. In some embodiments of the present invention, by adjusting n1 to the above numerical range, the solubility of the photosensitive resin composition in a solvent and the solubility of the polymer compound in a developer, which are in a trade-off relationship, can be simultaneously increased. Accordingly, sensitivity performance can be further improved.

[0112] In some embodiments of the present invention, in Formula 1, X 11 is a C1–C3 substituted or unsubstituted alkylene group, and X 12 can be a direct bond. For example, X in Chemical Formula 1 above. 11 The number of carbon atoms in the alkylene group of can be 1 or 2. In some embodiments of the present invention, in Formula 1, X 11 is a C1–C3 substituted or unsubstituted alkylene group, and X 12 By being composed of direct bonding, the adhesion of the insulating film and the reliability of the electronic device can be further improved. For example, X 11 is a C1–C3 substituted or unsubstituted alkylene group, and X 12In the case of direct bonding, an ether group may be formed. This ether group may be formed through a dehydration reaction between the hydroxyl group of a diamine-derived moiety and a reactive compound having a hydroxyl group (e.g., HEMA) under acidic conditions.

[0113] In some embodiments of the present invention, the polymer compound is a compound produced by the reaction of a reactive compound comprising a diamine; an acid dianhydride; and at least one of an epoxy group and a hydroxyl group, and the content of the diamine having a hydroxyl group may be 50 mol% or more relative to 100 mol% of the total diamine. Specifically, the content of the diamine having a hydroxyl group relative to 100 mol% of the total diamine may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, or 92 mol% or more, and specifically, any one or more of the plurality of lower limits; and may be 99 mol% or less or 100 mol% or less. In some non-limiting examples, the diamine having a hydroxyl group may include at least one of the compounds represented by Bis-APAF, BAP, and 9,9-Bis(3-amino-4-hydroxyphenyl)fluorene (F1 described below). In some embodiments of the present invention, by controlling the content of the diamine having a hydroxyl group to the above numerical range, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is achieved, and an effect of having no residue in the insulating film can be achieved.

[0114] In some other embodiments of the present invention, the polymer compound may include a repeating unit represented by General Formula 1 and may not include a repeating unit represented by General Formula 2. Here, the above embodiments can be realized by imidizing all repeating units of the polyamic acid structure by increasing the imidization reaction temperature. At this time, relative to 100 mol% of the total diamine synthesizing the polymer compound in General Formula 1, the content of the diamine having a hydroxyl group may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, 90 mol% or more, or 92 mol% or more, and specifically, any one or more of the plurality of lower limits; and may be 99 mol% or less or 100 mol% or less. In some embodiments of the present invention, the content of the diamine having the hydroxyl group is controlled to the above numerical range, thereby enabling a synergistic effect on sensitivity, reliability of electronic devices, and adhesion, and enabling the effect of having no residue in the insulating film.

[0115] In some cases, R2-(OX1) a The structural content is 1 H-NMR, 13 It can be analyzed using any one selected from the group consisting of C-NMR, FT-IR (Fourier transform-infrared spectroscopy), Py-GC / MS (Pyrolysis Gas Chromatography-Mass Spectrometry) and combinations thereof.

[0116] In this specification, “weight-average molecular weight” or “number-average molecular weight” refers to the standard polystyrene equivalent molecular weight and can be analyzed using a Gel Permeation Chromatography (GPC) device. For example, in the case of the GPC analysis method, the developing solvent may be set to tetrahydrofuran (THF), the column to be PL Olexis from Polymer Laboratories, the sample concentration to be 5 mg / mL, the sample injection volume to be 100 µl, the flow rate to be 1 mL / min, the detector to be an Agilent High Temperature RI detector, and the column temperature to be 40℃.

[0117] In some embodiments of the present invention, the weight-average molecular weight (M) of the polymer compound w ) may be 1,000 g / mol or more and 100,000 g / mol or less. Specifically, the weight-average molecular weight (M) of the polymer compound w ) may be 1,000 g / mol or more, or 2,000 g / mol or more; and 3,000 g / mol or less, 4,000 g / mol or less, 7,000 g / mol or less, 10,000 g / mol or less, 20,000 g / mol or less, 30,000 g / mol or less, 50,000 g / mol or less, 70,000 g / mol or less, 90,000 g / mol or less; or 100,000 g / mol or less. In some embodiments of the present invention, by controlling the weight-average molecular weight of the polymer compound to the above numerical range, it is possible to achieve a viscosity of the photosensitive resin composition suitable for a coating process and solubility of the photosensitive resin composition in a solvent, and to achieve the effect of having no residue in the insulating film.

[0118] In this specification, "derived structure" is defined as a structure formed by the reaction of a polyimide and / or polyamic acid, synthesized by the reaction of a diamine having one or more hydroxyl groups and an acid dianhydride, with a functional group (e.g., an epoxy group or a hydroxyl group) of a reactive compound to be described later. For example, if the functional group of the reactive compound is an epoxy group, the hydroxyl group of the diamine-derived moiety may act as a nucleophile under basic conditions to carry out a ring-opening reaction of the epoxy group. For another example, if the functional group of the reactive compound is a hydroxyl group, the hydroxyl group of the diamine-derived moiety and the hydroxyl group of the reactive compound may undergo a dehydration reaction under acidic conditions to form an ether structure.

