Positive photosensitive resin composition, photosensitive resin film, and display device using the same

Abstract

The present invention relates to a positive photosensitive resin composition, a photosensitive resin film and a display device using the same. The positive photosensitive resin composition according to the present invention not only has excellent sensitivity, chemical resistance, heat resistance and other properties, but also greatly improves resolution, penetration, heat discoloration resistance and the like, and can be used to make high-brightness, high-resolution panels. Therefore, in the display, it can be effectively applied not only to interlayer insulating films, passivation insulating films, gate insulating films, but also to planarization films, retaining walls (Bank), pixel defining layers, etc.

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition and a display using the same. More specifically, the present invention relates to a positive photosensitive resin composition having excellent resolution, photolithography process margin, heat resistance, etc.

[0002] In particular, the present invention relates to a positive photosensitive resin composition having excellent sensitivity and transparency and significantly improved adhesion, thereby being suitable for forming an interlayer insulating film and PDL (pixel definition layer), columnar spacers, etc. in the process of LCD and OLED. Background Art

[0003] In the manufacturing process of TFT type liquid crystal display device (LCD) and organic light emitting display device (OLED), the interlayer insulating film is used to insulate the wiring arranged between each layer. However, due to the recent development of high-speed reaction and high-resolution devices, high aperture ratio and low-resistance wiring technology are required, so the width of the circuit is reduced and the thickness is formed to be higher, resulting in a trend of increasing the height difference of the TFT. In this case, the thickness of the interlayer insulating film used for flattening will increase, which will become the cause of the decrease in sensitivity and transparency, thereby causing the productivity and quality of the display device panel to decrease. Therefore, it is urgent to develop an insulating film with excellent sensitivity, transparency, etc. Summary of the invention

[0004] Technical issues

[0005] The present invention aims to provide a positive photosensitive resin composition, which has excellent resolution, photolithography process margin, heat resistance, especially excellent sensitivity and transparency, and significantly improved adhesion, so that it is suitable for forming interlayer insulating films and PDL, columnar spacers, etc. in LCD and OLED processes.

[0006] In addition, the present invention is intended to provide a display comprising a cured product of the positive photosensitive resin composition.

[0007] Technical Solution

[0008] The positive photosensitive resin composition disclosed in the present specification comprises: a) a first copolymer comprising i) a repeating unit derived from an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group, ii) a repeating unit derived from an unsaturated carboxylic acid compound, and iii) a repeating unit derived from an ethylenically unsaturated compound;

[0009] b) a second copolymer, at least a portion of the terminal hydroxyl groups of which are protected by an acid-decomposable protecting group;

[0010] c) a photoacid generator; and

[0011] d) a solvent,

[0012] The second copolymer includes repeating units represented by Chemical Formulas 1 and 2 below.

[0013] [Chemical formula 1]

[0014]

[0015] [Chemical formula 2]

[0016]

[0017] In the above chemical formula 2,

[0018] R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

[0019] The present specification also provides a photosensitive resin film comprising a cured product of the positive photosensitive resin composition.

[0020] This specification also provides a display device, which includes the above-mentioned photosensitive resin film.

[0021] Effects of the Invention

[0022] According to the embodiment, the positive photosensitive resin composition has excellent resolution, photolithography process margin, heat resistance, and in particular has excellent sensitivity and penetration, and significantly improves adhesion, so that it is suitable for forming interlayer insulating films and PDL, columnar spacers, etc. in LCD and OLED processes. In addition, the present invention provides a method for forming a pattern of an LCD and OLED substrate and a display substrate of the photosensitive resin composition using a cured body of the photosensitive resin composition. The pattern can be used as a material for a passivation insulating film, a gate insulating film, a planarizing film, a columnar spacer, an isolation wall, etc. of TFT-LCD, TSP (touch screen panel), OLED, O-TFT, EPD, EWD, etc. DETAILED DESCRIPTION

[0023] Hereinafter, a positive photosensitive resin composition, a photosensitive resin film, and a display device according to specific embodiments of the present invention will be described in more detail.

[0024] The embodiments are described in detail below to facilitate those skilled in the art to implement the present invention. The embodiments can be implemented in various ways and are not limited to the specific embodiments described herein.

[0025] The present invention relates to a positive photosensitive resin composition that can be used in various fields such as interlayer insulating films, passivation insulating films, gate insulating films, overcoats, columnar spacers, and PDL isolation walls arranged between various layers of displays such as liquid crystal displays (LCDs) and organic light-emitting displays (OLEDs).

[0026] 1. Positive photosensitive resin composition

[0027] According to one embodiment of the present invention, a positive photosensitive resin composition comprises: a) a first copolymer, which comprises i) a repeating unit derived from an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group, ii) a repeating unit derived from an unsaturated carboxylic acid compound, and iii) a repeating unit derived from an ethylenically unsaturated compound; and b) a second copolymer, at least a portion of whose terminal hydroxyl groups are protected by an acid-decomposable protective group. The first copolymer may be polymerized as follows: relative to 100 moles of the total content of the monomers used for synthesis, the content of the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group is 1 to 50 mol%, the content of the unsaturated carboxylic acid compound is 5 to 40 mol%, and the content of the ethylenically unsaturated compound is greater than or equal to 10 mol% and less than 70 mol%. A positive photosensitive resin composition may be provided, wherein the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group may include at least any one of the compounds represented by the following chemical formula 3 or 4, and the second copolymer includes any one of the main chains represented by the following chemical formulas 5 to 7.

[0028] In one embodiment of the present invention, the first copolymer of a) can be synthesized by a free radical reaction in the presence of i) an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group, ii) an unsaturated carboxylic acid compound and iii) a monomer of an ethylenically unsaturated compound, a solvent and a polymerization initiator.

[0029] Specifically, the ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group may include any one of the compounds represented by the following Chemical Formula 3 or 4.

[0030] [Chemical formula 3]

[0031]

[0032] In the above Chemical Formula 3, R1 is one of a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group,

[0033] [Chemical formula 4]

[0034]

[0035] In the above Chemical Formula 4, R2 is hydrogen or a C1 to C10 alkyl group, R3 is one of a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group or an acetoxyethoxyethyl group, and n is an integer from 0 to 4.

[0036] Since the first copolymer includes as a monomer the above-mentioned ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group, when a photolithography pattern is formed, the contrast (Contrst) can be improved by maximizing the difference in developer dissolution rate between the exposed part and the unexposed part. Therefore, the insulating film prepared from the positive photosensitive resin composition according to one embodiment of the present invention can achieve excellent sensitivity, resolution, transmittance, heat discoloration resistance, photolithography process margin, adhesion and heat resistance.

