WO2020141854A1 - Positive photosensitive resin composition - Google Patents

Positive photosensitive resin composition Download PDF

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Publication number
WO2020141854A1
WO2020141854A1 PCT/KR2019/018795 KR2019018795W WO2020141854A1 WO 2020141854 A1 WO2020141854 A1 WO 2020141854A1 KR 2019018795 W KR2019018795 W KR 2019018795W WO 2020141854 A1 WO2020141854 A1 WO 2020141854A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive resin
ether
resin composition
positive photosensitive
weight
Prior art date
Application number
PCT/KR2019/018795
Other languages
French (fr)
Korean (ko)
Inventor
김동명
윤혁민
여태훈
신경순
이기선
황현민
박아름
Original Assignee
주식회사 동진쎄미켐
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 주식회사 동진쎄미켐 filed Critical 주식회사 동진쎄미켐
Priority to CN201980087219.0A priority Critical patent/CN113260922A/en
Priority to JP2021538380A priority patent/JP7491933B2/en
Publication of WO2020141854A1 publication Critical patent/WO2020141854A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays

Definitions

  • the present invention relates to a positive photosensitive resin composition, and more specifically, to a positive photosensitive resin composition having excellent performance such as sensitivity, heat discoloration resistance, gas generation, moisture absorption rate, etc. by including a siloxane polymer and an olefin polymer. will be.
  • photosensitive organic insulating films are used to insulate between wirings arranged between layers and to improve aperture ratio.
  • an acrylic insulating film is mainly applied, but outgassing due to a decrease in heat resistance continues to be an issue.
  • polyimide is applied as an interlayer insulating film for an OLED display device and a pixel definition film, but there are issues such as sensitivity, heat discoloration resistance, gas generation, and moisture absorption.
  • One task of the present invention is not only excellent in performances such as sensitivity, heat discoloration resistance, gas generation, moisture absorption rate, etc., but also in particular, due to its excellent heat resistance, crack resistance and chemical resistance are improved to secure excellent panel reliability. It is to provide a mold photosensitive resin composition.
  • Another object of the present invention is to provide a display element comprising a cured body of a positive photosensitive resin composition and a pattern forming method of a display element using the positive photosensitive resin composition.
  • One aspect of the present invention is a siloxane-based polymer obtained by polymerizing at least one reactive silane represented by Formula 1 below;
  • An olefin-based polymer comprising a repeating unit represented by the following Chemical Formula 2 or a repeating unit represented by the following Chemical Formulas 2 and 3; 1,2-quinonediazide compounds;
  • a positive photosensitive resin composition comprising a solvent:
  • R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms
  • R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group
  • i is an integer from 0 to 3.
  • the reactive silane is one or more reactive silane represented by the following formula 1-1; And one or more tetrafunctional reactive silanes represented by Formula 1-2 below:
  • R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms
  • R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, It is a phenoxy or acetoxy group
  • R 3 is independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group
  • n is a natural number of 1 to 3 carbon atoms.
  • the siloxane-based copolymer is a reactive silane represented by the formula 1-1 and a tetrafunctional reactive silane represented by the formula 1-2 in a weight ratio of 2:8 to 8:2 It may be decomposition and condensation polymerization.
  • the repeating units represented by Chemical Formulas 2 and 3 may be provided in a ratio of 99:1 to 60:40.
  • the ratio of (Q3+T3) in Si NMR analysis results of the siloxane-based polymer may be 40% or more of the total silicon.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the siloxane polymer may be 1,000 to 20,000, and the polystyrene-equivalent weight average molecular weight (Mw) of the olefin polymer may be 1,000 to 30,000.
  • the siloxane-based polymer and the olefin-based polymer may be provided in a weight ratio of 95:5 to 10:90.
  • the 1,2-quinonediazide compound may be obtained by reacting a phenol compound represented by the following Chemical Formula 4 with a naphthoquinonediazide sulfonic acid halogen compound:
  • R 1 to R 6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxy group
  • R 7 and R 8 are each independently hydrogen, halogen or carbon number It is an alkyl group of 1 to 4
  • R 9 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
  • the solvent is propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Cypionate, 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, dibutylene glycol dimethyl ether, and Dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether
  • the 1,2-quinonediazide compound based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer, contains 5 to 50 parts by weight, and the solvent has a solid content of 10 to 50% by weight.
  • the positive photosensitive resin composition may further include at least one UV absorber of benzotriazine-based and benzotriazole-based.
  • the UV absorber may be provided in 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer.
  • Another aspect of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.
  • Another aspect of the present invention provides a display device including a cured body of the positive photosensitive resin composition.
  • the positive photosensitive resin composition according to the present invention not only has excellent performances such as sensitivity, heat discoloration resistance, gas generation, moisture absorption, etc., but also can improve crack resistance and chemical resistance due to particularly excellent heat resistance.
  • the positive photosensitive resin composition according to the present invention can be usefully applied not only to an interlayer insulating film, a protective insulating film, or a gate insulating film in a display device, but also to a planarizing film, a bank, a pixel defining film, etc., and a positive photosensitive resin composition according to the present invention By using it, excellent panel reliability can be secured.
  • One aspect of the present invention is a siloxane-based polymer; Olefin-based polymers; 1,2-quinonediazide compounds; And it provides a positive photosensitive resin composition comprising a solvent.
  • the hybrid composition of the siloxane-based polymer and the olefin-based polymer used in the present invention not only has excellent performances such as sensitivity, resolution, adhesion, permeability, and heat discoloration resistance, but also reduces gas generation due to particularly excellent heat resistance and low moisture. By maintaining the moisture absorption rate, it can function as a binder that can secure excellent panel reliability.
  • the siloxane-based polymer used in the present invention can be obtained by polymerizing at least one reactive silane represented by Formula 1 below:
  • R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms
  • R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group
  • i is an integer from 0 to 3.
  • the reactive silane is at least one reactive silane represented by the following Chemical Formula 1-1; And one or more tetrafunctional reactive silanes represented by Formula 1-2 below:
  • R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms
  • R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, It is a phenoxy or acetoxy group
  • R 3 is independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group
  • n is a natural number of 1 to 3 carbon atoms.
  • the reactive silane represented by Chemical Formula 1-1 is, for example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenylmethyldimethoxysilane, phenyltriacetoxysilane, or phenyltriphenoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane , Hexyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and the like, or may be used alone or in combination of two or more.
  • the tetrafunctional reactive silane represented by Chemical Formula 1-2 includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and the like, or by mixing two or more. Can be used.