[0119] In some embodiments of the present invention, in general formulas 1 and 2, R1 is a structure derived from acid dianhydrides that are independently identical or different from each other, and R2-(OX1) a Each may be a structure produced by the reaction of a diamine that is independently identical or different from each other and a reactive compound comprising at least one of an epoxy group and a hydroxyl group. Here, X1 and a are as described above.

[0120] In some embodiments of the present invention, the acid dianhydride may include at least one of the compounds represented by the following general formula 3.

[0121] [General Formula 3]

[0122]

[0123] In the above general formula 3, R 12 is an oxygen atom; a ketone group; a C1–C5 substituted or unsubstituted alkylene group; C6–C 30 A substituted or unsubstituted arylene group of; or -COO-R a -OOC-; and, here R a is a C1–C3 substituted or unsubstituted alkylene group, and R 13Each is independently a hydrogen atom; a C1-C5 straight-chain or branched alkyl group; or a C2-C5 substituted or unsubstituted alkenyl group, and n2 is 3.

[0124] In this specification, a single ring is defined as meaning a single aliphatic ring or a single aromatic ring structure. In some examples, the number of carbon atoms in the single ring may be 5 or more and 40 or less.

[0125] In this specification, a polyring is defined as any one selected from the group consisting of aliphatic rings, aromatic rings, and combinations thereof, comprising two or more ring structures that are identical or different from each other. For example, the two or more ring structures may include a spiro or a fused ring. In some examples, the number of carbon atoms in the polyring may be 6 or more and 50 or less.

[0126] In some embodiments of the present invention, the diamine may include at least one of the compounds represented by the following general formula 4.

[0127] [General Formula 4]

[0128]

[0129] R in the above general formula 4 21 is an oxygen atom; or a C1–C5 substituted or unsubstituted alkylene group; and R 22 and R 23 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; -CF3; or is absent, or R 22 and R 23 They can combine with each other to form a single ring or multiple rings. In this case, R 21 In the case of this oxygen atom, R 22 and R 23 It may not exist.

[0130] In the above general formula 4, n3 and n4 are identical or different natural numbers satisfying n3+n4=4, and R 24 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; and C5–C 30 A substituted or unsubstituted cycloalkyl group of; or C6~C 30 A substituted or unsubstituted aryl group of; or, if n4 is 2 or greater, R 24 It can combine with adjacent substituents to form a single ring or multiple rings.

[0131] In some examples, the above n3 can be 1 or 2, respectively.

[0132] In some examples, the single ring may be a cyclopentane structure, a cyclohexane structure, or a benzene ring structure.

[0133] In some examples, the above multiple rings may have a fluorene structure.

[0134] In some examples, the -OH group bonded to the benzene ring in the above general formula 4 may be a reactive functional group that enables the introduction of the structure represented by the above formula 1 into the polymer compound described above. Specifically, the -OH group of the above general formula 4 may react with a reactive compound containing at least one of the epoxy group and the hydroxyl group described later to form the structure represented by the above formula 1.

[0135] In some embodiments of the present invention, the reactive compound comprising at least one of the epoxy group and the hydroxyl group may comprise a (meth)acrylate having at least one of the hydroxyl group and the epoxy group at one end. In this specification, "(meth)acrylate" is defined as comprising any one selected from the group consisting of acrylate groups (-OOC-C(H)=CH2), methacrylate groups (-OOC-C(CH3)=CH2), and combinations thereof. For example, by the reactive compound comprising at least one of the epoxy group and the hydroxyl group, a reaction may proceed with a diamine moiety having a hydroxyl group of a polyimide and / or polyamic acid to form a repeating unit represented by General Formula 1 and / or 2.

[0136] In some examples, the reactive compound comprising at least one of the epoxy group and the hydroxyl group may be any one selected from the group consisting of 3,4-epoxycyclohexylmethyl methacrylate, 2-hydroxyethyl methacrylate, and combinations thereof, although not particularly limited.

[0137] In some other embodiments of the present invention, the polymer compound may further include at least one of the repeating units represented by the following general formulas 5 and 6.

[0138] [General Formula 5]

[0139]

[0140] [General Formula 6]

[0141]

[0142] In the above General Formulas 5 and 6, R3 may each independently be a structure derived from a diamine that does not contain an intramolecular hydroxyl group, and R1 and X2 may be the same as described above. For example, R1 may each independently be a tetravalent organic group that is identical or different from one another, and specifically may be derived from at least one of the compounds represented by General Formula 3. For example, X2 is a hydrogen atom; or C1 to C 20 It may be a substituted or unsubstituted organic group.

[0143] As described above, the content of the R2 structure relative to the total structure derived from the diamine of the polymer compound may be the content of the R2 structure relative to the total sum of the contents of R2 and R3 in general formulas 1, 2, 5 and 6, which is 100 mol%.

[0144] In some examples, the acid dianhydride for introducing the above R1 structure may include one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-8. In some examples, the above R1 may be a structure derived from one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-8.