[0037] On the other hand, if the first copolymer including the ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protective group is not used as a monomer during polymerization, there may be technical problems of poor sensitivity, resolution and photolithography process margin.

[0038] Since the first copolymer includes an ethylenically unsaturated compound having a terminal hydroxyl group protected by an acid-decomposable protecting group as a monomer, the repeating unit derived from the ethylenically unsaturated compound having a terminal hydroxyl group protected by an acid-decomposable protecting group may include any one of the repeating units represented by the following Chemical Formula 3-1 or 4-1.

[0039] [Chemical formula 3-1]

[0040]

[0041] In the above chemical formula 3-1, R1′ is one of a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group,

[0042] [Chemical formula 4-1]

[0043]

[0044] In the above chemical formula 4-1, R2' is hydrogen or a C1 to C10 alkyl group, R3' is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group or an acetoxyethoxyethyl group, and n' is an integer from 0 to 4.

[0045] The first copolymer may be a copolymer obtained by copolymerizing a monomer mixture of the first copolymer, wherein the monomer mixture of the first copolymer contains, relative to 100 mol % of the total monomer mixture of the first copolymer, greater than or equal to 1 mol % and less than or equal to 50 mol %, or greater than or equal to 1 mol % and less than or equal to 20 mol % of i) an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group.

[0046] If the first copolymer is a copolymer obtained by copolymerizing a monomer mixture of an olefinic unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group in an amount of less than 1 mol %, then when a photolithographic pattern is formed, the difference in dissolution rate of the developer between the exposed portion and the unexposed portion is reduced, and it is impossible to improve the contrast (Contrst). Therefore, not only the sensitivity and resolution are deteriorated, but there will also be technical problems such as poor transmittance, heat discoloration resistance, photolithographic process margin, adhesion and heat resistance.

[0047] If the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing more than 50 mol % of the above-mentioned terminal hydroxyl group protected by an acid-decomposable protective group, then when forming a photolithography pattern, even if the exposure process is carried out, the residual rate of the above-mentioned terminal acid-decomposable protective group will be high, and technical problems such as poor sensitivity, resolution and poor photolithography process margin may occur.

[0048] Alternatively, the first copolymer may contain 1 mol% to 50 mol% or 1 mol% to 20 mol% of the repeating units derived from ethylenically unsaturated compounds in which the terminal hydroxyl groups are protected by acid-decomposable protecting groups, relative to the total repeating units.

[0049] If the first copolymer contains less than 1 mol % of the repeating units derived from olefinically unsaturated compounds in which the terminal hydroxyl groups are protected by acid-decomposable protecting groups, relative to the overall repeating units, then when forming a photolithographic pattern, the difference in dissolution rate of the developer between the exposed portion and the unexposed portion is reduced, and it is impossible to improve the contrast (Contrst). Therefore, not only the sensitivity and resolution are deteriorated, but there will also be technical problems such as poor transmittance, heat discoloration resistance, photolithography process margin, adhesion and heat resistance.

[0050] Relative to the overall repeating units, the first copolymer contains more than 50 mol % of the repeating units derived from olefinically unsaturated compounds in which the terminal hydroxyl groups are protected by acid-decomposable protecting groups. When forming a photolithographic pattern, even if an exposure process is performed, the residual rate of the terminal acid-decomposable protecting groups will be relatively high, which may lead to technical problems such as poor sensitivity, resolution and poor photolithographic process margin.

[0051] The unsaturated carboxylic acid compound may be an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, etc.; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, etc.; or an anhydride of an unsaturated dicarboxylic acid thereof, used alone or in combination of at least two. In particular, the use of acrylic acid, methacrylic acid or maleic anhydride can improve copolymerization reactivity and solubility in an alkaline aqueous developer solution.

[0052] The unsaturated carboxylic acid compound may be mixed in an amount of 1 mol% or more and 50 mol% or more and 50 mol% or more and 25 mol% or less and 35 mol% relative to 100 mol% of the total monomer mixture of the first copolymer. If the content of the unsaturated carboxylic acid compound is less than 1 mol%, it will be difficult to dissolve in an alkaline aqueous solution. If it is greater than 50 mol%, the solubility in an alkaline aqueous solution will become too large.

[0053] Specifically, if the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing more than 50 mol % of the above-mentioned unsaturated carboxylic acid compound, the solubility in aqueous alkali solution becomes too large, and technical problems such as poor sensitivity, resolution, adhesion, heat resistance and photolithography process margin may occur.

[0054] The ethylenically unsaturated compound may be methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyl oxyethylmethacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethylmethacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethylmethacrylate, isoboronyl methacrylate, phenylmethacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, methacrylate), styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene, 2-[methacryloyloxy]ethyl 6-hydroxyhexanoate, 4-vinylphenol, 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, methyl [[4-hydroxymethyl]cyclohexyl] methacrylate, 3-hydroxy-1-methacryloyloxyadamantyl ester, 2-oxotetrahydrofuran-3-yl methacrylate methacrylate), 4-hydroxycyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 3-ethyl-3-oxetane methacrylate, 3-ethyl-3-oxetane acrylate, 3-butyl-3-oxetane methacrylate, 3-butyl-3-oxetane acrylate, 3-propyl-3-oxetane methacrylate, 3-propyl-3-oxetane acrylate, 3-oxetane methacrylate, 3-oxetane acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxypropyl acrylate. The compounds mentioned can be used alone or in combination of at least two.

[0055] The ethylenically unsaturated compound may be mixed in an amount of 1 mol% or more and 50 mol% or more, or 20 mol% or more and 50 mol% or more, or 20 mol% or more and 30 mol% or less relative to 100 mol% of the total monomer mixture of the first copolymer. When the content is within this range, swelling does not occur after development, and the ideal solubility in the developer alkaline aqueous solution can be maintained.

[0056] Specifically, if the first copolymer is a copolymer obtained by copolymerizing a monomer mixture containing more than 50 mol % of the above-mentioned ethylenically unsaturated compound, technical problems such as poor sensitivity, resolution, adhesion, heat resistance and photolithography process margin may occur due to reduced development speed and photosensitivity.

[0057] In addition, for the a) first copolymer, the weight average molecular weight (Mw) of the first copolymer in terms of polystyrene may be greater than or equal to 3000 g / mol and less than or equal to 30000 g / mol.

[0058] As a solvent for solution polymerization of the monomer, methanol, tetrahydroxyfuran, toluene, dioxane, etc. can be used. A polymerization initiator used for solution polymerization can be a free radical polymerization initiator, specifically, 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis(cyclohexane-1-carbonitrile), or 2,2'-azobisisobutylate, etc. can be used.