  • the siloxane-based copolymer is a hydrolysis and condensation polymerization by providing a reactive silane represented by the formula 1-1 and a tetrafunctional reactive silane represented by the formula 1-2 in a weight ratio of 2:8 to 8:2.
  • a reactive silane represented by the formula 1-1 and a tetrafunctional reactive silane represented by the formula 1-2 in a weight ratio of 2:8 to 8:2.
  • the reactive silane represented by Chemical Formula 1-1 may be included in an amount of 20 to 80 parts by weight with respect to the total monomer constituting the siloxane polymer.
  • the content of the reactive silane represented by Chemical Formula 1-1 is less than 20 parts by weight, cracks may occur during film formation, and when it exceeds 80 parts by weight, reactivity during polymerization may be reduced and molecular weight may be difficult to control.
  • the tetrafunctional reactive silane represented by Chemical Formula 1-2 may be included in an amount of 80 to 20 parts by weight based on the total monomer constituting the siloxane polymer.
  • the content of the tetrafunctional reactive silane represented by Chemical Formula 1-2 is less than 20 parts by weight, solubility in an aqueous alkali solution may be deteriorated when forming a pattern of the photosensitive siloxane resin composition, and when it exceeds 80 parts by weight It is difficult to control the molecular weight due to the high reactivity during polymerization, and the resulting siloxane oligomer may have too high solubility in an aqueous alkali solution.
  • the siloxane-based polymer may further comprise i) a reactive silane represented by Formula 1-1 and ii) a tetrafunctional reactive silane represented by Formula 1-2, and iii) a reactive silane represented by Formula 5 below. It can be obtained by hydrolysis and condensation polymerization under and removal of unreacted monomers and catalysts:
  • R 4 are each independently vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxy phenyl)alkyl, 2-(p-hydroxy phenyl)alkyl, 3- Glycidoxy alkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl or oxetanealkyl, R 5 is an alkoxy group having 1 to 4 carbon atoms, phenoxy or acetoxy, n is 1 to It is an integer of 3.
  • the reactive silane represented by the formula (5) is, for example, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyl triethoxysilane, 1-(p- Hydroxy phenyl) ethyl trimethoxysilane, 2-(p-hydroxy phenyl) ethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycine Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane , 3-isocyanate propyl trimethoxysilane, oxetane
  • the content of the reactive silane represented by the formula (5) may be included in 5 to 50 parts by weight with respect to the total monomer constituting the siloxane-based polymer.
  • the content of the reactive silane represented by Chemical Formula 5 is within the above range, adhesiveness and film hardening degree may be further improved.
  • the siloxane-based polymer may be obtained by bulk polymerization or solution polymerization of the above-described reactive silane and the like under water and an acid or base catalyst. Specifically, the siloxane-based polymer may be obtained through hydrolysis and condensation polymerization of the reactive silanes acting as a monomer, and removal of unreacted monomers and catalysts.
  • the acid catalyst that can be used in the polymerization includes, for example, hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, oxalic acid, propionic acid, butanoic acid, pentanoic acid, etc.
  • the basic catalyst is, for example, ammonia, organic And amine and alkylammonium hydrochloride salts, and these may be used alone or in combination of two or more, simultaneously or in stages.
  • the siloxane-based polymer finally obtained may have a weight average molecular weight (Mw) in terms of polystyrene through GPC of 1,000 to 20,000.
  • Mw weight average molecular weight
  • the weight average molecular weight in terms of polystyrene of the siloxane-based polymer is less than 1,000, when evaluating a positive type photosensitive resin composition, there is a problem that the residual film rate decreases during the development process or the heat resistance falls and the moisture absorption rate is vulnerable, and when it exceeds 20,000, the positive type photosensitive resin There is a problem that the sensitivity of the composition is lowered or the developability of the pattern is poor.
  • the ratio of (Q3+T3) in Si NMR analysis results of the siloxane-based polymer may be 40% or more of the total silicon.
  • the siloxane copolymer includes a ladder structure, and the proportion of the siloxane-based polymer having a ladder structure is 40% or more based on Si(Silicon) NMR analysis results.
  • the proportion of the ladder structure of the siloxane copolymer is less than 40%, chemical resistance to strippers and etching solutions may be weak.
  • the olefin-based polymer used in the present invention may include repeating units represented by the following Chemical Formula 2 or repeating units represented by the following Chemical Formulas 2 and 3.
  • the olefin-based polymer may be a homopolymer containing only the repeating unit represented by Formula 2 or a copolymer containing both the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3:
  • the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 are 99:1 to 60:40, for example, 99:1 to 70:30, for example, 95:5 To 70:30.
  • the ratio represents the molar ratio of two repeating units, and can be confirmed, for example, based on results obtained from analysis results of 2D-NMR (H-NMR, C-NMR, etc.).
  • the olefin-based polymer is excellent in crack resistance and chemical resistance, and when used, serves as a binder to ensure excellent panel reliability in a display.
  • the weight average molecular weight (Mw) in terms of polystyrene through GPC of the olefin-based polymer may be 1,000 to 30,000.
  • Mw weight average molecular weight in terms of polystyrene of the olefin-based polymer
  • the weight average molecular weight in terms of polystyrene of the olefin-based polymer is less than 1,000, there is a problem that a residual film rate decreases or heat resistance decreases during the development process when evaluating a positive photosensitive resin composition, and when it exceeds 30,000, the sensitivity of the positive photosensitive resin composition decreases Or a problem in which the developability of the pattern is poor may occur.
  • the siloxane-based polymer and the olefin-based polymer may be provided in a weight ratio of 95:5 to 10:90, for example, 80:20 to 40:60.
  • the content ratio of the olefin-based polymer is less than 5, there is a problem that chemical resistance is deteriorated or flexibility is poor when evaluating a positive photosensitive resin composition, and when it exceeds 90, a developing speed is slow and a sensitivity is deteriorated.
  • the 1,2-quinonediazide compound used in the present invention is a photosensitive compound, and may be obtained by reacting a phenol compound represented by Formula 4 with a naphthoquinonediazide sulfonic acid halogen compound:
  • R 1 to R 6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxy group
  • R 7 and R 8 are each independently hydrogen, halogen or carbon number It is an alkyl group of 1 to 4
  • R 9 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
  • the 1,2-quinonediazide compound may be prepared by reacting a phenol compound, naphthoquinonediazide sulfonate halogen, and the like under a weak base.
  • the degree of esterification thereof may be 50 to 85%.
