Positive photosensitive resin composition

Abstract

The positive photosensitive resin composition of the present invention comprises: a siloxane polymer obtained by polymerizing one or more reactive silanes; an olefin polymer comprising a repeating unit, wherein the repeating unit comprises one or more hydroxyphenyl or phenyl groups; a 1,2-quinonediazide compound; and a solvent. The positive photosensitive resin composition of the present invention has excellent sensitivity, heat discoloration resistance and other properties, and in particular, has excellent heat resistance. Therefore, when it is used in a display panel, cracks are prevented and chemical resistance is improved, thereby ensuring excellent panel reliability.

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition, and more specifically, to a positive photosensitive resin composition having excellent properties such as sensitivity, heat discoloration resistance, gas release property, and moisture absorption rate by containing a siloxane polymer and an olefin polymer. Background Art

[0002] Recently, photosensitive organic insulating films are used in liquid crystal display devices, organic light emitting diode (OLED) display devices, and integrated circuit devices to insulate the wiring arranged between layers and increase the aperture ratio. Interlayer insulating films for liquid crystal display devices mainly use acrylic insulating films, but they still have the problem of outgassing caused by reduced heat resistance. In addition, interlayer insulating films and pixel definition films for organic light emitting diode display devices use polyimide, but they have problems with sensitivity, heat discoloration resistance, outgassing, moisture absorption rate, etc. Recently, in order to ensure the panel reliability of organic light emitting diode display devices, the demand for materials with crack resistance and chemical resistance has increased.

[0003] As a result, recently, the demand for materials based on siloxane-based and olefin-based resin technologies has greatly increased, and technology research and development has been actively carried out. Summary of the invention

[0004] Technical issues

[0005] One object of the present invention is to provide a positive photosensitive resin composition that has excellent sensitivity, heat discoloration resistance, degassing properties, moisture absorption rate and other properties, and in particular, has excellent heat resistance, thereby improving crack resistance and chemical resistance, thereby ensuring excellent panel reliability.

[0006] Another object of the present invention is to provide a method for forming a pattern of a display device using the positive photosensitive resin composition and a display device including a cured product of the positive photosensitive resin composition.

[0007] Means of solving the problem

[0008] One embodiment of the present invention provides a positive photosensitive resin composition, comprising: a siloxane polymer obtained by polymerizing one or more reactive silanes represented by the following chemical formula 1; an olefin polymer comprising a repeating unit represented by the following chemical formula 2 or a repeating unit represented by the following chemical formula 2 and chemical formula 3; a 1,2-quinonediazide compound; and a solvent.

[0009] Chemical formula 1: Si(R 1 ) i (R 2 ) 4-i

[0010] In the above chemical formula, R 1 are independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 2 Each of them is independently a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group or an acetoxy group; and i is an integer from 0 to 3.

[0011] Chemical formula 2:

[0012] Chemical formula 3:

[0013] According to an embodiment of the present invention, the reactive silane may include one or more reactive silanes represented by the following chemical formula 1-1 and one or more tetrafunctional reactive silanes represented by the following chemical formula 1-2.

[0014] Chemical formula 1-1: (R 1 ) n Si(R 2 ) 4-n

[0015] Chemical formula 1-2: Si(R 3 ) 4

[0016] In the above Chemical Formula 1-1 and Chemical Formula 1-2, R 1 are independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 2 are independently hydroxyl, alkoxy, phenoxy or acetoxy having 1 to 4 carbon atoms, wherein R 3 They are independently one of an alkoxy group, a phenoxy group or an acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.

[0017] According to an embodiment of the present invention, the siloxane copolymer may be formed by hydrolyzing and polycondensing the reactive silane represented by the chemical formula 1-1 and the tetrafunctional reactive silane represented by the chemical formula 1-2 at a weight ratio of 2:8 to 8:2.

[0018] According to an embodiment of the present invention, in the olefin polymer, the repeating units represented by Chemical Formula 2 and Chemical Formula 3 may be provided in a ratio of 99:1 to 60:40.

[0019] According to an embodiment of the present invention, in the siloxane polymer, the ratio of (Q3+T3) in the silicon nuclear magnetic resonance (NMR) analysis result may account for more than 40% of the total silicon.

[0020] According to an embodiment of the present invention, the polystyrene-equivalent weight average molecular weight (Mw) of the siloxane-based polymer may be 1,000 to 20,000, and the polystyrene-equivalent weight average molecular weight of the olefin-based polymer may be 1,000 to 30,000.

[0021] According to an embodiment of the present invention, the siloxane-based polymer and the olefin-based polymer may be provided in a weight ratio of 95:5 to 10:90.

[0022] According to an embodiment of the present invention, the 1,2-quinonediazide compound can be obtained by reacting a phenol compound represented by the following Chemical Formula 4 with a naphthoquinonediazidesulfonic acid halogen compound.