[0145] [Chemical Formula 3-1]

[0146]

[0147] [Chemical Formula 3-2]

[0148]

[0149] [Chemical Formula 3-3]

[0150]

[0151] [Chemical Formula 3-4]

[0152]

[0153] [Chemical Formula 3-5]

[0154]

[0155] [Chemical Formula 3-6]

[0156]

[0157] [Chemical Formula 3-7]

[0158]

[0159] [Chemical Formula 3-8]

[0160]

[0161] In some examples, the diamine for introducing the above R3 structure may include one or more selected from the group consisting of compounds represented by the following chemical formulas 4-1 to 4-10. In some examples, the diamine that does not contain a hydroxyl group within the molecule may be one or more selected from the group consisting of compounds represented by the following chemical formulas 4-1 to 4-10. That is, in the above general formulas 5 and 6, R3 may be a structure derived from one or more selected from the group consisting of compounds represented by the following chemical formulas 4-1 to 4-10.

[0162] [Chemical Formula 4-1]

[0163]

[0164] [Chemical Formula 4-2]

[0165]

[0166] [Chemical Formula 4-3]

[0167]

[0168] [Chemical Formula 4-4]

[0169]

[0170] [Chemical Formula 4-5]

[0171]

[0172] [Chemical Formula 4-6]

[0173]

[0174] [Chemical Formula 4-7]

[0175]

[0176] [Chemical Formula 4-8]

[0177]

[0178] [Chemical Formula 4-9]

[0179]

[0180] [Chemical Formula 4-10]

[0181]

[0182] In some embodiments of the present invention, the degree of substitution of the structure represented by Formula 1 in the polymer compound may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 99% or more, and specifically, any one of the plurality of lower limits may be 100% or less, and more specifically, 100%. Specifically, the degree of substitution may refer to the ratio of the number of hydroxyl groups converted by (i) carrying out an epoxy ring-opening reaction between the reactive compound and the moiety under basic conditions, or (ii) carrying out an ether-forming reaction between the reactive compound and the moiety under acidic conditions, relative to the total number of hydroxyl groups of a diamine-derived moiety having hydroxyl groups in a polyimide and / or polyamic acid intermediate. For example, if all 100 -OH groups of a diamine-derived moiety in a polyimide and / or polyamic acid are substituted with the structure represented by Chemical Formula 1, the degree of substitution may be 100%. In some embodiments of the present invention, by controlling the degree of substitution to the above numerical range, synergistic effects on sensitivity, reliability of electronic devices, and adhesion are realized, and the effect of having no residue in the insulating film can be realized. For example, the degree of substitution of the structure represented by Chemical Formula 1 is determined by the change in the concentration of hydroxyl groups before and after the reaction using an acid value measurement method; and 1 H-NMR, 13It can be analyzed by a combination of C-NMR and FT-IR.

[0183] 2. Photosensitive resin composition

[0184] According to another aspect of the present invention, a photosensitive resin composition is provided comprising an alkali-soluble resin comprising a polymer compound of some embodiment; an initiator; and a coloring agent. According to another aspect of the present invention, by providing an alkali-soluble resin comprising the polymer compound, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is achieved, and a residue-free effect can be achieved.

[0185] In this specification, "alkali-soluble resin" is defined as a polymer resin having the property of being soluble in an alkaline solution. For example, the solubility of the alkali-soluble resin in a water-soluble alkaline solution may be 50 g / 100 g or more, 60 g / 100 g or more, 70 g / 100 g or more, 80 g / 100 g or more, 90 g / 100 g or more, or 99 g / 100 g or more at about 23°C, and specifically may be 100 g / 100 g.

[0186] In some embodiments of the present invention, the content of the alkali-soluble resin may be 1 part by weight or more and 50 parts by weight or less per 100 parts by weight of the photosensitive resin composition. Specifically, by controlling the content of the alkali-soluble resin within the above numerical range, a synergistic effect on sensitivity, reliability of electronic devices, and adhesion is achieved, and a residue-free effect can be achieved.

[0187] In some embodiments of the present invention, the degree of imidation of the polymer compound may be 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, or 99% or more, and specifically, any one or more of the plurality of lower limits may be 100% or less. In some embodiments of the present invention, by controlling the degree of imidation of the polymer compound to the above numerical range, the glass transition temperature and thermal decomposition temperature of the polymer compound may be increased, thereby improving heat resistance; further, mechanical properties may be further improved due to the rigid structural characteristics of the polyimide; and resolution may be further improved by suppressing the swelling phenomenon in which the exposure part absorbs the developer and expands in volume. In another aspect, by controlling the degree of imidation of the polymer compound to the above numerical range, the generation of outgas may be minimized, thereby further improving the reliability of the electronic device.

[0188] In some examples, the degree of imidation in the above polymer compounds was determined by measuring the infrared absorption spectrum of the polyimide, specifically the absorption peak at 1377 cm⁻¹ derived from the imide structure. -1 A step of measuring the peak intensity P1 in the vicinity; after heat-treating the polyimide at 350°C for 1 hour, measuring the infrared absorption spectrum to 1377 cm⁻¹ -1 It can be calculated through the steps of: measuring the peak intensity P2 in the vicinity; and calculating the degree of imidization of the polyimide using the peak intensities P1 and P2 through the following Equation 1.

[0189] [Equation 1]

[0190] Imidization[%]=(P1 / P2) χ100

[0191] In some embodiments of the present invention, the content of the initiator may be 1 part by weight or more and 30 parts by weight or less per 100 parts by weight of the alkali-soluble resin. Specifically, the content of the initiator may be 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more; and 25 parts by weight or less, or 30 parts by weight or less, per 100 parts by weight of the alkali-soluble resin. In some embodiments of the present invention, by controlling the content of the initiator to the above numerical range, the sensitivity of the photosensitive resin composition can be controlled, and a finer and more precise insulating film can be formed by achieving high resolution. Accordingly, when the insulating film is applied to an electronic device, the effect of separating each pixel and preventing light mixing can be further enhanced.