  • the esterification degree is less than 50%, the residual film rate may be deteriorated, and when it is more than 85%, storage stability may be deteriorated.
  • the 1,2-quinonediazide compound includes 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, and the like, It is not limited to this.
  • the 1,2-quinonediazide compound may have an amine and/or halogen-based impurity content of 500 ppm or less, respectively. When the content of the impurities exceeds 500ppm, storage stability and baking dispersion may be deteriorated.
  • the 1,2-quinonediazide compound may be included in 5 to 50 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer.
  • the content of the 1,2-quinone diazide compound is less than 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part becomes small, making pattern formation difficult, and when it exceeds 50 parts by weight, unreacted when irradiated with light for a short time 1 Due to the large amount of ,2-quinone diazide compound remaining, the solubility in an aqueous alkali solution as a developer may be too low, and development may be difficult.
  • the solvent used in the present invention does not generate flatness and coating unevenness of the positive photosensitive resin composition, so that a uniform pattern profile can be formed.
  • the solvent is propylene glycol methyl ether acetate, propylene glycol 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, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, di Ethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glyco
  • the solvent may be included so that the content of the solid content of the positive photosensitive resin composition is 10 to 50% by weight. If the content of the solid content is less than 10% by weight, the coating thickness may be too thin and the coating uniformity may be deteriorated. If it is more than 50% by weight, the coating thickness may be too thick and may impair coating equipment during coating. When the solid content of the total composition is 10 to 25% by weight, it is easy to be used in a slit coater, and when it is 25 to 50% by weight, a spin coater or a slit and spin coater Spin Coater).
  • the positive photosensitive resin composition may further include at least one UV absorber of benzotriazine-based and benzotriazole-based.
  • the UV absorber can prevent a polymerization reaction due to diffuse reflection on the unpatterned portion, which was unexpected due to wavelengths of ultraviolet rays or the like generated during exposure.
  • the UV absorber may be provided in 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer.
  • the positive photosensitive resin composition of the present invention is preferably used after filtering using a millipore filter of 0.1 to 0.2 ⁇ m.
  • Another aspect of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.
  • the pattern forming method may be performed by a known method in a method of forming an insulating layer, a bank, or a pixel defining layer pattern in a display manufacturing process.
  • a method of forming a pattern of a display device using the positive photosensitive resin composition is as follows.
  • the positive photosensitive resin composition according to an embodiment of the present invention is coated on a substrate surface with spin coating, slit & spin coating, slit coating, roll coating, etc., and then vacuum dried to remove the solvent by prebaking to form a coating film.
  • the pre-baking may be performed at a temperature of 100 to 120 °C for 1 to 3 minutes.
  • a predetermined pattern is formed by irradiating visible coating, ultraviolet rays, far ultraviolet rays, electron beams, X-rays or the like to the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.
  • an aqueous alkali solution can be used, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate.
  • Primary amines such as ethylamine, n-propylamine, diethylamine, and n-propylamine.
  • Amines Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine Dimethylethanolamine, alcoholamines such as methyldiethanolamine, triethanolamine or tetramethylammonium hydroxide, tetraethylammonium hydroxide And quaternary ammonium salt aqueous solutions.
  • the developer is used by dissolving the alkaline compound in a concentration of 0.1 to 5 parts by weight, and an appropriate amount of a water-soluble organic solvent and surfactant such as methanol and ethanol can be added.
  • the final pattern may be obtained by heat treatment at a temperature of 400° C. for 30 to 90 minutes.
  • Another aspect of the present invention provides a display device including a cured body of the positive photosensitive resin composition.
  • the cured body of the positive photosensitive resin composition is at least one or more of an insulating film and a planarizing film in a display device, more specifically, an interlayer insulating film, a protective insulating film (Passivation), a gate insulating film in a display device , It can be usefully applied to planarization films, banks, pixel definition films, and the like.
  • the positive photosensitive resin composition not only has excellent performances such as sensitivity, heat discoloration resistance, gas discharge, and moisture absorption, but also has particularly excellent heat resistance, thereby improving crack resistance and chemical resistance of the cured body of the resin composition. Excellent panel reliability can be ensured.
  • Mw polystyrene-equivalent weight average molecular weight
  • Example 1 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.
  • Example 1 a positive-type 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.
  • Example 1 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.
  • Example 1 a positive type 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.
  • Example 1 a positive-type 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.
  • Example 1 a positive-type 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.
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 1,000 was used.
  • Mw weight average molecular weight
  • a positive type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 5,000 in Example 5 was used.
  • Mw weight average molecular weight
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 8,000 was used.
  • Mw weight average molecular weight
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 15,000 was used.
  • Mw weight average molecular weight
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 20,000 was used.
  • Mw weight average molecular weight
  • a positive type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 30,000 in Example 5 was used.
  • Mw weight average molecular weight
  • Example 5 except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 9.5:0.5 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
  • PHS polyhydroxystyrene
  • Mw weight average molecular weight
  • Example 5 except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 8:2 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
  • PHS polyhydroxystyrene
  • Mw weight average molecular weight
  • Example 5 except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 7:3 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
  • PHS polyhydroxystyrene
  • Mw weight average molecular weight
  • Example 5 Except that 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester was further used as the UV absorber in Example 5, In the same manner as in Example 5, a positive photosensitive resin composition was prepared.
  • Example 6 Except that in Example 6, 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester was further used as a UV absorber. A positive type photosensitive resin composition was prepared in the same manner as in Example 6.
  • Example 4 except for using 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoate octyl ester as a UV absorber.
  • a positive type photosensitive resin composition was prepared in the same manner as in Example 4.
  • Example 3 except for using 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoate octyl ester as a UV absorber
  • a positive photosensitive resin composition was prepared in the same manner as in Example 3.
  • Example 2 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.
  • Example 2 a positive-type 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.
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 500 was used.
  • Mw weight average molecular weight
  • Example 5 a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 40,000 was used.
  • Mw weight average molecular weight
  • Example 5 the olefin-based copolymer was polymerized with only hydroxy-styrene (PHS), and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 represented by the following formula was used.
  • PHS hydroxy-styrene
  • Mw weight average molecular weight
  • Example 5 except that the olefin-based copolymer of polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 6.5:4.5 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, In the same manner as in Example 5, a positive photosensitive resin composition was prepared.
  • PHS polyhydroxystyrene
  • Mw weight average molecular weight
  • 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 in Example 5.
  • Example 2 a positive photosensitive resin composition was prepared in the same manner as in Example 2, except that 100 parts by weight of the siloxane-based copolymer was used and no olefin-based copolymer was used.