[0023] Chemical formula 4:

[0024] In the above chemical formula 4, R 1 To R 6 are independently hydrogen, halogen, alkyl having 1 to 4 carbon atoms, alkenyl having 1 to 4 carbon atoms, or hydroxyl, R 7 and R 8 are independently hydrogen, halogen or alkyl having 1 to 4 carbon atoms, R 9 It is hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0025] According to one embodiment of the present invention, the above-mentioned solvent may include at least one of 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 ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutyl glycol dimethyl ether, dibutyl glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol ethyl 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.

[0026] According to one embodiment of the present invention, based on 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer, the 1,2-quinonediazide compound may be included in an amount of 5 to 50 parts by weight, and the solvent may contain 10 to 50 parts by weight of a solid component.

[0027] According to an embodiment of the present invention, the positive photosensitive resin composition may further include at least one ultraviolet absorber selected from the group consisting of benzotriazine and benzotriazole.

[0028] According to an embodiment of the present invention, based on 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer, 1 part by weight to 20 parts by weight of the ultraviolet absorber may be provided.

[0029] Still another embodiment of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.

[0030] Another embodiment of the present invention provides a display device including a cured product of the positive photosensitive resin composition.

[0031] Effects of the Invention

[0032] The positive photosensitive resin composition of the present invention has excellent properties such as sensitivity, heat discoloration resistance, degassing property, and moisture absorption rate, and in particular, has excellent heat resistance, thereby improving crack resistance and chemical resistance.

[0033] The positive photosensitive resin composition of the present invention is not only effectively applicable to interlayer insulating films, protective insulating films, and gate insulating films in display devices, but can also be effectively applied to planarizing films, stacks, pixel definition films, etc., and excellent panel reliability can be ensured by using the positive photosensitive resin composition of the present invention.

[0034] It should be understood that the effects of the present invention are not limited to the above effects, and include all effects that can be inferred from the inventive constitution described in the detailed description of the present invention or the scope of the claims. DETAILED DESCRIPTION

[0035] Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention can be implemented in various forms and is not limited to the embodiments described here.

[0036] The terms used in this specification are only used to illustrate specific embodiments and do not limit the present invention. Unless the context clearly indicates otherwise, singular expressions include plural expressions. In this specification, terms such as "including" or "having" are used to specify the existence of features, numbers, steps, actions, structural elements, components, or combinations thereof recorded in the specification, rather than excluding in advance the existence or additional possibility of one or more other features, numbers, steps, actions, structural elements, components, or combinations thereof.

[0037] Hereinafter, the present invention will be described in detail.

[0038] One embodiment of the present invention provides a positive photosensitive resin composition including a siloxane-based polymer, an olefin-based polymer, a 1,2-quinonediazide compound, and a solvent.

[0039] The mixed composition of the above-mentioned siloxane polymer and olefin polymer used in the present invention not only has excellent properties such as sensitivity, resolution, adhesion, permeability, and heat discoloration resistance, but also has especially excellent heat resistance, thereby reducing outgassing and maintaining low moisture absorption rate, and can be used as an adhesive that can ensure excellent panel reliability.

[0040] The siloxane polymer used in the present invention can be obtained by polymerizing one or more reactive silanes represented by the following Chemical Formula 1.

[0041] Chemical formula 1: Si(R 1 ) i (R 2 ) 4-i

[0042] In the above chemical formula, R 1 are independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 2 Each of them is independently a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group or an acetoxy group; and i is an integer from 0 to 3.

[0043] More specifically, the reactive silane may include one or more reactive silanes represented by the following Chemical Formula 1-1 and one or more tetrafunctional reactive silanes represented by the following Chemical Formula 1-2.

[0044] Chemical formula 1-1: (R 1 ) n Si(R 2 ) 4-n

[0045] Chemical formula 1-2: Si(R 3 ) 4

[0046] In the above Chemical Formula 1-1 and Chemical Formula 1-2, R 1 are independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 2 are independently hydroxyl, alkoxy, phenoxy or acetoxy having 1 to 4 carbon atoms, wherein R 3 They are independently one of an alkoxy group, a phenoxy group or an acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.

[0047] The reactive silane represented by the above chemical formula 1-1 may include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, benzyldimethoxysilane, phenyltriacetic acid oxide silane, phenyltriphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, etc., and they may be used alone or in combination of two or more.

[0048] The tetrafunctional reactive silane represented by the above Chemical Formula 1-2 includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, etc., and they may be used alone or in combination of two or more.

[0049] The siloxane-based copolymer may be prepared by hydrolyzing and polycondensing the reactive silane represented by the chemical formula 1-1 and the tetrafunctional reactive silane represented by the chemical formula 1-2 provided at a weight ratio of 2:8 to 8:2.

[0050] That is, the reactive silane represented by the above chemical formula 1-1 may be included in an amount of 20 to 80 parts by weight relative to the total monomers forming the siloxane-based polymer. When the content of the reactive silane represented by the above chemical formula 1-1 is less than 20 parts by weight, cracks may be generated when a film is formed, and when the content of the reactive silane represented by the above chemical formula 1-1 is greater than 80 parts by weight, the reactivity is reduced during polymerization, and thus it is difficult to control the molecular weight.