[0192] In some examples, the initiator is not particularly limited but may specifically be any one selected from the group consisting of thermal polymerization initiators, photopolymerization initiators, and combinations thereof, and may be a photopolymerization initiator.

[0193] For example, the photopolymerization initiator may be any one selected from the group consisting of radical photoinitiators, ionic photoinitiators, and combinations thereof. In some examples, the radical photoinitiator may include one or more selected from the group consisting of benzoin-based, acetophenone-based, benzophenone-based, thioxantone-based, alpha-hydroxyketone-based, alpha-aminoketone-based, and phosphine oxide-based compounds. In some examples, the ionic photoinitiator may be any one selected from the group consisting of sulfonium salts, iodonium salts, and combinations thereof.

[0194] In some embodiments of the present invention, the coloring agent may be any one selected from the group consisting of pigments, dyes, and combinations thereof, specifically may include a pigment, and more specifically may include a black pigment. In some embodiments of the present invention, by including a black pigment, the coloring agent may be applied to a black PDL (Pixel define layer) that separates each pixel and prevents light mixing, and / or a black column spacer that prevents light mixing.

[0195] In this specification, the average particle size of a particle is the particle size (D) at which the cumulative percentage in the volume-based particle size distribution curve reaches 50% when measured by a laser diffraction particle size distribution measuring device. 50 It can be defined as ). For example, the average particle size of the above particles can be calculated by dispersing the particles to be measured in a dispersion medium, introducing them into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500), and measuring the difference in diffraction patterns according to particle size as the particles pass through a laser beam.

[0196] In some embodiments of the present invention, the average particle size (D) of the pigment is 50 ) may be 50 nm or more and 190 nm or less. Specifically, the average particle size (D) of the pigment said above. 50The average particle size of the pigment may be 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, 170 nm or more, or 180 nm or more, and may be 60 nm or less, 70 nm or less, 80 nm or less, 90 nm or less, 100 nm or less, 110 nm or less, 120 nm or less, 130 nm or less, 140 nm or less, 150 nm or less, 160 nm or less, 170 nm or less, 180 nm or less, or 190 nm or less. In some embodiments of the present invention, by controlling the average particle size of the pigment to the above numerical range, a fine pattern with excellent heat resistance and light resistance can be effectively formed.

[0197] In some embodiments of the present invention, the content of the coloring agent may be 50 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin. Specifically, the content of the coloring agent with respect to 100 parts by weight of the alkali-soluble resin may be 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more, 100 parts by weight or more, 110 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, or 140 parts by weight or more; and 150 parts by weight or less, 160 parts by weight or less, 170 parts by weight or less, 180 parts by weight or less, 190 parts by weight or less, or 200 parts by weight or less. Specifically, by controlling the content of the colorant to the above numerical range, a photosensitive resin composition can be applied to a black PDL (Pixel define layer) that separates each pixel and prevents light mixing, and / or a black column space that prevents light mixing. In another aspect, by controlling the content of the colorant to the above numerical range, the color reproduction rate is excellent, and the curability and adhesion of the pattern can be further improved.

[0198] In some other embodiments of the present invention, the photosensitive resin composition may further include a solvent. For example, the solvent may include an organic solvent, and specifically, may include one or more selected from the group consisting of gamma-butyrolactone (GBL), N-methylpyrrolidinone (NMP), propylene glycol methyl ether acetate (PGME), ethyl lactate (EL), methyl 3-methoxypropionate (MMP), propylene glycol monomethyl ether (PGME), diethylene glycol methyl ether (MEDG), diethylene glycol butyl methyl ether (MBDG), diethylene glycol dimethyl ether (DMDG), and diethylene glycol diethyl ether (DEDG). It is possible.

[0199] In some examples, the content of the solvent is not particularly limited, but specifically, it may be 50% by weight or more and 90% by weight or less based on the total weight of the photosensitive resin composition.

[0200] In some other embodiments of the present invention, the photosensitive resin composition may further include one or more additives selected from the group consisting of acid generators and UV absorbers. When the additives are further included, the heat resistance of the photosensitive resin composition is improved, thereby enabling the realization of even better reliability of the electronic device. For example, the content of the additive may be 0.1 parts by weight or more and 1 part by weight or less per 100 parts by weight of the alkali-soluble resin.

[0201] In some examples, the above acid generating agent may include one or more selected from the group consisting of iodium salts, sulfonium salts, diazonium salts, ammonium salts, and pyridinium salts.

[0202] In some examples, the acid generating agent may be a diazoketone compound such as a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, or a diazonaphthoquinone compound; a sulfone compound such as a β-ketosulfone or a β-sulfonylsulfone; a sulfonate such as an alkylsulfonate, a haloalkylsulfonate, an arylsulfonate, or an iminosulfonate; or a naphthalimide such as N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(p-toluenesulfonyloxy)-1,8-naphthalimide, N-(methylsulfonyloxy)-1,8-naphthalimide, or N-(camposulfonyloxy)-1,8-naphthalimide.