  • Example 2 a positive type 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 without using the siloxane-based copolymer.
  • the positive type photosensitive resin compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 9 were respectively coated on a glass substrate using a spin coater, followed by vacuum drying and 100° C. for 2 minutes. It was prebaked on a hot plate to form a film having a thickness of 4.0 ⁇ m.
  • the ultraviolet rays having a strength of 20 mW/cm2 in broadband are 5 ⁇ m contact hole CD formation reference dose (Dose)
  • Dose contact hole CD formation reference dose
  • the pattern developed in the above was irradiated with ultraviolet light having a strength of 20 mW/cm 2 at a broadband of 500 mJ/cm 2, and cured in an oven at 230° C. for 60 minutes to have a thickness of 3.5 ⁇ m and a contact hole CD of 5 ⁇ m.
  • a phosphorus pattern film was obtained.
  • the measurement substrate formed during the sensitivity measurement in Experimental Example 1.2. was further cured in an oven at 300° C. for 60 minutes to evaluate heat discoloration resistance by 400 nm transmittance change before and after curing. At this time, when the rate of change was less than 3%, ⁇ 3 to 5%, ⁇ 5 to 10%, and ⁇ 10% or more were indicated by X.
  • Heat resistance was measured using TGA. After sampling the pattern film formed during the sensitivity measurement in Experimental Example 1.2., the temperature was raised by 10° C. per minute from room temperature to 900° C. using TGA.
  • TGA thermal decomposition temperature
  • the case where the thermal decomposition temperature (Td) is less than 350°C is denoted by X.
  • the sensitivity evaluation board was observed by visual inspection and a microscope at 100 times magnification, and X was observed when cracks were observed and ⁇ when cracks were observed only at the coating edge, ⁇ when no cracks were observed.
  • the sensitivity evaluation substrate was immersed in 40° C. NMP for 120 seconds, and the rate of change in the thickness of the cured film before and after immersion was measured. Notation.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Siloxane polymer Content (parts by weight) 95 90 80 70 50 30 Molecular Weight 3,000 3,000 3,000 3,000 3,000 3,000 3,000 3,000 3,000 3,000 3,000 Olefin polymer Content (parts by weight) 5 10 20 30 50 70 Molecular Weight 10,000 10,000 10,000 10,000 10,000 10,000 PHS 9 9 9 9 9 9 Styrene One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One
  • the positive photosensitive resin compositions prepared in Examples 1 to 28 according to the present invention were excellent in properties such as resolution, sensitivity, scum, discoloration, heat resistance, and crack resistance.

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Abstract

A positive photosensitive resin composition of the present invention comprises: a siloxane-based polymer obtained by polymerization of one or more reactive silanes; an olefin-based polymer comprising repeating units comprising one or more hydroxyphenyl groups or phenyl groups; a 1,2-quinone diazide compound; and a solvent. The positive photosensitive resin composition of the present invention has excellent performance in terms of sensitivity, thermochromic resistance, and the like, and in particular, has excellent heat resistance such that, when used in display panels, excellent panel reliability may be secured due to the improvement in cracks and heat resistance.

Description

포지티브형 감광성 수지 조성물Positive photosensitive resin composition
본 발명은 포지티브형 감광성 수지 조성물에 관한 것으로, 보다 구체적으로는 실록산계 중합체 및 올레핀계 중합체를 포함함으로써 감도, 내열변색성, 가스 발생, 수분흡습율 등 우수한 성능을 갖는 포지티브형 감광성 수지 조성물에 관한 것이다.The present invention relates to a positive photosensitive resin composition, and more specifically, to a positive photosensitive resin composition having excellent performance such as sensitivity, heat discoloration resistance, gas generation, moisture absorption rate, etc. by including a siloxane polymer and an olefin polymer. will be.
최근 액정 표시소자, OLED 표시소자, 집적 회로 소자에는 층간에 배치되는 배선의 사이를 절연하고 개구율 향상을 위해서 감광성 유기 절연막을 사용하고 있다. 액정 표시소자용 층간 절연막으로는 주로 아크릴계 절연막이 적용되고 있으나, 내열성 저하로 인한 가스 발생(Outgassing)이 계속적으로 이슈가 되고 있다. 또한 OLED 표시소자용 층간 절연막 및 화소정의막으로는 폴리이미드가 적용되고 있으나, 감도, 내열변색성, 가스 발생, 수분흡습율 등의 이슈가 있다. 최근 들어서는 OLED 표시소자의 패널 신뢰성의 확보를 위해 내크랙성 및 내화학성을 갖는 재료의 요구가 증가되고 있다. Recently, in liquid crystal display devices, OLED display devices, and integrated circuit devices, photosensitive organic insulating films are used to insulate between wirings arranged between layers and to improve aperture ratio. As the interlayer insulating film for liquid crystal display devices, an acrylic insulating film is mainly applied, but outgassing due to a decrease in heat resistance continues to be an issue. In addition, polyimide is applied as an interlayer insulating film for an OLED display device and a pixel definition film, but there are issues such as sensitivity, heat discoloration resistance, gas generation, and moisture absorption. Recently, in order to secure panel reliability of OLED display devices, there is an increasing demand for materials having crack resistance and chemical resistance.
이에 따라 최근 실록산계 및 올레핀계 수지 기술을 기반으로 한 재료에 대한 필요성이 크게 요청되고 있으며, 이에 대한 기술개발이 활발히 이루어지고 있다.Accordingly, in recent years, the need for materials based on siloxane-based and olefin-based resin technologies has been greatly requested, and technology development has been actively conducted.
본 발명의 일 과제는 감도, 내열변색성, 가스 발생, 수분흡습율 등의 성능이 우수할 뿐만 아니라, 특히 뛰어난 내열성으로 인해 내크랙성 및 내화학성이 향상되어 우수한 패널 신뢰성을 확보할 수 있는 포지티브형 감광성 수지 조성물을 제공하는 것에 있다. One task of the present invention is not only excellent in performances such as sensitivity, heat discoloration resistance, gas generation, moisture absorption rate, etc., but also in particular, due to its excellent heat resistance, crack resistance and chemical resistance are improved to secure excellent panel reliability. It is to provide a mold photosensitive resin composition.