[0051] In addition, the tetrafunctional reactive silane represented by the above chemical formula 1-2 may be included in an amount of 80 to 20 parts by weight relative to the total monomers forming the siloxane-based polymer. When the content of the tetrafunctional reactive silane represented by the above chemical formula 1-2 is less than 20 parts by weight, when the pattern of the photosensitive siloxane resin composition is formed, the solubility in an alkaline aqueous solution is reduced, resulting in a defect. When the content of the tetrafunctional reactive silane represented by the above chemical formula 1-2 is greater than 80 parts by weight, when polymerized, the reactivity is too fast, so it is difficult to control the molecular weight, and the solubility of the generated siloxane oligomer in an alkaline aqueous solution is too large.

[0052] The siloxane polymer further includes i) the reactive silane represented by the chemical formula 1-1, ii) the tetrafunctional reactive silane represented by the chemical formula 1-2, and iii) the reactive silane represented by the following chemical formula 5, and can be obtained by hydrolyzing and polycondensing in a catalyst and removing unreacted monomers and catalyst.

[0053] Chemical formula 5: (R4 ) n Si(R 5 ) 4-n

[0054] In the above chemical formula 5, R 4 Each of the following is independently vinyl, 3-propylene oxide, 3-methacryl oxide, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidyl oxide alkyl, 2-(3,4-epoxycyclohexyl)alkyl, 3-isocyanate oxide alkyl or oxetane oxide alkyl, R 5 It is an alkoxy group, a phenoxy group or an acetoxy group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.

[0055] The reactive silane represented by the above Chemical Formula 5 may include, for example, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, oxetaneethyltrimethoxysilane, and the like, and may be used alone or in combination of two or more.

[0056] When the reactive silane represented by the above chemical formula 5 or a mixture thereof is used, the reactive silane represented by the above chemical formula 5 may be included in an amount of 5 to 50 parts by weight relative to the total monomers forming the siloxane-based polymer. When the content of the reactive silane represented by the above chemical formula 5 is within the above range, the adhesiveness and the degree of film curing may be further improved.

[0057] The siloxane polymer can be obtained by subjecting the reactive silane described above to bulk polymerization or solution polymerization in the presence of water, an acid or a base catalyst. Specifically, the siloxane polymer can be obtained by subjecting the reactive silane, which acts as a monomer, to hydrolysis and polycondensation and removing unreacted monomers and catalysts.

[0058] Acidic catalysts that can be used in the above-mentioned polymerization include hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, oxalic acid, propionic acid, butyric acid, valeric acid, etc., and basic catalysts can include ammonia, organic amines and alkyl ammonium hydroxide salts, etc., which can be used alone or in combination of two or more to be used simultaneously or in stages.

[0059] The polystyrene-equivalent weight average molecular weight of the siloxane polymer finally obtained by gel permeation chromatography (GPC) may be 1000 to 20000. When the polystyrene-equivalent weight average molecular weight of the siloxane polymer is less than 1000, when evaluating a positive photosensitive resin composition, there are problems such as a reduced residual rate in a development process or reduced heat resistance and weak moisture absorption rate. When the polystyrene-equivalent weight average molecular weight of the siloxane polymer is greater than 20000, there are problems such as reduced sensitivity of the positive photosensitive resin composition or reduced developability of the pattern.

[0060] In the above-mentioned siloxane polymer, the ratio of (Q3+T3) in the silicon nuclear magnetic resonance analysis result can account for more than 40% of the total silicon. This means that the above-mentioned siloxane copolymer includes a ladder structure, and the ratio of the siloxane polymer having a ladder structure is more than 40% based on the silicon (Si) nuclear magnetic resonance analysis result. In the case where the ratio of the ladder structure of the above-mentioned siloxane copolymer is less than 40%, the chemical resistance to the stripper and etching solution may be weakened.

[0061] The olefin polymer used in the present invention may include a repeating unit represented by the following Chemical Formula 2 or a repeating unit represented by the following Chemical Formula 2 and Chemical Formula 3. For example, the olefin polymer may be an independent polymer including only the repeating unit represented by Chemical Formula 2 or a copolymer including the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3.

[0062] Chemical formula 2:

[0063] Chemical formula 3:

[0064] In the above olefin polymer, the repeating unit represented by the above Chemical Formula 2 and the repeating unit represented by the Chemical Formula 3 may be provided at a ratio of 99:1 to 60:40, for example, the repeating unit represented by the above Chemical Formula 2 and the repeating unit represented by the Chemical Formula 3 may be provided at a ratio of 99:1 to 70:30, for example, the repeating unit represented by the above Chemical Formula 2 and the repeating unit represented by the Chemical Formula 3 may be provided at a ratio of 95:5 to 70:30. The above ratio represents a molar ratio of the two repeating units, and can be confirmed, for example, by a result obtained from an analysis result of two-dimensional nuclear magnetic resonance (H-nuclear magnetic resonance, C-nuclear magnetic resonance, etc.).

[0065] The olefin polymer has excellent crack resistance and chemical resistance, and when the olefin polymer is used, it can function as an adhesive that ensures excellent panel reliability in a display.