[0203] In some embodiments of the present invention, the UV absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based, triazine-based, and salicylate-based types. Specifically, each of the UV absorbers may independently include one or more hydroxyl groups. In some embodiments of the present invention, by including one or more hydroxyl groups in the UV absorber, unwanted reactions (e.g., photodegradation, discoloration) caused by the insulating film being exposed to excessive ultraviolet rays during the exposure process can be prevented, and the clarity and uniformity of the pattern can be maintained.

[0204] In some examples, the above UV absorbers are 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole It may include one or more selected from the group consisting of (2-(2-Hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole), 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, phenyl salicylate, and octyl salicylate. there is.

[0205] In some examples, the photosensitive resin composition may be a negative-type photosensitive resin composition in which the light-exposed portion is cured and remains during the development process, while the light-unexposed portion is removed.

[0206] 3. Insulating films and electronic devices

[0207] In this specification, a “layer” or “film” may include cases where, when observing the region in which the layer or film exists, it is formed over the entire region, or cases where it is formed only in a part of the region. For example, the surface of the layer or film may be defined as having a flat shape, a non-flat shape, and combinations thereof; or a continuous shape, a discontinuous shape, and combinations thereof. For example, when another member is composed of a layer or film directly on a member, the coverage of the other member on the surface of the member may be defined as 1% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more. For example, it may also be defined as a “layer” or “film” when a plurality of particles form a clustered structure.

[0208] According to another aspect of the present invention, an insulating film is provided in which a photosensitive resin composition of some embodiment is cured.

[0209] According to another aspect of the present invention, an electronic device comprising an insulating film of some embodiment is provided. For example, the electronic device may be an organic light-emitting diode (OLED).

[0210] In some embodiments of the present invention, the organic light-emitting diode may comprise a substrate; a first electrode formed on the substrate; a second electrode disposed on the first electrode; and an organic light-emitting layer interposed between the first and second electrodes. For example, the first electrode may be an anode, and the second electrode may be a cathode.

[0211] In some embodiments of the present invention, the organic light-emitting diode may further include a pixel define layer (PDL) that separates each subpixel of the organic light-emitting layer. For example, if the pixel define layer is a black PDL, a cured body formed by curing a photosensitive resin composition of some embodiments may be included in the black PDL. In some embodiments of the present invention, the effect of preventing light mixing and improving contrast ratio may be further enhanced by including the cured body in the black PDL.

[0212] In some embodiments of the present invention, the insulating film may be formed in a pattern that partially exposes the upper surface of the first electrode.

[0213] In some embodiments of the present invention, the insulating film may be formed to partially cover the edge of the first electrode.

[0214] In some embodiments of the present invention, the organic light-emitting diode may further include a column spacer formed on the pixel separation layer. Specifically, the column spacer can maintain the spacing between pixels together with the black PDL described above and prevent light mixing. In some embodiments of the present invention, the column spacer may include a cured body in which the photosensitive resin composition described above is cured. In some embodiments of the present invention, the effect of preventing light mixing and improving contrast ratio may be further enhanced by including an insulating film in which the photosensitive resin composition is cured in the column spacer.

[0215] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the present invention; however, this is merely an example, and the scope of the present invention is not limited by the following.

[0216] [Synthetic Preparation Example 1: Preparation of Materials]

[0217] To synthesize an alkali-soluble resin, the compounds listed in Table 1 below were prepared as materials.

[0218] Classification Chemical Formula Bis-APAF 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropaneODA 4,4′-OxydianilineBAP 2,2-Bis(3-amino-4-hydroxylphenyl)propaneF1 9,9-Bis(3-amino-4-hydroxyphenyl)fluoreneODPA 4,4'-Oxydiphthalic AnhydrideTMEG Ethylene glycol bis(4-trimellitate anhydride)Cis-CHA cis-1,2-Cyclohexanedicarboxylic AnhydrideECMMA 3,4-Epoxycyclohexylmethyl methacrylateHEMA 2-hydroxyethyl methacrylateTEA Triethylamine

[0219] [Preparation Example 1: Synthesis of Polymer Compounds]

[0220] Diamine dissolution step:

[0221] A solution was prepared by adding the diamines of the table below to gamma-butyrolactone (GBL) and dissolving them at 70°C.

[0222] Dihydrogen dissolution step:

[0223] After adding the dianhydride of the table below to the above solution, the mixture was stirred at 70°C for 4 hours.

[0224] End-capping step:

[0225] After adding a terminal capping agent (Cis-CHA) to the stirred product, the mixture was reacted at 70°C for 2 hours, then the temperature was raised to 90°C and heptane was added.

[0226] Imidization stage:

[0227] After removing the water produced by the imidation condensation reaction at 110℃ with heptane using a Dean-Stark extractor, the stirring and imidation reaction was carried out at 180℃ for 4 hours.

[0228] Methacrylate group introduction step:

[0229] After lowering the temperature of the above imidization reaction product to 70℃, ECMMA and TEA were added and stirred for 12 hours to form a polymer compound (M w =2,000~4,000 g / mol) was synthesized.

[0230] At this time, the content of each of the above compositions was adjusted to the values ​​listed in the table below, and the unit of each composition is mol.