[0059] That is, the positive photosensitive resin composition of the above-mentioned embodiment may include a first copolymer polymerized as follows: the first copolymer is polymerized in the presence of greater than or equal to 2 parts by weight and less than or equal to 24 parts by weight, greater than or equal to 2 parts by weight and less than or equal to 10 parts by weight, or greater than or equal to 5 parts by weight and less than or equal to 10 parts by weight of a free radical polymerization initiator, relative to 100 parts by weight of the total weight of the monomer mixture of the first copolymer.

[0060] If the first copolymer is polymerized with less than 2 parts by weight of a free radical polymerization initiator, the first copolymer will be over-polymerized. Since it is polymerized into an acrylic copolymer with an excessively large molecular weight, technical problems such as poor lithography process margin, poor adhesion and heat resistance of the positive photosensitive resin composition containing the copolymer may occur.

[0061] On the contrary, if the first copolymer is polymerized by more than 24 parts by weight of the free radical polymerization initiator, the positive photosensitive resin composition containing the copolymer may have poor photolithography process margin, adhesion and heat resistance due to polymerization into an acrylic copolymer with too small a molecular weight.

[0062] The monomers are subjected to a free radical reaction in the presence of a solvent and a polymerization initiator, and the unreacted monomers are removed by precipitation, filtration and vacuum drying processes, thereby obtaining a first copolymer, the weight average molecular weight (Mw) of which is 3000 to 20000 in terms of polystyrene. For an interlayer insulating film (organic insulating film) having a weight average molecular weight in terms of polystyrene of less than 3000, the developability and residual film rate may decrease, or the pattern development and heat resistance may deteriorate. For an interlayer insulating film having a weight average molecular weight in terms of polystyrene of more than 20000, the pattern development may deteriorate.

[0063] On the other hand, the second copolymer in which at least a portion of the terminal hydroxyl groups are protected by an acid-decomposable protecting group may include a repeating unit derived from an olefinic compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group; and a repeating unit derived from an olefinic compound having a terminal hydroxyl group, for example, may include repeating units represented by the following Chemical Formulas 1 and 2.

[0064] [Chemical formula 1]

[0065]

[0066] [Chemical formula 2]

[0067]

[0068] In the above chemical formula 2,

[0069] R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

[0070] Specifically, the second copolymer may include a main chain represented by Chemical Formula 5 below.

[0071] [Chemical formula 5]

[0072]

[0073] In the above Chemical Formula 5, a+b=100, a is 50 to 99, b is 1 to 50, and R1 may be one of a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

[0074] Alternatively, the second copolymer may include a main chain represented by Chemical Formula 6 or Chemical Formula 7 below.

[0075] [Chemical formula 6]

[0076]

[0077] In the above Chemical Formula 6, a+b+c+d=100, b+d is 1 to 50, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, R2 is hydrogen or a C1 to C10 alkyl group, and n can be an integer from 0 to 4.

[0078] [Chemical formula 7]

[0079]

[0080] In the above Chemical Formula 7, a+b+c+d=100, b+d is 1 to 50, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group or an acetoxyethoxyethyl group, R2 is hydrogen or a C1 to C10 alkyl group, and n can be an integer from 0 to 4.

[0081] Preferably, the second copolymer in which at least a portion of the terminal hydroxyl groups is protected by an acid-decomposable protecting group may include a main chain represented by Chemical Formula 6 or Chemical Formula 7.

[0082] If the second copolymer includes the main chain represented by the chemical formula 6 or 7, it is more conducive to yellowing than the chemical formula 5, and can achieve the technical effects of excellent penetration and heat discoloration resistance.

[0083] In the above Chemical Formulas 5 to 7, a to d represent the molar ratio between the repeating units, and Chemical Formulas 5 to 7 do not limit the order of the repeating units.

[0084] In addition, the second copolymer may include 0.01 mol % to 50 mol % or 1 mol % to 50 mol % of the repeating units as a whole, or 1 mol % to 50 mol % of the repeating units in which the terminal hydroxyl group is protected by an acid-decomposable protecting group.

[0085] When the olefinic copolymer contains repeating units in which the terminal hydroxyl groups are protected by acid-decomposable protecting groups in an amount greater than 50 mol % relative to the overall repeating units, not only the sensitivity and resolution become poor, but also the transmittance, heat discoloration resistance and photolithography process margin are reduced.

[0086] The second copolymer may be included in an amount of 1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the total of the first copolymer and the second copolymer.

[0087] When the content of the second copolymer is greater than 50 parts by weight relative to the total of 100 parts by weight of the first copolymer and the second copolymer, not only the sensitivity and resolution will deteriorate, but also technical problems such as reduced penetration, heat discoloration resistance and photolithography process margin, as well as reduced adhesion and heat resistance will occur.

[0088] In addition, the second copolymer may have a polystyrene-equivalent weight average molecular weight (Mw) of greater than or equal to 3,000 g / mol and less than or equal to 30,000 g / mol.

[0089] According to one embodiment of the present invention, the positive photosensitive resin composition may further include c) a photoacid generator.

[0090] The photoacid generator c) may be included in an amount of 0.1 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the first copolymer and the second copolymer.

[0091] There is no great restriction on the type of the above-mentioned c) photoacid generator, and for example, it may include at least one selected from the group consisting of oxime sulfonates, imide sulfonates, diazo disulfones, diazonium salts, disulfones, phosphonium salts, sulfonates, iodonium salts, o-nitrobenzyl sulfonates, and triazine compounds.

[0092] Specifically, the above-mentioned c) photoacid generator may include at least one of the compounds represented by the following Chemical Formulas 8 to 13.

[0093] [Chemical formula 8]

[0094]

[0095] [Chemical formula 9]

[0096]

[0097] [Chemical formula 10]

[0098]

[0099] [Chemical formula 11]

[0100]

[0101] [Chemical formula 12]

[0102]

[0103] [Chemical formula 13]

[0104]

[0105] In the above chemical formulas 8 to 13, X is hydrogen or a C1 to C14 linear or branched alkyl group, and R3 is a C1 to C18 aliphatic hydrocarbon group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, a C7 to C20 aryl group substituted with an acyl group, or a C1 to C8 haloalkyl group.

[0106] In addition, according to one embodiment of the present invention, the positive photosensitive resin composition may further include d) a solvent.

[0107] The solvent d) is used for coating the photosensitive resin composition on a substrate, and specific examples thereof include diethylene glycol dimethyl ether, diethylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, ether), butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether, etc., can be used alone or in combination of at least two.