본 발명의 다른 일 과제는 상기 포지티브형 감광성 수지 조성물을 이용한 디스플레이 소자의 패턴형성방법, 및 포지티브형 감광성 수지 조성물의 경화체를 포함하는 디스플레이 소자를 제공하는 것에 있다.Another object of the present invention is to provide a display element comprising a cured body of a positive photosensitive resin composition and a pattern forming method of a display element using the positive photosensitive resin composition.
본 발명의 일 양태는 1종 이상의 하기 화학식 1로 표시되는 반응성 실란을 중합하여 얻어진 실록산계 중합체; 하기 화학식 2로 표시되는 반복단위를 포함하거나 하기 화학식 2 및 3으로 표시되는 반복단위를 포함하는 올레핀계 중합체; 1,2-퀴논디아지드 화합물; 및 용매를 포함하는 포지티브형 감광성 수지 조성물을 제공한다: One aspect of the present invention is a siloxane-based polymer obtained by polymerizing at least one reactive silane represented by Formula 1 below; An olefin-based polymer comprising a repeating unit represented by the following Chemical Formula 2 or a repeating unit represented by the following Chemical Formulas 2 and 3; 1,2-quinonediazide compounds; And it provides a positive photosensitive resin composition comprising a solvent:
[화학식 1] [Formula 1]
Si(R 1) i(R 2) 4-i Si(R 1 ) i (R 2 ) 4-i
상기 화학식에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시기 또는 아세톡시기이고, i는 0 내지 3의 정수이다. In the above formula, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, i is an integer from 0 to 3.
[화학식 2][Formula 2]
Figure PCTKR2019018795-appb-img-000001
Figure PCTKR2019018795-appb-img-000001
[화학식 3][Formula 3]
Figure PCTKR2019018795-appb-img-000002
Figure PCTKR2019018795-appb-img-000002
본 발명의 일 실시예에 따르면, 상기 반응성 실란은 1종 이상의 하기 화학식 1-1로 표시되는 반응성 실란; 및 1종 이상의 하기 화학식 1-2로 표시되는 4관능 반응성 실란을 포함할 수 있다:According to an embodiment of the present invention, the reactive silane is one or more reactive silane represented by the following formula 1-1; And one or more tetrafunctional reactive silanes represented by Formula 1-2 below:
[화학식 1-1][Formula 1-1]
(R 1) nSi(R 2) 4-n (R 1 ) n Si(R 2 ) 4-n
[화학식 1-2][Formula 1-2]
Si(R 3) 4 Si(R 3 ) 4
상기 화학식 1-1 및 화학식 1-2에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기이고, 상기 R 3은 서로 독립적으로 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기중 어느 하나이고, n은 1 내지 3의 자연수이다. In Formula 1-1 and Formula 1-2, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, It is a phenoxy or acetoxy group, and R 3 is independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3 carbon atoms.
본 발명의 일 실시예에 따르면, 상기 실록산계 공중합체는 상기 화학식 1-1로 표시되는 반응성 실란 및 상기 화학식 1-2로 표시되는 4관능 반응성 실란이 2:8 내지 8:2의 중량비로 가수 분해 및 축합 중합한 것일 수 있다. According to an embodiment of the present invention, the siloxane-based copolymer is a reactive silane represented by the formula 1-1 and a tetrafunctional reactive silane represented by the formula 1-2 in a weight ratio of 2:8 to 8:2 It may be decomposition and condensation polymerization.
본 발명의 일 실시예에 따르면, 상기 올레핀계 중합체에서, 상기 화학식 2 및 3으로 표시되는 반복단위는 99:1 내지 60:40의 비로 제공될 수 있다. According to an embodiment of the present invention, in the olefin-based polymer, the repeating units represented by Chemical Formulas 2 and 3 may be provided in a ratio of 99:1 to 60:40.
본 발명의 일 실시예에 따르면, 상기 실록산계 중합체는 Si NMR 분석 결과 중 (Q3+T3)의 비율이 전체 실리콘 중 40% 이상일 수 있다. According to an embodiment of the present invention, the ratio of (Q3+T3) in Si NMR analysis results of the siloxane-based polymer may be 40% or more of the total silicon.
본 발명의 일 실시예에 따르면, 상기 실록산계 중합체의 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 20,000이고, 상기 올레핀계 중합체의 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 30,000일 수 있다. According to an embodiment of the present invention, the polystyrene-equivalent weight average molecular weight (Mw) of the siloxane polymer may be 1,000 to 20,000, and the polystyrene-equivalent weight average molecular weight (Mw) of the olefin polymer may be 1,000 to 30,000.
본 발명의 일 실시예에 따르면, 상기 실록산계 중합체 및 올레핀계 중합체는 95:5 내지 10:90의 중량비로 제공될 수 있다. 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.
본 발명의 일 실시예에 따르면, 상기 1,2-퀴논디아지드 화합물은 하기 화학식 4로 표시되는 페놀 화합물과 나프토퀴논디아지드술폰산 할로겐 화합물을 반응시켜 얻어진 것일 수 있다:According to an embodiment of the present invention, the 1,2-quinonediazide compound may be obtained by reacting a phenol compound represented by the following Chemical Formula 4 with a naphthoquinonediazide sulfonic acid halogen compound:
[화학식 4][Formula 4]
Figure PCTKR2019018795-appb-img-000003
Figure PCTKR2019018795-appb-img-000003
상기 화학식 4에서, R 1 내지 R 6은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 4의 알킬기, 탄소수 1 내지 4의 알케닐기 또는 히드록시기이고, R 7 및 R 8은 각각 독립적으로 수소, 할로겐 또는 탄소수 1 내지 4의 알킬기이고, R 9는 수소 또는 탄소수 1 내지 4의 알킬기이다. In Formula 4, R 1 to R 6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxy group, and R 7 and R 8 are each independently hydrogen, halogen or carbon number It is an alkyl group of 1 to 4, and R 9 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
본 발명의 일 실시예에 따르면, 상기 용매는 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르 프로피오네이트, 프로필렌글리콜에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 디프로필렌글리콜디메틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에테르, 트리에티렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디프로필렌글리콜에틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르 중 적어도 하나 이상을 포함할 수 있다. According to an embodiment of the present invention, the solvent is propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Cypionate, 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, dibutylene glycol dimethyl ether, and Dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, di Propylene 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.
본 발명의 일 실시예에 따르면, 상기 실록산계 중합체 및 올레핀계 중합체의 총중량 100 중량부를 기준으로, 상기 1,2-퀴논디아지드 화합물은 5 내지 50 중량부로 포함하고, 상기 용매는 고형분의 함량이 10 내지 50 중량%가 되도록 포함할 수 있다. According to an embodiment of the present invention, based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer, the 1,2-quinonediazide compound contains 5 to 50 parts by weight, and the solvent has a solid content of 10 to 50% by weight.