[0231] Classification (Unit: mol) Bis-APAFODAODPATMEGCis-CHAECMMATEA Synthetic Example 1881276-48502 Synthetic Example 2861476-48502 Synthetic Example 3841676-48502 Synthetic Example 4821876-48502 Synthetic Example 5802076-48502 Synthetic Example 6881276-48102 Synthetic Example 7881276-48802 Synthetic Example 8-1928383848502 Synthetic Example 8-2928383848102 Synthetic Example 9928323272502 Synthetic Example 10928363656502 Synthetic Example 11928404040502 Synthetic Example 12928404040102 Synthetic Example 13928404040802

[0232] Classification (Unit: mol) Bis-APAFODABAPTMEGCis-CHAECMMATEA Synthesis Example 14718217648502 Synthesis Example 15468467648502 Synthesis Example 16218717648502 Synthesis Example 1770-307648502 Synthesis Example 1884-167648502

[0233] Classification (Unit: mol) Bis-APAFODAF1a) TMEGCis-CHAECMMATEA Synthesis Example 19-8927648502 Synthesis Example 20468467648502a) F1: 9,9-Bis(3-amino-4-hydroxyphenyl)fluorene

[0234] Classification (Unit: mol) Bis-APAFODAODPATMEGCis-CHAECMMATEA Comparative Synthesis Example 1881276-48--

[0235] [Preparation Example 2: Synthesis of Polymer Compounds]

[0236] The imidization step was carried out in the same manner as in Preparation Example 1. Subsequently, the temperature of the imidization reaction product was lowered to 70°C, HEMA and TsOH (p-Toluenesulfonic acid) were added, and after stirring for 12 hours, the reaction was performed to produce a polymer compound (M w =2,000~4,000 g / mol) was synthesized.

[0237] Classification (Unit: mol) Bis-APAFODAODPATMEGCis-CHAHEMATsOH Synthesis Example 21881276-48505 Synthesis Example 22881276-48105 Synthesis Example 23881276-48805

[0238] [Synthetic Preparation Example 2: Preparation of Photoinitiator]

[0239] The photoinitiator listed in Table 7 below was prepared.

[0240] Classification Chemical Formula PHT-23 Structural Formula: Name: 1-((((11-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl)(2-(1,1,2,2,3,3,4,4-octafluorobutoxy)phenyl)methylene)amino)oxy)ethan-1-onePHT-21 Structural formula: Name: [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate

[0241] [Preparation Example 3: Preparation of Photosensitive Resin Composition]

[0242] A photosensitive resin composition comprising the composition and solvent described in Tables 8 to 10 below was prepared. Propylene glycol methyl ether acetate (PGMEA) was used as the solvent, and the content of the solvent was adjusted to about 75% by weight based on the total weight of the photosensitive resin composition.

[0243] Classification: Alkali-soluble resin, photoinitiator, black pigment c) Additive (Content) Structure Content Structure Content Content Example 1 Synthesis Example 1 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 2 Synthesis Example 2 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 3 Synthesis Example 3 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 4 Synthesis Example 4 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 5 Synthesis Example 5 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 6 Synthesis Example 6 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 7 Synthesis Example 7 100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 8 Synthesis Example 8 1100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 9 Synthesis Example 8 1100 Parts by weight PHT-2315 parts by weight 140 parts by weight Example 10 Synthesis Example 8-1100 parts by weight PHT-2320 parts by weight 140 parts by weight UVA 477 a) (7.5 parts by weight) Example 11 Synthesis Example 8-1100 parts by weight PHT-2120 parts by weight 140 parts by weight Example 12 Synthesis Example 8-2100 parts by weight PHT-2320 parts by weight 140 parts by weight a) UVA 477: Lotsorb UV 477 (UVA containing hydroxyphenyl triazine and 1-methoxy-2-propyl acetate at 18-20 wt%) c) Average particle size (D 50 A black pigment with a thickness of 100 nm; the same applies to the table below.

[0244] Classification: Alkali-soluble resin, photoinitiator, black pigment c)Structure Content Structure Content Content Example 13 Synthesis Example 9,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 14 Synthesis Example 10,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 15 Synthesis Example 11,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 16 Synthesis Example 12,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 17 Synthesis Example 13,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 18 Synthesis Example 14,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 19 Synthesis Example 15,100 parts by weight PHT-2,320 parts by weight 140 parts by weight Example 20 Synthesis Example 16,100 parts by weight PHT-2,320 parts by weight 140 Parts by weight Example 20 Synthesis Example 17,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 21 Synthesis Example 18,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 22 Synthesis Example 19,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 23 Synthesis Example 20,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 24 Synthesis Example 21,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 25 Synthesis Example 22,100 parts by weight PHT-2320 parts by weight 140 parts by weight Example 26 Synthesis Example 23,100 parts by weight PHT-2320 parts by weight 140 parts by weight

[0245] Classification: Alkali-soluble resin, photoinitiator, black pigment c) Imide Reaction Conditions Structure Content Structure Content Content Comparative Example 1 Comparative Synthesis Example 1 100 parts by weight PHT-2 320 parts by weight 140 parts by weight 180℃ / 4hr

[0246] [Experimental Example: Evaluation of Polymer, Photosensitive Resin Composition, and Insulating Film]

[0247] Imidation degree measurement:

[0248] The degree of imidization in polyimide is determined by measuring the infrared absorption spectrum of the polyimide, specifically the absorption peak at 1377 cm⁻¹ derived from the imide structure. -1 A step of measuring the peak intensity P1 in the vicinity; after heat-treating the polyimide at 350°C for 1 hour, measuring the infrared absorption spectrum to 1377 cm⁻¹ -1It can be calculated through the steps of: measuring the peak intensity P2 in the vicinity; and calculating the degree of imidization of the polyimide using the peak intensities P1 and P2 through the following Equation 1.