[0108] The solvent of d) may be included so that the solid content of the positive photosensitive resin composition reaches 10 to 50% by weight. If the solid content is less than 10% by weight, the coating thickness becomes thinner and the coating uniformity (Uniformity) will decrease. If the solid content is greater than 50% by weight, the coating thickness becomes thicker, which will burden the coating equipment during coating. When the solid content of the total composition is 10 to 25% by weight, it is convenient to use in a slit coater (Slit Coater), and when the solid content of the total composition is 25 to 50% by weight, it is convenient to use in a spin coater (Spin Coater) or a slit spin coater (Slit & Spin Coater).

[0109] The positive photosensitive resin composition may be prepared to have a solid concentration of 10 to 50% by weight, and may be filtered using a 0.1 to 0.2 μm millipore filter or the like before use.

[0110] According to another embodiment of the present invention, a positive photosensitive resin composition may be provided, which further comprises at least one additive selected from the group consisting of e) a basic compound, f) an adhesive aid, g) an antioxidant, and h) a photosensitizer.

[0111] When it further comprises at least one additive selected from the group consisting of e) a basic compound, f) a bonding aid, g) an antioxidant, and h) a photosensitizer, the positive photosensitive resin composition may comprise, relative to 100 parts by weight of the total of the first copolymer and the second copolymer, 0.01 parts by weight or more and 3 parts by weight of e) a basic compound, 0.5 parts by weight or more and 10 parts by weight of f) a bonding aid, 0.1 parts by weight or more and 10 parts by weight of g) an antioxidant, and 0.1 parts by weight or more and 10 parts by weight of h) a photosensitizer.

[0112] The alkaline compound may include at least one selected from the group consisting of trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, methyldicyclohexylamine, benzylamine, N,N-dimethylaniline, diphenylamine, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

[0113] In addition, the above-mentioned bonding aid may include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, At least one of the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl)triethoxysilane, and (3-isocyanatepropyl)trimethoxysilane.

[0114] In addition, the above-mentioned antioxidant may include at least one selected from the group consisting of phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxylamine derivatives.

[0115] In addition, the photosensitizer may include at least one selected from the group consisting of pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropoxyanthracene.

[0116] 2. Photosensitive resin film

[0117] According to one embodiment of the present invention, a photosensitive resin film may be provided, comprising a cured product of the positive photosensitive resin composition. The positive photosensitive resin composition comprises all of the above contents.

[0118] The above-mentioned cured product includes not only the case where all components of the unsaturated group that can be cured or cross-linked in the chemical structure are cured, but also the case where a part of them is cured, cross-linked or polymerized.

[0119] The photosensitive resin film according to the above embodiment can be used not only as an interlayer insulating film, a passivation insulating film, and a gate insulating film, but also as a planarizing film, a bank, and a pixel define layer.

[0120] 3. Display device

[0121] According to one embodiment of the present invention, a display device may be provided, which includes the above-mentioned photosensitive resin film. The above-mentioned photosensitive resin film includes all of the above-mentioned contents.

[0122] That is, when an insulating film is formed in a manufacturing process of a display (Display), the positive photosensitive resin composition according to one embodiment of the present invention may be used.

[0123] First, the positive photosensitive resin composition is applied on the substrate surface of the display panel by spin coating, slit spin coating, slit coating, roller coating, etc., and the solvent is removed by pre-baking to form a coating film. At this time, the pre-baking can be performed at a temperature of 100°C to 120°C for 1 minute to 3 minutes. Then, the formed coating film is irradiated with visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. according to a pre-prepared pattern, and developed with a developer to remove unnecessary parts, thereby forming a predetermined pattern.

[0124] The developer preferably uses an alkaline aqueous solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate; primary amines such as ethylamine, n-propylamine; secondary amines such as diethylamine, n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc.; alcoholamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; or quaternary ammonium salt aqueous solution such as tetramethylammonium hydroxide, tetraethylammonium hydroxide. In this case, the developer is used by dissolving the alkaline compound in a concentration of greater than or equal to 0.1 parts by weight and less than or equal to 10 parts by weight, and an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, and a surfactant may also be added.

[0125] In addition, after development with a developer, the film is washed with ultrapure water for 30 seconds to 90 seconds to remove excess parts, and then dried to form a pattern. After irradiating the formed pattern with ultraviolet light or the like, the pattern is heated at a temperature of 150°C to 400°C for 30 minutes to 90 minutes using a heating device such as an oven, so that the final pattern can be obtained.

[0126] The positive photosensitive resin composition according to the embodiment has excellent planarization, penetration, and outgassing properties, especially excellent sensitivity, and significantly improves adhesion, contrast, and chemical resistance under high temperature and high humidity, so that it is suitable for forming interlayer insulating films and PDL isolation walls in the processes of LCD and OLED.

[0127] Preferred embodiments are given below to help understand the present invention, but the following embodiments are only used to illustrate the present invention, and the scope of the present invention is not limited to the following embodiments.

[0128] [Synthesis Example and Comparative Synthesis Example: Preparation of First Copolymer]

[0129] [Synthesis Example 1] Preparation of the first copolymer (A)

[0130] Tetrahydrofuran is prepared as a synthetic solvent in a flask equipped with a cooler and an agitator, and then a mixed solution of an olefinic unsaturated compound represented by the following chemical formula 1A, methacrylic acid, styrene and glycidyl methacrylate is added in a molar ratio of 30:20:20:30. The above-mentioned liquid composition is fully mixed at 600rpm in a mixing container, and then 2,2-azobis(2,4-dimethylvaleronitrile) is added in a ratio of 10 parts by weight relative to 100 parts by weight of the total monomer. The above-mentioned polymerization mixed solution is slowly heated to 55°C, kept at this temperature for 48 hours, and then cooled to room temperature, and tetrahydrofuran is completely removed by a drying process to prepare a first copolymer (A). The weight average molecular weight of the above-mentioned first copolymer is 10000. At this time, the weight average molecular weight is the weight average molecular weight converted to polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (gel permeation chromatography, GPC) using Waters e2695 Alliance Seperation Module.