본 발명의 일 실시예에 따르면, 상기 포지티브형 감광성 수지조성물은 벤조트리아진계 및 벤조트리아졸계 중 적어도 하나 이상의 UV 흡광제를 추가로 포함할 수 있다. According to one embodiment of the present invention, the positive photosensitive resin composition may further include at least one UV absorber of benzotriazine-based and benzotriazole-based.
본 발명의 일 실시예에 따르면, 상기 UV 흡광제는, 상기 실록산계 중합체 및 올레핀계 중합체의 총중량 100 중량부를 기준으로, 1 내지 20 중량부로 제공될 수 있다. According to an embodiment of the present invention, the UV absorber may be provided in 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer.
본 발명의 다른 일 양태는 상기 포지티브형 감광성 수지 조성물을 사용하는 디스플레이 소자의 패턴 형성 방법을 제공한다. Another aspect of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.
본 발명의 또 다른 일 양태는 상기 포지티브형 감광성 수지 조성물의 경화체를 포함하는 디스플레이 소자를 제공한다.Another aspect of the present invention provides a display device including a cured body of the positive photosensitive resin composition.
본 발명에 따른 포지티브형 감광성 수지 조성물은 감도, 내열변색성, 가스 발생, 수분흡습율 등의 성능이 우수할 뿐만 아니라, 특히 뛰어난 내열성으로 인해 내크랙성 및 내화학성이 향상될 수 있다. The positive photosensitive resin composition according to the present invention not only has excellent performances such as sensitivity, heat discoloration resistance, gas generation, moisture absorption, etc., but also can improve crack resistance and chemical resistance due to particularly excellent heat resistance.
본 발명에 따른 포지티브형 감광성 수지 조성물은 디스플레이 소자에서의 층간 절연막, 보호 절연막, 게이트 절연막뿐만 아니라 평탄화막, 뱅크, 화소정의막 등에도 유용하게 적용할 수 있으며, 본 발명에 따른 포지티브형 감광성 수지 조성물을 사용함으로써 우수한 패널 신뢰성을 확보할 수 있다. The positive photosensitive resin composition according to the present invention can be usefully applied not only to an interlayer insulating film, a protective insulating film, or a gate insulating film in a display device, but also to a planarizing film, a bank, a pixel defining film, etc., and a positive photosensitive resin composition according to the present invention By using it, excellent panel reliability can be secured.
본 발명의 효과는 상기한 효과들로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.
이하에서는 첨부한 도면을 참조하여 본 발명을 설명하기로 한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 따라서 여기에서 설명하는 실시예로 한정되는 것은 아니다. Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and thus is not limited to the embodiments described herein.
본 명세서에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "include" or "have" are intended to indicate that there are features, numbers, steps, operations, components, parts or combinations thereof described in the specification, and one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.
이하, 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명의 일 양태는 실록산계 중합체; 올레핀계 중합체; 1,2-퀴논디아지드 화합물; 및 용매를 포함하는 포지티브형 감광성 수지 조성물을 제공한다. One aspect of the present invention is a siloxane-based polymer; Olefin-based polymers; 1,2-quinonediazide compounds; And it provides a positive photosensitive resin composition comprising a solvent.
본 발명에 사용되는 상기 실록산계 중합체 및 올레핀계 중합체의 하이브리드 조성물은 감도, 해상도, 접착력, 투과도, 내열변색성 등의 성능이 우수할 뿐만 아니라, 특히 뛰어난 내열성으로 인해 가스 발생을 저감시키고, 낮은 수분흡습율을 유지함으로써 우수한 패널 신뢰성을 확보할 수 있는 바인더로 기능할 수 있다. The hybrid composition of the siloxane-based polymer and the olefin-based polymer used in the present invention not only has excellent performances such as sensitivity, resolution, adhesion, permeability, and heat discoloration resistance, but also reduces gas generation due to particularly excellent heat resistance and low moisture. By maintaining the moisture absorption rate, it can function as a binder that can secure excellent panel reliability.
본 발명에서 사용되는 상기 실록산계 중합체는 1종 이상의 하기 화학식 1로 표시되는 반응성 실란을 중합함으로써 얻어질 수 있다:The siloxane-based polymer used in the present invention can be obtained by polymerizing at least one reactive silane represented by Formula 1 below:
[화학식 1] [Formula 1]
Si(R 1) i(R 2) 4-i Si(R 1 ) i (R 2 ) 4-i
상기 화학식에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시기 또는 아세톡시기이고, i는 0 내지 3의 정수이다.In the above formula, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, i is an integer from 0 to 3.
보다 구체적으로는, 상기 반응성 실란은 1종 이상의 하기 화학식 1-1로 표시되는 반응성 실란; 및 1종 이상의 하기 화학식 1-2로 표시되는 4관능 반응성 실란을 포함할 수 있다:More specifically, the reactive silane is at least one reactive silane represented by the following Chemical Formula 1-1; And one or more tetrafunctional reactive silanes represented by Formula 1-2 below:
[화학식 1-1][Formula 1-1]
(R 1) nSi(R 2) 4-n (R 1 ) n Si(R 2 ) 4-n
[화학식 1-2][Formula 1-2]
Si(R 3) 4 Si(R 3 ) 4
상기 화학식 1-1 및 화학식 1-2에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기이고, 상기 R 3은 서로 독립적으로 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기중 어느 하나이고, n은 1 내지 3의 자연수이다. In Formula 1-1 and Formula 1-2, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, It is a phenoxy or acetoxy group, and R 3 is independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3 carbon atoms.
상기 화학식 1-1로 표시되는 반응성 실란은, 예를 들어, 페닐트리메톡시실란, 페닐트리에톡시실란, 페닐트리부톡시실란, 페닐메틸디메톡시실란, 페닐트리아세톡시실란, 페닐트리페녹시실란, 디페닐디메톡시실란, 디페닐디에톡시실란, 디페닐디페녹시실란, 트리페닐메톡시실란, 트리페닐에톡시실란, 메틸트리메톡시실란, 에틸트리메톡시실란, 부틸트리메톡시실란, 헥실트리메톡시실란, 메틸트리에톡시실란, 디메틸디메톡시실란 등을 포함하며, 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The reactive silane represented by Chemical Formula 1-1 is, for example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenylmethyldimethoxysilane, phenyltriacetoxysilane, or phenyltriphenoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane , Hexyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and the like, or may be used alone or in combination of two or more.