[0249] [Equation 1]

[0250] Degree of imidization [%] = (P1 / P2) X 100

[0251] Degree of substitution of Chemical Formula 1:

[0252] The degree of substitution of Formula 1 refers to the ratio of the number of hydroxyl groups converted by (i) proceeding an epoxy ring-opening reaction between ECMMA and a diamine-derived moiety having hydroxyl groups under basic conditions, or (ii) proceeding an ether-forming reaction between HEMA and said moiety under acidic conditions, relative to the total number of hydroxyl groups of the intermediate (polyamic acid and / or polyimide) during the polymer synthesis process. Here, the degree of substitution of Formula 1 is the change in the concentration of hydroxyl groups before and after the reaction using an acid value measurement method; and 1 H-NMR, 13 It was analyzed using a combination of C-NMR and FT-IR.

[0253] Sample manufacturing:

[0254] After applying the photosensitive resin composition according to the above preparation example onto an ITO substrate using a slit coater, a VCD (vacuum drying) process was carried out up to a pressure of 66 Pa, and a cured film with a thickness of 1.5 μm was formed by pre-baking on a hot plate at 120°C for 2 minutes.

[0255] Sensitivity measurement:

[0256] Using a predetermined pattern mask, the above sample was irradiated with ultraviolet light having a broadband intensity of 20 mW / cm² at a dose amount based on a sensitivity of 2.5 μm Contact Hole CD, then developed at 23°C for 1 minute with an aqueous solution of 2.38 wt% tetramethylammonium hydroxide, and then washed with ultrapure water for 1 minute. Next, the sample was cured in an oven at 250°C for 60 minutes to obtain a pattern film (insulating film) with a thickness of 2.0 μm. At this time, a sensitivity of 80 mJ or less was indicated as ◎, a sensitivity of 80 mJ or more and 100 mJ or less as O, a sensitivity of 100 mJ or more and 120 mJ or less as △, and a sensitivity of 120 mJ or more as X.

[0257] Adhesion strength measurement:

[0258] A pattern film was formed in the same manner as in the sensitivity measurement above, but the adhesion strength was compared and evaluated based on the minimum CD of the attached dot pattern. ◎ was indicated when adhesion strength was secured at a minimum CD of less than 5㎛, O when adhesion strength was secured at 5㎛ or more but less than 10㎛, △ when adhesion strength was secured at 10㎛ or more but less than 15㎛, and X when adhesion strength was secured or not secured at 15㎛ or more.

[0259] Residue measurement:

[0260] Using a predetermined pattern mask, the above sample was irradiated with ultraviolet light having a broadband intensity of 20 mW / cm² at a dose based on the formation of a 10 μm contact hole CD, then developed at 23°C for 1 minute with an aqueous solution of 2.38 parts by weight of tetramethylammonium hydroxide, and washed with ultrapure water for 1 minute. Afterward, the sample was cured in an oven at 250°C for 60 minutes to obtain a pattern film with a contact hole CD of 10 μm. ○ was indicated if there was no residue in the pattern film, and × was indicated if there was residue.

[0261] OLED Reliability:

[0262] FIG. 1 shows an electronic device according to an embodiment of the present invention. Referring to FIG. 1, an electronic device according to an embodiment of the present invention may include a via (1), an anode (2), a pixel define layer (PDL, 3), an organic light-emitting layer (4, EL), a cathode (5), and a capping layer (CPL, 6).

[0263] A pattern film was formed on a substrate as shown in FIG. 1 in the same manner as in the sensitivity measurement above, and EL (4) was deposited. Mg / Ag was deposited as a cathode (5) on top, and an encapsulation process was performed. The time (T) at which a 3% brightness drop occurs with the OLED device in the On state, based on 85°C and 85% RH. 97 ) was evaluated. ◎ was marked if 1,500 hours or more were secured, ○ if 1,000 hours or more but less than 1,500 hours were secured, △ if 700 hours or more but less than 1,000 hours were secured, and X if less than 700 hours were secured.

[0264] Classification Degree of Imide Chemical Formula 1 Substitution Sensitivity Adhesion Residue OLED Reliability Example 1 ≥ 50% ≥ 50% ◎○○○ Example 2 ≥ 50% ≥ 50% ○○○○ Example 3 ≥ 50% ≥ 50% ○○○○ Example 4 ≥ 50% ≥ 50% ○○○○ Example 5 ≥ 50% ≥ 50% ○○○○ Example 6 ≥ 50% ≥ 50% △○○○ Example 7 ≥ 50% ≥ 50% ◎◎○○ Example 8 ≥ 50% ≥ 50% ○○○○ Example 9 ≥ 50% ≥ 50% ○◎○○ Example 10 ≥ 50% ≥ 50% ○○○○ Example 11 ≥ 50% ≥ 50% ○○○○ Example 12 ≥ 50% ≥ 50% △○○○ Example 13≥50%≥50%◎○○○Example 14≥50%≥50%○○○○Example 15≥50%≥50%○○○◎Example 16≥50%≥50%△△○○Example 17≥50%≥50%○◎○○Example 18≥50%≥50%○◎○◎Example 19≥50%≥50%○◎○○Example 20≥50%≥50%○○○○Example 21≥50%≥50%○○○◎Example 22≥50%≥50%◎◎○○Example 23≥50%≥50%○◎○○Example 24≥50%≥50%○○○◎Example 25≥50%≥50%○◎○○Example 26≥50%≥50%○◎○○