[0131] [Chemical Formula 1A]

[0132]

[0133] [Synthesis Example 2] (Preparation of the first copolymer (B))

[0134] The first copolymer (B) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 1B was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0135] [Chemical formula 1B]

[0136]

[0137] [Synthesis Example 3] (Preparation of the first copolymer (C))

[0138] The first copolymer (C) was prepared by the same method as in Synthesis Example 1, except that the olefinic unsaturated compound represented by the following Chemical Formula 1C was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0139] [Chemical formula 1C]

[0140]

[0141] [Synthesis Example 4] (Preparation of the first copolymer (D))

[0142] The first copolymer (D) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 2A was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 12000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0143] [Chemical Formula 2A]

[0144]

[0145] [Synthesis Example 5] (Preparation of the first copolymer (E))

[0146] The first copolymer (E) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 2B was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 12000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0147] [Chemical formula 2B]

[0148]

[0149] [Synthesis Example 6] (Preparation of the first copolymer (F))

[0150] The first copolymer (F) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 2C was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 12000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0151] [Chemical formula 2C]

[0152]

[0153] [Synthesis Example 7] (Preparation of the first copolymer (G))

[0154] The first copolymer (G) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 2D was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 13000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0155] [Chemical Formula 2D]

[0156]

[0157] [Synthesis Example 8] (Preparation of the first copolymer (H))

[0158] The first copolymer (H) was prepared by the same method as in Synthesis Example 1 except that the olefinic unsaturated compound represented by the following Chemical Formula 2E was used instead of the olefinic unsaturated compound represented by the above Chemical Formula 1A in Synthesis Example 1. The weight average molecular weight of the above first copolymer was 12000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 AllianceSeperation Module.

[0159] [Chemical formula 2E]

[0160]

[0161] [Synthesis Example 9] (Preparation of the first copolymer (I))

[0162] The first copolymer (I) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene and glycidyl methacrylate in a molar ratio of 50:30:10:10 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0163] [Synthesis Example 10] (Preparation of the first copolymer (J))

[0164] The first copolymer (J) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the olefinic unsaturated compound represented by the above chemical formula 1B, methacrylic acid, styrene and 3-ethyl-3-oxetanyl acrylate in a molar ratio of 25:40:15:20 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0165] [Synthesis Example 11] (Preparation of the first copolymer (K))

[0166] The first copolymer (K) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A in Synthesis Example 1, methacrylic acid, styrene, glycidyl methacrylate and 3-ethyl-3-oxetanyl acrylate was added in a molar ratio of 5:15:35:25:20. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0167] [Synthesis Example 12] (Preparation of the first copolymer (L))

[0168] The first copolymer (L) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene and glycidyl methacrylate in a molar ratio of 40:15:30:15 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using e2695 Alliance Seperation Module of Waters Company.

[0169] [Synthesis Example 13] (Preparation of the first copolymer (M))

[0170] The first copolymer (M) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A in Synthesis Example 1, methacrylic acid, styrene, glycidyl methacrylate and hydroxyethyl acrylate was added in a molar ratio of 1:5:34:25:35. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0171] [Synthesis Example 14] (Preparation of the first copolymer (N))

[0172] The first copolymer (N) was prepared by the same method as in Synthesis Example 1 except that 5 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during polymerization in Synthesis Example 1. The weight average molecular weight of the first copolymer was 19000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0173] [Synthesis Example 15] (Preparation of the first copolymer (O))

[0174] The first copolymer (O) was prepared by the same method as in Synthesis Example 1 except that 2 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during polymerization in Synthesis Example 1. The weight average molecular weight of the first copolymer was 30,000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0175] [Synthesis Example 16] (Preparation of the first copolymer (P))

[0176] The first copolymer (P) was prepared by the same method as in Synthesis Example 1 except that 24 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during polymerization in Synthesis Example 1. The weight average molecular weight of the first copolymer was 3000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0177] [Comparative Synthesis Example 1] (Preparation of the First Copolymer (Q))

[0178] The first copolymer (Q) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the chemical formula 1A in Synthesis Example 1, methacrylic acid, styrene and glycidyl methacrylate was added at a molar ratio of 0:30:30:40. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0179] [Comparative Synthesis Example 2] (Preparation of the First Copolymer (R))

[0180] The first copolymer (R) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene and glycidyl methacrylate in a molar ratio of 52:13:15:20 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0181] [Comparative Synthesis Example 3] (Preparation of the First Copolymer (S))

[0182] The first copolymer (S) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the ethylenically unsaturated compound represented by the above chemical formula 1A, methacrylic acid, styrene, glycidyl methacrylate and hydroxyethyl acrylate in a molar ratio of 1:4:35:25:35 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using e2695 Alliance Seperation Module of Waters Company.

[0183] [Comparative Synthesis Example 4] (Preparation of the First Copolymer (T))

[0184] The first copolymer (T) was prepared by the same method as in Synthesis Example 1 except that a mixed solution of the olefinic unsaturated compound represented by the above chemical formula 1B, methacrylic acid, styrene and 3-ethyl-3-oxetanyl acrylate in a molar ratio of 25:42:13:20 was added. The weight average molecular weight of the first copolymer was 10000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method of gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0185] [Comparative Synthesis Example 5] (Preparation of the First Copolymer (U))

[0186] The first copolymer (U) was prepared by the same method as in Synthesis Example 1 except that 1.8 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during polymerization in Synthesis Example 1. The weight average molecular weight of the first copolymer was 31000. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0187] [Comparative Synthesis Example 6] (Preparation of the First Copolymer (V))

[0188] The first copolymer (V) was prepared by the same method as in Synthesis Example 1 except that 25 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was used instead of 10 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) used as a catalyst during polymerization in Synthesis Example 1. The weight average molecular weight of the first copolymer was 2800. At this time, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured using GPC, and the weight average molecular weight is measured using a standard analytical method using gel permeation chromatography (GPC) using Waters e2695 Alliance Seperation Module.

[0189]

Table 1

[0190]

[0191]

[0192] *Monomer i: an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group

[0193] *Monomer ii: unsaturated carboxylic acid compound

[0194] *Monomer iii: ethylenically unsaturated compound

[0195] *Monomer iv: unsaturated compound containing cross-linking group

[0196] *MAA: Methacrylic acid

[0197] *GMA: Glycidyl Methacrylate

[0198] *St:Styrene

[0199] *EOA: 3-Ethyl-3-oxetanyl acrylate

[0200] *HEA: Hydroxyethyl acrylate

[0201] *ADVN: 2,2-azobis(2,4-dimethylvaleronitrile)

[0202] [Examples, Comparative Examples and Reference Examples: Preparation of Positive Photosensitive Resin Compositions]

[0203] As shown in Table 2 below, the first copolymer prepared in the above synthesis example, the second copolymer represented by the following chemical formulas 3A to 5E, the photoacid generator represented by the following chemical formulas 12 to 28, the basic compound, the bonding aid and the antioxidant were added, mixed and dissolved with propylene glycol methyl ether acetate to a solid content of 25% by weight, and then filtered with a 0.1 μm microporous filter to prepare a positive photosensitive resin composition.