[0066] The polystyrene-equivalent weight average molecular weight of the olefin polymer as measured by gel permeation chromatography may be 1000 to 30000. When the polystyrene-equivalent weight average molecular weight of the olefin polymer is less than 1000, when evaluating a positive photosensitive resin composition, there may be a problem of reduced residual rate or reduced heat resistance in a development process, and when the polystyrene-equivalent weight average molecular weight of the olefin polymer is greater than 30000, there may be a problem of reduced sensitivity of the positive photosensitive resin composition or reduced developability of a pattern.

[0067] In the positive photosensitive resin composition, the siloxane polymer and the olefin polymer may be provided in a weight ratio of 95:5 to 10:90, for example, the siloxane polymer and the olefin polymer may be provided in a weight ratio of 80:20 to 40:60. When the content ratio of the olefin polymer is less than 5, when evaluating the positive photosensitive resin composition, there is a problem of reduced chemical resistance or reduced flexibility. When the content ratio of the olefin polymer is greater than 90, there may be a problem of reduced development speed and sensitivity.

[0068] The 1,2-quinonediazide compound used in the present invention is a photosensitive compound, which can be obtained by reacting a phenol compound represented by the following Chemical Formula 4 with a naphthoquinonediazidesulfonic acid halogen compound.

[0069] Chemical formula 4:

[0070] In the above chemical formula 4, R 1 To R 6 are independently hydrogen, halogen, alkyl having 1 to 4 carbon atoms, alkenyl having 1 to 4 carbon atoms, or hydroxyl, R 7 and R 8 are independently hydrogen, halogen or alkyl having 1 to 4 carbon atoms, R 9 It is hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0071] The 1,2-quinonediazide compound can be prepared by reacting a phenolic compound, a naphthoquinonediazide sulfonic acid halogen, etc. in the presence of a weak base. When the 1,2-quinonediazide compound is synthesized using the phenolic compound and the naphthoquinonediazide sulfonic acid halogen compound, the degree of esterification can be 50% to 85%. When the degree of esterification is less than 50%, the residual rate can be reduced, and when the degree of esterification is greater than 85%, the storage stability can be reduced.

[0072] The 1,2-quinonediazide compound includes 1,2-quinonediazide 4-sulfonate, 1,2-quinonediazide 5-sulfonate, 1,2-quinonediazide 6-sulfonate, etc., but is not limited thereto.

[0073] In the 1,2-quinonediazide compound, the content of amine and / or halogen impurities may be 500 ppm or less, respectively. If the content of the impurities is greater than 500 ppm, the storage stability and baking scatter point may be reduced.

[0074] The 1,2-quinonediazide compound may be included in an amount of 5 to 50 parts by weight relative to 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer. When the content of the 1,2-quinonediazide compound is less than 5 parts by weight, the difference in solubility between the exposed portion and the non-exposed portion becomes small, making it difficult to form a pattern. When the content of the 1,2-quinonediazide compound is greater than 50 parts by weight, when light is irradiated in a short time, a large amount of unreacted 1,2-quinonediazide compound remains, making it difficult to develop due to low solubility in an alkaline aqueous solution as a developer.

[0075] The solvent used in the present invention can ensure the flatness of the positive photosensitive resin composition and prevent coating stains, thereby forming a uniform pattern profile.

[0076] The above-mentioned solvent may include at least one of 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 ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutyl glycol dimethyl ether, dibutyl glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol ethyl 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.

[0077] The solvent may contain 10 to 50 weight percent of the solid content of the positive photosensitive resin composition. When the content of the solid content is less than 10 weight percent, the coating thickness is too thin and the coating uniformity is reduced. When the content of the solid content is greater than 50 weight percent, the coating thickness is too thick, which may cause a burden on the coating equipment during coating. When the content of the solid content of the overall total composition is 10 to 25 weight percent, it is advantageous to use it in a slit coater. When the content of the solid content of the overall total composition is 25 to 50 weight percent, it is advantageous to use it in a spin coater or a slit spin coater.

[0078] According to an embodiment of the present invention, the positive photosensitive resin composition may further include at least one ultraviolet absorber selected from the group consisting of benzotriazine and benzotriazole.

[0079] The ultraviolet absorber can prevent the polymerization reaction of the unintended non-patterned portion by scattering the wavelength of ultraviolet rays generated during exposure.

[0080] Based on 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer, 1 to 20 parts by weight of the ultraviolet absorber can be provided. When the content of the ultraviolet absorber is less than 1 part by weight, the ultraviolet light absorption efficiency is reduced. When the content of the ultraviolet absorber is greater than 20 parts by weight, the curing degree of the total composition is reduced, and it is difficult to achieve a normal shape due to low sensitivity. Preferably, the positive photosensitive resin composition of the present invention can be filtered using a 0.1 μm to 0.2 μm microporous filter or the like before use.

[0081] Still another embodiment of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.

[0082] The above pattern forming method can be performed by a known method for forming patterns of an insulating film, a stack, and a pixel definition film in a display manufacturing process.

[0083] As a specific example, a method for forming a pattern of a display device using the positive photosensitive resin composition is as follows.