[0265] Classification Degree of Imide Chemical Formula 1 Degree of Substitution Sensitivity Adhesion Residue OLED Reliability Comparison Example 110% 0% △XXX

[0266] [Explanation of the symbol]

[0267] 1: Via

[0268] 2: Anode

[0269] 3: Pixel Separation Layer

[0270] 4: Organic light-emitting layer

[0271] 5: Cathode

[0272] 6: Capping layer

Claims

Polymer compound comprising at least one of the repeating units represented by the following general formulas 1 and 2: [General Formula 1] [General Formula 2] In the above general formulas 1 and 2: R1 are each independently identical or different tetravalent organic groups, and R2 are each independently identical or different divalent organic groups, and X1 is each independently a hydrogen atom; or a structure represented by the following Chemical Formula 1; and at least one of X1 is a structure represented by the following Chemical Formula 1, and a is each independently an integer between 1 and 8. [Chemical Formula 1] In the above chemical formula 1: X 11 and X 12 Each is independently directly bonded; a substituted or unsubstituted alkylene group at C1–C5; or a C5–C5 group substituted with a hydroxyl group. 30 The cycloalkylene group of; and, X 13 It is a hydrogen atom; or a C1-C5 substituted or unsubstituted alkyl group, and In the above general formula 2: X2 are each independently hydrogen atoms; or C1~C 20 It is a substituted or unsubstituted organic group of. In paragraph 1, The above chemical formula 1 is: A structure represented by the following chemical formula 2, Polymer compounds: [Chemical Formula 2] In the above chemical formula 2: X a is C5~C 30 It is a substituted or unsubstituted cycloalkylene group, and n1 is an integer between 1 and 5 inclusive, and X 13 is as defined in Paragraph 1. In paragraph 2, The above chemical formula 2 is a structure represented by the following chemical formula 2a, Polymer compounds: [Chemical Formula 2a] In the above chemical formula 2a: R 11 Each is independently a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; or a C2–C5 straight-chain or branched alkenyl group, and n1 and X 13 is as defined in Paragraph 2. In paragraph 1, In the above chemical formula 1: X 11 is a C1–C3 substituted or unsubstituted alkylene group, and X 12 is a direct combination, Polymer compound. In paragraph 1, The above polymer compound is: A compound produced by the reaction of a reactive compound comprising a diamine; an acid dianhydride; and at least one of an epoxy group and a hydroxyl group, and The content of the diamine having a hydroxyl group is 50 mol% or more relative to 100 mol% of the total diamine, Polymer compound. In paragraph 1, In the above general formulas 1 and 2: R1 is a structure derived from each independently identical or different acid anhydride, and R2-(OX1) a is a structure produced by the reaction of a reactive compound comprising at least one of an epoxy group and a hydroxyl group, with a moiety derived from each independently identical or different diamines. Polymer compound. In paragraph 6, The above acidic anhydride is: Comprising at least one of the compounds represented by the following general formula 3, Polymer compounds: [General Formula 3] In the above general formula 3: R 12 is an oxygen atom; a ketone group; a C1–C5 substituted or unsubstituted alkylene group; C6–C 30 A substituted or unsubstituted arylene group of; or -COO-R a -OOC-; and, here R a is a C1~C3 substituted or unsubstituted alkylene group, and R 13 Each is independently a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; or a C2–C5 substituted or unsubstituted alkenyl group, and n2 is 3. In paragraph 6, The above diamine is: Comprising at least one of the compounds represented by the following general formula 4, Polymer compounds: [General Formula 4] In the above general formula 4: R 21 It is an oxygen atom; or a C1-C5 substituted or unsubstituted alkylene group; and R 22 and R 23 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; -CF3; or is absent, or R 22 and R 23 They combine with each other to form a single ring or multiple rings, and R 21 In the case of this oxygen atom, R 22 and R 23 ...does not exist, n3 and n4 are identical or distinct natural numbers satisfying n3+n4=4, and R 24 Each independently consists of a hydrogen atom; a C1–C5 straight-chain or branched alkyl group; and C5–C 30 A substituted or unsubstituted cycloalkyl group of; or C6~C 30 A substituted or unsubstituted aryl group of; or, if n4 is 2 or greater, R 24 It combines with adjacent substituents to form a single ring or multiple rings. In paragraph 1, In the above polymer compound, the degree of substitution of the structure represented by Chemical Formula 1 is 50% or more, Polymer compound. Alkali-soluble resin comprising a polymer compound according to any one of claims 1 to 9; Initiator; and Colorant; including Photosensitive resin composition. In Paragraph 10, The degree of imidization of the above polymer compound is 50% or more, Photosensitive resin composition. In Paragraph 10, The content of the above initiator is 5 parts by weight or more and 30 parts by weight or less per 100 parts by weight of the above alkali-soluble resin, Photosensitive resin composition. In Paragraph 10, The above coloring agent includes a black pigment, Photosensitive resin composition. In Paragraph 10, solvent; further comprising, Photosensitive resin composition. An insulating film cured from a photosensitive resin composition according to Clause 10. An electronic device comprising an insulating film according to paragraph 15.

Images