상기 화학식 1-2로 표시되는 4관능 반응성 실란은 테트라메톡시실란, 테트라에톡시실란, 테트라부톡시실란, 테트라페녹시실란, 테트라아세톡시실란 등을 포함하며, 단독 또는 2종 이상을 혼합하여 사용할 수 있다. The tetrafunctional reactive silane represented by Chemical Formula 1-2 includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and the like, or by mixing two or more. Can be used.
상기 실록산계 공중합체는 상기 화학식 1-1로 표시되는 반응성 실란 및 상기 화학식 1-2로 표시되는 4관능 반응성 실란을 2:8 내지 8:2의 중량비로 제공하여 이를 가수 분해 및 축합 중합한 것일 수 있다. The siloxane-based copolymer is a hydrolysis and condensation polymerization by providing a reactive silane represented by the formula 1-1 and a tetrafunctional reactive silane represented by the formula 1-2 in a weight ratio of 2:8 to 8:2. Can.
즉, 상기 화학식 1-1로 표시되는 반응성 실란은 실록산계 중합체를 이루는 총단량체에 대하여 20 내지 80 중량부로 포함될 수 있다. 상기 화학식 1-1로 표시되는 반응성 실란의 함량이 20 중량부 미만일 경우에는 필름형성 시 크랙이 생길 수 있으며, 80 중량부를 초과일 경우에는 중합 시 반응성이 떨어져 분자량을 제어하기 어려울 수 있다. That is, the reactive silane represented by Chemical Formula 1-1 may be included in an amount of 20 to 80 parts by weight with respect to the total monomer constituting the siloxane polymer. When the content of the reactive silane represented by Chemical Formula 1-1 is less than 20 parts by weight, cracks may occur during film formation, and when it exceeds 80 parts by weight, reactivity during polymerization may be reduced and molecular weight may be difficult to control.
또한 상기 화학식 1-2로 표시되는 4관능 반응성 실란은 실록산계 중합체를 이루는 총단량체에 대하여 80 내지 20 중량부로 포함될 수 있다. 상기 화학식 1-2로 표시되는 4관능 반응성 실란의 함량이 20 중량부 미만일 경우에는 감광성 실록산 수지 조성물의 패턴 형성 시 알칼리 수용액에 대한 용해성이 떨어져 불량을 발생시킬 수 있으며, 80 중량부를 초과일 경우에는 중합 시 반응성이 빨라 분자량 제어가 어렵고, 생성된 실록산 올리고머는 알칼리 수용액에 대한 용해성이 지나치게 커질 수 있다. In addition, the tetrafunctional reactive silane represented by Chemical Formula 1-2 may be included in an amount of 80 to 20 parts by weight based on the total monomer constituting the siloxane polymer. When the content of the tetrafunctional reactive silane represented by Chemical Formula 1-2 is less than 20 parts by weight, solubility in an aqueous alkali solution may be deteriorated when forming a pattern of the photosensitive siloxane resin composition, and when it exceeds 80 parts by weight It is difficult to control the molecular weight due to the high reactivity during polymerization, and the resulting siloxane oligomer may have too high solubility in an aqueous alkali solution.
상기 실록산계 중합체는 i) 상기 화학식 1-1로 표시되는 반응성 실란 및 ii) 상기 화학식 1-2로 표시되는 4관능 반응성 실란과 더불어 iii) 하기 화학식 5로 표시되는 반응성 실란을 추가로 포함하여 촉매 하에 가수분해 및 축합중합하고 미반응 단량체 및 촉매를 제거하여 얻을 수 있다: The siloxane-based polymer may further comprise i) a reactive silane represented by Formula 1-1 and ii) a tetrafunctional reactive silane represented by Formula 1-2, and iii) a reactive silane represented by Formula 5 below. It can be obtained by hydrolysis and condensation polymerization under and removal of unreacted monomers and catalysts:
[화학식 5][Formula 5]
(R 4) nSi(R 5) 4-n (R 4 ) n Si(R 5 ) 4-n
상기 화학식 5에서, R 4는 각각 독립적으로 비닐, 3-아크릴옥시알킬, 3-메타크릴옥시알킬, 1-(p-하이드록시 페닐)알킬, 2-(p-하이드록시 페닐)알킬, 3-글리시독시 알킬, 2-(3,4-에폭시 사이클로헥실)알킬, 3-이소시아네이트알킬 또는 옥세탄알킬이고, R 5는 탄소수 1~4의 알콕시기, 페녹시 또는 아세톡시이며, n은 1~3의 정수이다.In Formula 5, R 4 are each independently vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxy phenyl)alkyl, 2-(p-hydroxy phenyl)alkyl, 3- Glycidoxy alkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl or oxetanealkyl, R 5 is an alkoxy group having 1 to 4 carbon atoms, phenoxy or acetoxy, n is 1 to It is an integer of 3.
상기 화학식 5로 표시되는 반응성 실란은, 예를 들어, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 1-(p-하이드록시 페닐)에틸트리메톡시실란, 2-(p-하이드록시 페닐)에틸트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시 사이클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시 사이클로헥실)에틸메틸디메톡시실란, 3-이소시아네이트프로필트리에톡시실란, 3-이소시아네이트프로필트리메톡시실란, 옥세탄에틸트리메톡시실란 등을 포함하며, 단독 또는 2종 이상을 혼합하여 사용할 수 있다. The reactive silane represented by the formula (5) is, for example, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyl triethoxysilane, 1-(p- Hydroxy phenyl) ethyl trimethoxysilane, 2-(p-hydroxy phenyl) ethyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycine Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane , 3-isocyanate propyl trimethoxysilane, oxetane ethyl trimethoxysilane, and the like, or may be used alone or in combination of two or more.
상기 화학식 5로 표시되는 반응성 실란 또는 이들의 혼합물을 사용할 경우, 상기 화학식 5로 표시되는 반응성 실란의 함량은 실록산계 중합체를 이루는 총단량체에 대하여 5~50 중량부로 포함될 수 있다. 화학식 5로 표시되는 반응성 실란의 함량이 상기 범위 내인 경우 접착성 및 막경화도가 더욱 우수해 질 수 있다. When using the reactive silane represented by the formula (5) or a mixture thereof, the content of the reactive silane represented by the formula (5) may be included in 5 to 50 parts by weight with respect to the total monomer constituting the siloxane-based polymer. When the content of the reactive silane represented by Chemical Formula 5 is within the above range, adhesiveness and film hardening degree may be further improved.