[0084] First, the positive photosensitive resin composition of one embodiment of the present invention is applied to the surface of the substrate by spin coating, slit spin coating, slit coating, roller coating, etc., and after vacuum drying, the solvent is removed by a pre-bake machine to form a coating film. At this time, the pre-bake machine can be implemented at a temperature of 100° C. to 120° C. for 1 minute to 3 minutes. Then, the coating film formed above 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 prescribed pattern.

[0085] The developer may be an alkaline aqueous solution, for example, inorganic bases such as sodium hydroxide, calcium hydroxide, sodium carbonate, etc.; primary amines such as ethylamine, n-propylamine, etc.; secondary amines such as diethylamine, n-propylamine, etc.; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc.; alcohol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine, etc.; or aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, etc. At this time, the developer may be used by dissolving the alkaline compound in a concentration of 0.1 to 5 parts by weight, and a water-soluble organic solvent such as methanol, ethanol, etc. and a surfactant may also be added in appropriate amounts.

[0086] After development using the developer as described above, the unnecessary parts are removed by washing with ultrapure water for 30 to 90 seconds, and the pattern is dried to form a pattern. After irradiating the pattern formed above with light such as ultraviolet rays, the pattern is heat treated at a temperature of 150°C to 400°C for 30 to 90 minutes using a heating device such as an oven, thereby obtaining the final pattern.

[0087] Another embodiment of the present invention provides a display device including a cured product of the positive photosensitive resin composition.

[0088] According to one embodiment of the present invention, the cured product of the positive photosensitive resin composition can be effectively applied to at least one of the insulating film and the planarizing film in the display device, and more specifically, can be effectively applied to the interlayer insulating film, protective insulating film (Passivation), gate insulating film, planarizing film, stack, pixel definition film, etc. in the display device.

[0089] The positive photosensitive resin composition has not only excellent sensitivity, heat discoloration resistance, degassing properties, moisture absorption rate and other properties, but also has especially excellent heat resistance. Therefore, the crack resistance and chemical resistance of the cured product of the resin composition can be improved, thereby ensuring excellent panel reliability.

[0090] Preferred examples are described below to help understand the present invention. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited to the following examples.

[0091] Example

[0092] Preparation Example 1: Preparation of siloxane copolymer

[0093] Into a flask with a refrigeration tube and a stirrer, 55 parts by weight of phenyltriethoxysilane, 20 parts by weight of tetraethoxysilane, and 25 parts by weight of methyltriethoxysilane as reactive silanes are added, and 100 parts by weight of methanol is added as a solvent, and the nitrogen is replaced and gently stirred. 50 parts by weight of ultrapure water and 4 parts by weight of oxalic acid as a catalyst are also added to the above reaction solution, and gently stirred. After 1 hour, the above reaction solution is heated to 60°C and maintained for 10 hours to polymerize, and then cooled to room temperature to terminate the reaction. In addition, the reactants are precipitated by rapid cooling to below 0°C, thereby removing the rising liquid containing unreacted monomers and catalysts.

[0094] Methanol is added and the purification process is repeated to completely remove unreacted monomers and catalysts. After the purification process, the residual alcohol solvent and residual water generated during the reaction are removed by vacuum drying to obtain a siloxane copolymer.

[0095] The gel permeation chromatography analysis was performed using KF-803, KF-802, and KF-801 columns as a Waters 2695 and PDA 996 apparatuses and tetrahydrofuran was measured as a mobile phase at a flow rate of 1 ml / min to prepare a siloxane copolymer (A) having a polystyrene-equivalent weight average molecular weight of 3000. Furthermore, the silica nuclear magnetic resonance analysis confirmed that the Q3+T3 ratio of the siloxane copolymer (A) accounted for 50% of the whole.

[0096] Preparation Example 2: Preparation of fluorine-containing siloxane copolymer

[0097] A siloxane copolymer (B) having a polystyrene-equivalent weight average molecular weight of 3,000 was prepared in the same manner as in Preparation Example 1 except that trifluoropropyltrimethoxysilane was used instead of methyltriethoxysilane.

[0098] Preparation Example 3: Preparation of 1,2-quinonediazide compounds

[0099] A 1,2-diazidenaphthoquinone-5-sulfonic acid ester compound having an esterification degree of 67% was obtained by condensing 1 mol of a phenol compound represented by the following chemical formula with 2 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride].

[0100]

[0101] Example 1: Preparation of positive photosensitive resin composition

[0102] 95 parts by weight of the siloxane copolymer (A) obtained in the above Preparation Example 1, polyhydroxystyrene (PHS) and styrene at a molar ratio of 9:1, 5 parts by weight of an olefin copolymer with a converted weight average molecular weight of 10,000, and 25 parts by weight of the 1,2-naphthoquinone diazide compound obtained in the above Preparation Example 3 were added, and mixed and dissolved with propylene glycol methyl ether acetate to make the solid content 25 parts by weight. Thereafter, the mixture was filtered with a 0.1 μm microporous filter to obtain a positive photosensitive resin composition.