[0204] In Table 2 below, the contents of the first copolymer and the second copolymer are in parts by weight relative to 100 parts by weight of the total of the first copolymer and the second copolymer, and the contents of the photoacid generator, the alkaline compound, the bonding aid and the antioxidant are in parts by weight relative to 100 parts by weight of the total of the first copolymer and the second copolymer.

[0205] [Chemical formula 3A] (Molecular weight: 10000 g / mol)

[0206]

[0207] [Chemical formula 3B] (Molecular weight: 12000 g / mol)

[0208]

[0209] [Chemical formula 3C] (Molecular weight: 5000 g / mol)

[0210]

[0211] [Chemical formula 3D] (Molecular weight: 8000 g / mol)

[0212]

[0213] [Chemical formula 3E] (Molecular weight: 16000 g / mol)

[0214]

[0215] [Chemical formula 3F] (Molecular weight: 11000 g / mol)

[0216]

[0217] [Chemical formula 3G] (Molecular weight: 22000 g / mol)

[0218]

[0219] [Chemical Formula 4A] (Molecular weight: 6000 g / mol)

[0220]

[0221] [Chemical formula 4B] (Molecular weight: 3000 g / mol)

[0222]

[0223] [Chemical formula 4C] (Molecular weight: 27000 g / mol)

[0224]

[0225] [Chemical formula 4D] (molecular weight: 9000 g / mol)

[0226]

[0227] [Chemical formula 4E] (molecular weight: 18000 g / mol)

[0228]

[0229] [Chemical Formula 5A] (Molecular weight: 25000 g / mol)

[0230]

[0231] [Chemical Formula 5B] (Molecular weight: 8000 g / mol)

[0232]

[0233] [Chemical formula 5C] (Molecular weight: 12000 g / mol)

[0234]

[0235] [Chemical formula 5D] (Molecular weight: 20000 g / mol)

[0236]

[0237] [Chemical Formula 5E] (Molecular weight: 15000 g / mol)

[0238]

[0239] [Chemical formula 12]

[0240]

[0241] [Chemical formula 13]

[0242]

[0243] [Chemical formula 14]

[0244]

[0245] [Chemical formula 15]

[0246]

[0247] [Chemical formula 16]

[0248]

[0249] [Chemical formula 17]

[0250]

[0251] [Chemical formula 18]

[0252]

[0253] [Chemical formula 19]

[0254]

[0255] [Chemical formula 20]

[0256]

[0257] [Chemical formula 21]

[0258]

[0259] [Chemical formula 22]

[0260]

[0261] [Chemical formula 23]

[0262]

[0263] [Chemical formula 24]

[0264]

[0265] [Chemical formula 25]

[0266]

[0267] [Chemical formula 26]

[0268]

[0269] [Chemical formula 27]

[0270]

[0271] [Chemical formula 28]

[0272]

[0273]

Table 2

[0274]

[0275]

[0276]

[0277] *DMA: N,N-dimethylaniline

[0278] *PP: Phenylpyridine

[0279] *TPA: Tri-n-propylamine

[0280] *DEA: Diethylamine

[0281] *TEA: Triethanolamine

[0282] *APES: N-2-(aminoethyl)-3-aminopropyltriethoxysilane

[0283] *GOPMS: (3-glycidoxypropyl)trimethoxysilane

[0284] *DBMP: 2,6-di-tert-butyl-4-methylphenol

[0285] [Experimental example]

[0286] The photosensitive resin compositions of the above-mentioned embodiments and comparative examples were coated on a glass substrate using a slit coater, and then subjected to a VCD (vacuum drying) process to a pressure of 40 Pa and pre-baked on a hot plate at 100° C. for 2 minutes to form a film with a thickness of 4.0 μm.

[0287] The properties of the film, such as sensitivity, resolution, transmittance, heat discoloration resistance, process margin, adhesion, and heat resistance, were measured and are shown in Table 3 below.

[0288] a) Sensitivity

[0289] The film formed as above was irradiated with a predetermined pattern mask at a standard dose of 20 mW / cm2 at a contact hole size of 10 μm. 2 After ultraviolet light was applied, the film was developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide at 23° C. for 1 minute, and then washed with ultrapure water for 1 minute.

[0290] Next, the film was cured in an oven at 230° C. for 30 minutes to obtain a pattern film having a thickness of 3.0 μm. The exposure energy (dose) when forming a 10 μm contact hole pattern (Pattern) of the prepared pattern film was measured as sensitivity.

[0291] b) Resolution

[0292] The resolution was measured based on the minimum size of the 10 μm contact hole pattern formed when measuring the sensitivity in a) above.

[0293] c) Penetration

[0294] Transmittance Evaluation The transmittance of the pattern film formed when measuring the sensitivity in a) above was measured using a spectrophotometer. At this time, the case where the transmittance is greater than or equal to 97% is represented by ◎, the case where it is greater than or equal to 95% is represented by ○, the case where it is greater than or equal to 90% and less than 95% is represented by △, and the case where it is less than 90% is represented by ×.

[0295] d) Resistance to heat discoloration

[0296] The substrate for evaluating the transparency of c) was further cured twice in an oven at 230°C, each time for 30 minutes, and the heat discoloration resistance was evaluated based on the change in the 400nm transmittance of the pattern film before and after curing. At this time, the case where the change rate is less than 1% is represented by ◎, the case where it is less than 3% is represented by ○, the case where it is 3% to 5% is represented by △, and the case where it is greater than 5% is represented by ×.

[0297] e) PED (Post Exposure Delay) process margin

[0298] The pattern film is formed by the same method as the sensitivity measurement in a) above, and the CD change rate based on the delay time before the development process after exposure is measured based on the contact hole size (Contact Hole CD) of 10μm. At this time, the case where the change rate is less than 3% is represented by ◎, the case where it is less than 5% is represented by ○, the case where it is greater than or equal to 5% and less than 10% is represented by △, and the case where it is greater than or equal to 10% is represented by ×.

[0299] f) Adhesion

[0300] The adhesive force of the pattern film formed when measuring the sensitivity in a) was evaluated based on whether the pattern was lost or not by scope.

[0301] The situation where adhesion is ensured when the pre-baking temperature is greater than or equal to 90°C is represented by ◎, the situation where adhesion is ensured when it is greater than or equal to 95°C is represented by ○, the situation where adhesion is ensured at 100°C-105°C is represented by △, and the situation where adhesion is ensured or pattern loss occurs when it is greater than 105°C is represented by ×.