[0103] Example 2: Preparation of positive photosensitive resin composition

[0104] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 90 parts by weight of the siloxane-based copolymer and 10 parts by weight of the olefin-based copolymer were used.

[0105] Example 3: Preparation of positive photosensitive resin composition

[0106] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of the siloxane-based copolymer and 20 parts by weight of the olefin-based copolymer were used.

[0107] Example 4: Preparation of positive photosensitive resin composition

[0108] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 70 parts by weight of the siloxane-based copolymer and 30 parts by weight of the olefin-based copolymer were used.

[0109] Example 5: Preparation of positive photosensitive resin composition

[0110] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 50 parts by weight of the siloxane-based copolymer and 50 parts by weight of the olefin-based copolymer were used.

[0111] Example 6: Preparation of positive photosensitive resin composition

[0112] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 30 parts by weight of the siloxane-based copolymer and 70 parts by weight of the olefin-based copolymer were used.

[0113] Example 7: Preparation of positive photosensitive resin composition

[0114] A positive photosensitive resin composition was prepared in the same manner as in Example 1, except that 10 parts by weight of the siloxane-based copolymer and 90 parts by weight of the olefin-based copolymer were used.

[0115] Example 8: Preparation of positive photosensitive resin composition

[0116] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin copolymer having a converted weight average molecular weight of 1,000 was used.

[0117] Example 9: Preparation of positive photosensitive resin composition

[0118] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that a siloxane copolymer having a converted weight average molecular weight of 5,000 was used.

[0119] Example 10: Preparation of positive photosensitive resin composition

[0120] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that a siloxane-based copolymer having a converted weight average molecular weight of 8,000 was used.

[0121] Example 11: Preparation of positive photosensitive resin composition

[0122] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that a siloxane copolymer having a converted weight average molecular weight of 15,000 was used.

[0123] Example 12: Preparation of positive photosensitive resin composition

[0124] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that a siloxane copolymer having a converted weight average molecular weight of 20,000 was used.

[0125] Example 13: Preparation of positive photosensitive resin composition

[0126] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin copolymer having a converted weight average molecular weight of 30,000 was used.

[0127] Example 14: Preparation of positive photosensitive resin composition

[0128] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that polyhydroxystyrene and styrene were polymerized at a molar ratio of 9.5:0.5 and an olefin copolymer having a converted weight average molecular weight of 10,000 was used.

[0129] Example 15: Preparation of positive photosensitive resin composition

[0130] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that polyhydroxystyrene and styrene were polymerized at a molar ratio of 8:2 and an olefin copolymer having a converted weight average molecular weight of 10,000 was used.

[0131] Example 16: Preparation of positive photosensitive resin composition

[0132] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that polyhydroxystyrene and styrene were polymerized at a molar ratio of 7:3 and an olefin copolymer having a converted weight average molecular weight of 10,000 was used.

[0133] Example 17: Preparation of positive photosensitive resin composition

[0134] A positive photosensitive resin composition was prepared in the same manner as in Example 5 except that 10 parts by weight of octyl 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-phenylpropanoate was used as an ultraviolet absorber.

[0135] Example 18: Preparation of positive photosensitive resin composition

[0136] A positive photosensitive resin composition was prepared in the same manner as in Example 6 except that 10 parts by weight of octyl 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-phenylpropanoate was used as an ultraviolet absorber.

[0137] Example 19: Preparation of positive photosensitive resin composition

[0138] A positive photosensitive resin composition was prepared in the same manner as in Example 4 except that 10 parts by weight of octyl 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-phenylpropanoate was used as an ultraviolet absorber.

[0139] Example 20: Preparation of positive photosensitive resin composition

[0140] A positive photosensitive resin composition was prepared in the same manner as in Example 3 except that 10 parts by weight of octyl 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-phenylpropanoate was used as an ultraviolet absorber.

[0141] Example 21: Preparation of positive photosensitive resin composition

[0142] The same method as in Example 17 was used except that 5 parts by weight of the ultraviolet absorber was used.

[0143] Example 22: Preparation of positive photosensitive resin composition

[0144] The same method as in Example 17 was used except that 20 parts by weight of the ultraviolet absorber was used.

[0145] Example 23: Preparation of positive photosensitive resin composition

[0146] A positive photosensitive resin composition was prepared in the same manner as in Example 2, except that 97 parts by weight of the siloxane-based copolymer and 3 parts by weight of the olefin-based copolymer were used.

[0147] Example 24: Preparation of positive photosensitive resin composition

[0148] A positive photosensitive resin composition was prepared in the same manner as in Example 2, except that 5 parts by weight of the siloxane-based copolymer and 95 parts by weight of the olefin-based copolymer were used.

[0149] Example 25: Preparation of positive photosensitive resin composition

[0150] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin copolymer having a converted weight average molecular weight of 500 was used.

[0151] Example 26: Preparation of positive photosensitive resin composition

[0152] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin copolymer having a converted weight average molecular weight of 40,000 was used.

[0153] Example 27: Preparation of positive photosensitive resin composition

[0154] A positive photosensitive resin composition was prepared in the same manner as in Example 5 except that the olefin copolymer was polymerized with only polyhydroxystyrene and the olefin copolymer having a converted weight average molecular weight of 10,000 represented by the following chemical formula was used.

[0155] Example 28: Preparation of positive photosensitive resin composition

[0156] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that the polyhydroxystyrene and styrene polymerized olefin copolymer was prepared in a molar ratio of 6.5:4.5 and the olefin copolymer had a converted weight average molecular weight of 10,000.

[0157] Comparative Example 1: Preparation of a positive photosensitive resin composition

[0158] A positive photosensitive resin composition was prepared in the same manner as in Example 5, except that the siloxane-based copolymer (B) prepared in Preparation Example 2 was used as the siloxane-based copolymer.

[0159] Comparative Example 2: Preparation of a positive photosensitive resin composition

[0160] A positive photosensitive resin composition was prepared in the same manner as in Example 2, except that 100 parts by weight of the olefin-based copolymer was used and the siloxane-based copolymer was not used.

[0161] Comparative Example 3: Preparation of a positive photosensitive resin composition

[0162] A positive photosensitive resin composition was prepared in the same manner as in Example 2, except that the olefin-based copolymer was not used and 100 parts by weight of the siloxane-based copolymer was used.

[0163] Experimental Example 1: Measurement of the physical properties of the positive photosensitive resin composition

[0164] For the above-mentioned Examples 1 to 28 and Comparative Examples 1 to 3, physical properties such as sensitivity, scum, resolution, heat discoloration resistance, heat resistance, cracking, chemical resistance, and adhesion were measured and shown in the following Table 1.

[0165] 1.1 Sample preparation

[0166] To this end, the positive photosensitive resin compositions obtained in the above-mentioned Examples 1 to 22 and Comparative Examples 1 to 9 were respectively applied to a glass substrate using a spin coater, vacuum dried, and pre-baked on a hot plate at 100° C. for 2 minutes to form a film with a thickness of 4.0 μm.

[0167] 1.2 Sensitivity

[0168] The film formed in the above-mentioned Experimental Example 1.1 was irradiated with a predetermined pattern mask and a standard dose of 20 mW / cm2 in broadband with a contact hole size (CD) of 5 μm. 2 After exposure to ultraviolet rays, the surface was developed with an aqueous solution of 2.38 weight percent tetramethylammonium hydroxide at 23° C. for 1 minute, and then washed with ultrapure water for 1 minute.

[0169] Then, the developed pattern was irradiated with 500 mJ / cm in a wide band. 2 The intensity is 20mW / cm 2 The film was exposed to ultraviolet rays and cured in an oven at 230° C. for 60 minutes to obtain a pattern film with a thickness of 3.5 μm and a contact hole size of 5 μm.

[0170] 1.3 Scum

[0171] The inside of the pattern formed when measuring the sensitivity in the above Experimental Example 1.2 was observed using a scanning electron microscope (SEM) to confirm whether there was residue in the Line & Space and the contact hole. The case where there was development residue was marked as ×, the case where the development residue existed only at the pattern boundary was marked as △, and the case where there was no development residue was marked as ○.

[0172] 1.4. Resolution

[0173] The measurement was performed using the minimum size of the contact hole pattern formed when the sensitivity was measured in the above-mentioned Experimental Example 1.2.

[0174] 1.5. Resistance to heat discoloration

[0175] The test substrate formed when measuring the sensitivity in the above Experimental Example 1.2 was further cured in an oven at 300°C for 60 minutes, and the heat discoloration resistance was evaluated by the change in the 400nm transmittance before and after curing. At this time, the case where the change rate is less than 3% is marked as ◎, the case where the change rate is 3-5% is marked as ○, the case where the change rate is 5-10% is marked as △, and the case where the change rate is greater than 10% is marked as ×.

[0176] 1.6. Heat resistance

[0177] Heat resistance was measured by TGA. After sampling the pattern film formed when measuring the sensitivity in the above Experimental Example 1.2, the temperature was raised at 10°C per minute to 900°C at room temperature by TGA. The case where the thermal decomposition temperature (Td) was above 450°C was marked as ○, the case where the thermal decomposition temperature (Td) was 350 to 400°C was marked as △, and the case where the thermal decomposition temperature (Td) was less than 350°C was marked as ×.

[0178] 1.7. Crack

[0179] The sensitivity evaluation substrate in the above-mentioned experimental example 1.2 was inspected by naked eye and observed under a microscope at a magnification of 100 times. The case where cracks were observed was marked as ×, the case where cracks were observed only at the coating edge was marked as △, and the case where no cracks were observed was marked as ○.

[0180] 1.8. Chemical resistance

[0181] The sensitivity evaluation substrate in the above Experimental Example 1.2 was immersed in N-methylpyrrolidone (NMP) at 40°C for 120 seconds, and the change rate of the cured film thickness before and after the immersion was measured. and less than The case of is marked as ○, and the change rate is The case of is marked as △, and the rate of change is The above situations are marked with ×.