[0302] g) Heat resistance

[0303] Heat resistance was measured by TGA. After sampling the pattern film formed when measuring the sensitivity in a) above, the temperature was raised from room temperature to 900°C by TGA at a rate of 10°C per minute. A temperature of 5% weight loss greater than 300°C was indicated as ○, a temperature of 5% weight loss between 280°C and 300°C was indicated as △, and a temperature of 5% weight loss less than 280°C was indicated as ×.

[0304]

Table 3

[0305]

[0306]

[0307]

[0308] As shown in Table 3 above, the insulating film of the cured product of the positive photosensitive resin composition comprising Examples 1 to 75 of the present application shows a sensitivity of 50mJ and a resolution of 3μm, which confirms that it has excellent sensitivity and resolution. Not only that, it also shows a penetration of greater than or equal to 95%, a heat discoloration resistance of less than 3%, and a CD change rate of less than 5%, which confirms that it has excellent penetration, heat discoloration resistance and photolithography process margin. In addition, at a low temperature of greater than or equal to 95°C, the adhesion can also be ensured, and the temperature at which 5% by weight is lost is greater than 300°C, which can confirm that excellent adhesion and heat resistance are achieved. In other words, the insulating film prepared by the positive photosensitive resin composition of the embodiment of the present application has excellent sensitivity, resolution, penetration, heat discoloration resistance, photolithography process margin, adhesion and heat resistance.

[0309] In particular, since the positive photosensitive resin compositions of Examples 52 to 67 and Example 75 further contain a basic compound, it can be confirmed that the insulating film of the cured product of the positive photosensitive resin compositions of Examples 52 to 67 and Example 75 exhibits very excellent heat discoloration resistance with a transmittance change rate of less than 1%.

[0310] In addition, since the positive photosensitive resin composition of Examples 65 to 71 and Example 75 further contains an adhesion aid, it can be confirmed that the insulating film of the cured product of the positive photosensitive resin composition of Examples 65 to 71 and Example 75 ensures excellent adhesion at a pre-bake temperature greater than or equal to 90°C.

[0311] In addition, since the positive photosensitive resin composition of Examples 72 to 75 further contains an antioxidant, it can be confirmed that the insulating film of the cured product of the positive photosensitive resin composition of Examples 72 to 75 shows very excellent transmittance greater than or equal to 97% and very excellent heat discoloration resistance with a transmittance change rate of less than 1%.

[0312] In contrast, the insulating film obtained from the positive photosensitive resin composition of Comparative Example 1 of the present application, which is composed of the first copolymer Q of the above-mentioned Comparative Synthesis Example 1, which contains as a monomer an olefinically unsaturated compound whose terminal hydroxyl group is not protected by an acid-decomposable protecting group, shows a sensitivity of 200 mJ and a resolution of 10 μm. Compared with the embodiments of the present application, it not only shows significantly poor sensitivity and resolution, but also shows a CD change rate greater than or equal to 10%, which confirms that the lithography process margin is also poor.

[0313] In addition, the insulating film obtained by the positive photosensitive resin composition of the comparative example 2 of the present application, which includes the first copolymer R of the comparative synthesis example 2 above, in which more than 50 mol% of the terminal hydroxyl group is protected by an acid-decomposable protective group, shows a sensitivity of 250mJ and a resolution of 8μm. Compared with the embodiments of the present application, it not only shows significantly poor sensitivity and resolution, but also shows a penetration of less than 90%, a heat discoloration resistance of greater than or equal to 5%, and a CD change rate of greater than or equal to 10%. It can be confirmed that it shows significantly poor penetration, heat discoloration resistance and photolithography process margin. In addition, the pattern loss leads to poor adhesion, and a 5% weight loss will also occur at a temperature of less than 280°C. It can be confirmed that the heat resistance at 300°C is also poor.

[0314] In addition, the insulating film obtained by the positive photosensitive resin composition of the comparative example 3 of the present application, which includes the first copolymer S of the comparative synthesis example 3 above, which is copolymerized by adding an excess of 70 mol% or more of an ethylenically unsaturated compound, shows a sensitivity of 200mJ and a resolution of 8μm. Compared with the examples of the present application, it not only shows significantly poor sensitivity and resolution, but also shows a CD change rate of 10% or more, which can be confirmed to show significantly poor photolithography process margin. In addition, the pattern loss leads to poor adhesion, and a 5% weight loss will also occur at a temperature of less than 280°C, and it can be confirmed that the heat resistance at 300°C is also poor.

[0315] On the other hand, the insulating film obtained from the positive photosensitive resin composition of Comparative Example 4 of the present application, which includes the first copolymer T of Comparative Synthesis Example 4 above, in which more than 40 mol% of an unsaturated carboxylic acid compound is added for copolymerization, shows a sensitivity of 60 mJ and a resolution of 5 μm. Compared with the examples of the present application, it not only shows poor sensitivity and resolution, but also shows a CD change rate of more than 10%, which can confirm that it shows a significantly poor photolithography process margin. In addition, the pattern loss leads to poor adhesion, and a 5% weight loss occurs at a temperature less than 280°C, and it can be confirmed that the heat resistance at 300°C is also poor.

[0316] In addition, the insulating film obtained from the positive photosensitive resin composition of Reference Examples 1 and 2 of the present application, which includes the first copolymers U and V of Comparative Synthesis Examples 5 and 6, which are copolymerized by adding less than 2 parts by weight or more than 24 parts by weight of a free radical polymerization initiator, shows a CD change rate of 10% or more, and it can be confirmed that a relatively poor photolithography process margin is shown. In addition, it can be confirmed that the characteristics in terms of adhesion and heat resistance are also reduced.

[0317] In particular, the insulating film obtained from the positive photosensitive resin composition of reference example 1 of the present application comprising the first copolymer U of the above-mentioned comparative synthesis example 5 showed a sensitivity of 200 mJ and a resolution of 10 μm, which showed a decrease in sensitivity and resolution compared with the examples of the present application. The insulating film obtained from the positive photosensitive resin composition of reference example 2 of the present application comprising the first copolymer V of the above-mentioned comparative synthesis example 6 was also measured to have a sensitivity of 120 mJ and a resolution of 8 μm, which can be confirmed to have a decrease in sensitivity and resolution compared with the examples of the present application.

[0318] On the other hand, the insulating film obtained from the positive photosensitive resin composition of Reference Examples 3 to 5 of the present application, which does not contain the olefinic copolymer unique to the present invention, shows a sensitivity of 120 mJ and a resolution of 5 μm. Compared with the examples of the present application, it not only shows relatively poor sensitivity and resolution, but also shows a transmittance of less than 90%, a heat discoloration resistance of 5% or more, and a CD change rate of 10% or more. It can be confirmed that the transmittance, heat discoloration resistance and photolithography process margin characteristics are also somewhat poor. In addition, it can be confirmed that the characteristics in terms of adhesion and heat resistance are also reduced.