[0182] 1.9. Adhesion

[0183] The pattern film was formed by the same method as that used in the above-mentioned Experimental Example 1.2 for measuring the sensitivity, and the adhesion according to the baking temperature was compared based on the case where the line width was 10 μm and the gap width was 1:1. At this time, the case where the adhesion was ensured at a baking temperature of 90°C to 100°C was marked as ○, the case where the adhesion was ensured at a baking temperature of 105°C to 115°C was marked as △, and the case where the adhesion was ensured or not ensured at a baking temperature of 120°C or more was marked as ×.

[0184] Table 1

[0185]

[0186] Table 2

[0187]

[0188] Table 3

[0189]

[0190] Table 4

[0191]

[0192] Table 5

[0193]

[0194] As shown in Table 1, according to the present invention, the positive photosensitive resin compositions prepared in Examples 1 to 28 have excellent properties such as resolution, sensitivity, scum, heat discoloration resistance, heat resistance, and crack resistance.

[0195] On the contrary, when any of the resins in Comparative Examples 1 and 2 was used, the characteristics were significantly degraded. When a siloxane resin was substituted for F, the characteristics were also significantly degraded.

[0196] It should be understood that the description of the present invention as described above is only for illustration, and without changing the technical idea or essential features of the present invention, a person skilled in the art of the present invention can easily transform the present invention into other specific forms. Therefore, the embodiments described above are only for illustration in all aspects and do not limit the present invention. For example, each structural element described in a single type can be implemented in a dispersed manner, and similarly, the structural elements described in a dispersed manner can be implemented in a combined form.

[0197] The scope of the present invention is defined by the scope of the claims for protection of the invention, and all changes or modifications derived from the meaning and scope of the claims for protection of the invention and their equivalents belong to the scope of the present invention.

Claims

1. A positive photosensitive resin composition, characterized in that: Include: A siloxane polymer obtained by polymerizing one or more reactive silanes represented by the following chemical formula 1-1 and one or more tetrafunctional reactive silanes represented by the following chemical formula 1-2; An olefin polymer comprising a repeating unit represented by the following chemical formula 2 or a repeating unit represented by the following chemical formula 2 and chemical formula 3; 1,2-Quinonediazide compounds; as well as Solvents, The siloxane polymer is prepared by hydrolyzing and polycondensing the reactive silane represented by the chemical formula 1-1 and the tetrafunctional reactive silane represented by the chemical formula 1-2 at a weight ratio of 2:8 to 8:

2. The siloxane polymer and the olefin polymer are provided in a weight ratio of 90:10 to 30:70, Based on 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer, 5 to 50 parts by weight of the 1,2-quinonediazide compound is included. The polystyrene-equivalent weight average molecular weight of the siloxane polymer is 1,000 to 20,000, and the polystyrene-equivalent weight average molecular weight of the olefin polymer is 1,000 to 30,000. Chemical formula 1-1: (R1) n Si(R2) 4-n , Chemical formula 1-2: Si(R3)4, In the above chemical formula 1-1 and chemical formula 1-2, R1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R2 is independently a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group or an acetoxy group, and the above R3 is independently one of an alkoxy group having 1 to 4 carbon atoms, a phenoxy group or an acetoxy group, and n is a natural number from 1 to 3. Chemical formula 2: Chemical formula 3:

2. The positive photosensitive resin composition according to claim 1, characterized in that: In the olefin-based polymer, the repeating units represented by Chemical Formula 2 and Chemical Formula 3 are provided in a ratio of 99:1 to 60:

40.

3. The positive photosensitive resin composition according to claim 1, characterized in that: In the above-mentioned siloxane polymer, the ratio of (Q3+T3) in the silicon nuclear magnetic resonance analysis result accounts for more than 40% of the total silicon.

4. The positive photosensitive resin composition according to claim 1, characterized in that: The 1,2-quinonediazide compound is obtained by reacting a phenol compound represented by the following chemical formula 4 with a naphthoquinonediazidesulfonic acid halogen compound. Chemical formula 4: In the above chemical formula 4, R1 to R6 are independently hydrogen, halogen, alkyl with 1 to 4 carbon atoms, alkenyl with 1 to 4 carbon atoms or hydroxyl, R7 and R8 are independently hydrogen, halogen or alkyl with 1 to 4 carbon atoms, and R9 is hydrogen or alkyl with 1 to 4 carbon atoms.

5. The positive photosensitive resin composition according to claim 1, characterized in that: The above-mentioned solvent includes at least one of 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 ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutyl glycol dimethyl ether, dibutyl glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol ethyl 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.

6. The positive photosensitive resin composition according to claim 1, characterized in that: The invention further comprises at least one ultraviolet absorber selected from the group consisting of benzotriazine and benzotriazole.

7. The positive photosensitive resin composition according to claim 6, characterized in that: The ultraviolet absorber is provided in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane polymer and the olefin polymer.

8. A method for forming a pattern of a display device, characterized in that: The positive photosensitive resin composition according to any one of claims 1 to 7 is used.

9. A display device, characterized in that: A cured product comprising the positive photosensitive resin composition according to any one of claims 1 to 7.

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