[0319] On the other hand, relative to the total of 100 parts by weight of the first copolymer and the second copolymer, the positive photosensitive resin composition of reference examples 6 to 8 of the present application contains more than 50 parts by weight of the second copolymer. The insulating film obtained from the positive photosensitive resin composition of reference examples 6 to 8 of the present application shows a sensitivity greater than or equal to 130mJ and a resolution of 5μm. Compared with the embodiments of the present application, it not only shows relatively poor sensitivity and resolution, but also shows a penetration of less than 90%, a heat discoloration resistance of greater than or equal to 5%, and a CD change rate of greater than or equal to 10%. It can be confirmed that the penetration, heat discoloration resistance and photolithography process margin characteristics are also somewhat poor. In addition, it can be confirmed that the characteristics in terms of adhesion and heat resistance are also reduced.

Claims

1. A positive photosensitive resin composition, comprising: a) a first copolymer comprising i) repeating units derived from an ethylenically unsaturated compound whose terminal hydroxyl group is protected by an acid-decomposable protecting group, ii) repeating units derived from an unsaturated carboxylic acid compound, and iii) repeating units derived from an ethylenically unsaturated compound; b) a second copolymer, at least a portion of the terminal hydroxyl groups of which are protected by an acid-decomposable protecting group; c) a photoacid generator; and d) a solvent, With respect to 100 parts by weight of the first copolymer and the second copolymer, the content of the second copolymer is greater than or equal to 1 part by weight and less than or equal to 50 parts by weight. The second copolymer comprises repeating units represented by the following chemical formulas 1 and 2, [Chemical formula 1] [Chemical formula 2] In the above chemical formula 2, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group.

2. The positive photosensitive resin composition according to claim 1, wherein Relative to 100 mol% of the total monomers used to synthesize the first copolymer The content of the olefinically unsaturated compound in which the terminal hydroxyl group in the above i) is protected by an acid-decomposable protecting group is 1 to 50 mol%. The content of the unsaturated carboxylic acid compound in the above ii) is 5 to 40 mol%. The content of the ethylenically unsaturated compound in the above iii) is greater than or equal to 10 mol % and less than 70 mol %.

3. The positive photosensitive resin composition according to claim 1, wherein The unsaturated carboxylic acid compound in the above ii) comprises at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, meconic acid, itaconic acid and anhydrides of unsaturated dicarboxylic acids thereof.

4. The positive photosensitive resin composition according to claim 1, wherein The ethylenically unsaturated compound in the above iii) comprises methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, propylene glycol acrylate, 1-propylene glycol meth ... Dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methacrylate Methyl glycidyl ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4- At least one of the group consisting of cyclohexylmethyl epoxy, 3-ethyl-3-oxetanyl methacrylate, 3-ethyl-3-oxetanyl acrylate, 3-butyl-3-oxetanyl methacrylate, 3-butyl-3-oxetanyl acrylate, 3-propyl-3-oxetanyl methacrylate, 3-propyl-3-oxetanyl acrylate, 3-oxetanyl methacrylate, 3-oxetanyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate and hydroxypropyl acrylate.

5. The positive photosensitive resin composition according to claim 1, wherein The ethylenically unsaturated compound in which the terminal hydroxyl group is protected by an acid-decomposable protecting group comprises any one of the compounds represented by the following chemical formula 3 or 4, [Chemical formula 3] In the above chemical formula 3, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, [Chemical formula 4] In the above chemical formula 4, R2 is hydrogen or a C1 to C10 alkyl group, R3 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, n is an integer of 0-4.

6. The positive photosensitive resin composition according to claim 1, wherein The second copolymer comprises any one of the main chains represented by the following chemical formulas 5 to 7, [Chemical formula 5] In the above chemical formula 5, a+b=100, a is 50 to 99, b is 1 to 50, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, [Chemical formula 6] In the above chemical formula 6, a+b+c+d=100, b+d is 1 to 50, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, R2 is hydrogen or a C1 to C10 alkyl group, n is an integer from 0 to 4, [Chemical formula 7] In the above chemical formula 7, a+b+c+d=100, b+d is 1 to 50, R1 is a monovalent functional group derived from an acetal group, an alkyl group, an alkylsilyl group, a siloxy group, a 2-tetrahydropyranyl group, a vinyl ether group, a 2-tetrahydrofuranyl group, a 2,3-propylene carbonate group, a methoxyethoxyethyl group, or an acetoxyethoxyethyl group, R2 is hydrogen or a C1 to C10 alkyl group, n is an integer of 0-4.

7. The positive photosensitive resin composition according to claim 1, wherein The second copolymer includes 0.01 mol % or more and 50 mol % or less of the repeating units in which the terminal hydroxyl group is protected by an acid-decomposable protecting group, based on the total repeating units.

8. The positive photosensitive resin composition according to claim 1, wherein Relative to 100 parts by weight of the total weight of the monomers used to synthesize the first copolymer, The first copolymer is polymerized in the presence of 2 parts by weight or more and 24 parts by weight or less of a radical polymerization initiator.

9. The positive photosensitive resin composition according to claim 1, wherein Relative to 100 parts by weight of the total of the first copolymer and the second copolymer, The content of the photoacid generator is greater than or equal to 0.1 parts by weight and less than or equal to 30 parts by weight.

10. The positive photosensitive resin composition according to claim 1, further comprising: e) at least one additive selected from the group consisting of a basic compound, f) an adhesive aid, g) an antioxidant, and h) a photosensitizer.

11. The positive photosensitive resin composition according to claim 10, wherein Relative to 100 parts by weight of the first copolymer and the second copolymer, The positive photosensitive resin composition comprises at least one of 0.01 parts by weight and less than 3 parts by weight of the above-mentioned e) alkaline compound, 0.5 parts by weight and less than 10 parts by weight of the above-mentioned f) bonding aid, 0.1 parts by weight and less than 10 parts by weight of the above-mentioned g) antioxidant, and 0.1 parts by weight and less than 10 parts by weight of the above-mentioned h) photosensitizer.

12. The positive photosensitive resin composition according to claim 1, wherein The first copolymer has a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 30,000.

13. The positive photosensitive resin composition according to claim 1, wherein The polystyrene-equivalent weight average molecular weight (Mw) of the first copolymer is 3,000 to 30,000, The second copolymer has a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 30,000. 14 . A photosensitive resin film comprising a cured product of the positive photosensitive resin composition according to claim 1 . 15 . A display device comprising the photosensitive resin film according to claim 14 .

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