상기 실록산계 중합체는 상기와 같은 반응성 실란 등을 물과 산 또는 염기 촉매 하에 벌크중합 또는 용액중합을 통해 얻어질 수 있다. 구체적으로, 상기 실록산계 중합체는 단량체로 작용하는 상기 반응성 실란들이 가수분해 및 축합중합하고, 미반응 단량체 및 촉매를 제거하는 과정 등을 거쳐 얻어질 수 있다. The siloxane-based polymer may be obtained by bulk polymerization or solution polymerization of the above-described reactive silane and the like under water and an acid or base catalyst. Specifically, the siloxane-based polymer may be obtained through hydrolysis and condensation polymerization of the reactive silanes acting as a monomer, and removal of unreacted monomers and catalysts.
상기 중합 시 사용될 수 있는 산촉매는, 예를 들어, 염산, 질산, 황산, 옥살산, 포름산, 아세트산, 옥살산, 프로피온산, 부탄산, 펜탄산 등을 포함하며, 염기촉매는, 예를 들어, 암모니아, 유기아민 및 알킬암모늄 하이드로옥사이드염 등을 포함할 수 있고, 이들을 단독 또는 2종 이상을 혼합하여 동시에 또는 단계적으로 사용할 수 있다. The acid catalyst that can be used in the polymerization includes, for example, hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, oxalic acid, propionic acid, butanoic acid, pentanoic acid, etc., and the basic catalyst is, for example, ammonia, organic And amine and alkylammonium hydrochloride salts, and these may be used alone or in combination of two or more, simultaneously or in stages.
최종적으로 얻어진 상기 실록산계 중합체는 GPC를 통한 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 20,000일 수 있다. 상기 실록산계 중합체의 폴리스티렌 환산중량평균분자량이 1,000 미만인 경우 포지티브형 감광성 수지 조성물 평가 시 현상 공정중 잔막율이 저하되거나 내열성이 떨어지고 수분흡습율이 취약한 문제가 있으며, 20,000 초과인 경우에는 포지티브형 감광성 수지 조성물의 감도가 저하되거나 패턴의 현상성이 떨어지는 문제점이 있다. The siloxane-based polymer finally obtained may have a weight average molecular weight (Mw) in terms of polystyrene through GPC of 1,000 to 20,000. When the weight average molecular weight in terms of polystyrene of the siloxane-based polymer is less than 1,000, when evaluating a positive type photosensitive resin composition, there is a problem that the residual film rate decreases during the development process or the heat resistance falls and the moisture absorption rate is vulnerable, and when it exceeds 20,000, the positive type photosensitive resin There is a problem that the sensitivity of the composition is lowered or the developability of the pattern is poor.
상기 실록산계 중합체는 Si NMR 분석 결과 중 (Q3+T3)의 비율이 전체 실리콘 중 40% 이상일 수 있다. 이는 상기 실록산 공중합체가 사다리 구조를 포함하고, 사다리 구조를 가지는 실록산계 중합체의 비율이 Si(Silicon) NMR 분석 결과를 기준으로 40% 이상임을 의미한다. 상기 실록산 공중합체의 사다리 구조의 비율이 40% 미만일 경우 스트리퍼, 에칭액에 대한 내화학성이 취약해질 수 있다. The ratio of (Q3+T3) in Si NMR analysis results of the siloxane-based polymer may be 40% or more of the total silicon. This means that the siloxane copolymer includes a ladder structure, and the proportion of the siloxane-based polymer having a ladder structure is 40% or more based on Si(Silicon) NMR analysis results. When the proportion of the ladder structure of the siloxane copolymer is less than 40%, chemical resistance to strippers and etching solutions may be weak.
본 발명에서 사용되는 올레핀계 중합체는 하기 화학식 2로 표시되는 반복단위를 포함하거나 하기 화학식 2 및 3으로 표시되는 반복단위를 포함할 수 있다. 예를 들어, 상기 올레핀계 중합체는 화학식 2으로 표시되는 반복단위만을 포함하는 단독중합체 또는 화학식 2로 표시되는 반복단위 및 화학식 3으로 표시되는 반복단위를 모두 포함하는 공중합체일 수 있다: The olefin-based polymer used in the present invention may include repeating units represented by the following Chemical Formula 2 or repeating units represented by the following Chemical Formulas 2 and 3. For example, the olefin-based polymer may be a homopolymer containing only the repeating unit represented by Formula 2 or a copolymer containing both the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3:
[화학식 2] [Formula 2]
Figure PCTKR2019018795-appb-img-000004
Figure PCTKR2019018795-appb-img-000004
[화학식 3][Formula 3]
Figure PCTKR2019018795-appb-img-000005
Figure PCTKR2019018795-appb-img-000005
상기 올레핀계 중합체에서, 상기 화학식 2로 표시되는 반복단위 및 화학식 3으로 표시되는 반복단위는 99:1 내지 60:40, 예를 들어, 99:1 내지 70:30, 예를 들어, 95:5 내지 70:30의 비로 제공될 수 있다. 상기 비율은 두 반복단위의 몰비를 나타내며, 예를 들어, 2D-NMR(H-NMR, C-NMR 등)의 분석 결과로부터 수득된 결과를 토대로 확인될 수 있다. In the olefin-based polymer, the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 are 99:1 to 60:40, for example, 99:1 to 70:30, for example, 95:5 To 70:30. The ratio represents the molar ratio of two repeating units, and can be confirmed, for example, based on results obtained from analysis results of 2D-NMR (H-NMR, C-NMR, etc.).
상기 올레핀계 중합체는 내크랙성 및 내화학성이 우수하여, 이를 사용한 경우 디스플레이에서 우수한 패널 신뢰성을 확보할 수 있도록 하는 바인더로서 역할한다. The olefin-based polymer is excellent in crack resistance and chemical resistance, and when used, serves as a binder to ensure excellent panel reliability in a display.
상기 올레핀계 중합체의 GPC를 통한 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 30,000일 수 있다. 상기 올레핀계 중합체의 폴리스티렌 환산중량평균분자량이 1,000 미만인 경우 포지티브형 감광성 수지 조성물 평가 시 현상 공정 중 잔막율이 저하되거나 내열성이 떨어지는 문제가 있으며, 30,000 초과인 경우에는 포지티브형 감광성 수지 조성물의 감도가 저하되거나 패턴의 현상성이 떨어지는 문제점이 발생할 수 있다. The weight average molecular weight (Mw) in terms of polystyrene through GPC of the olefin-based polymer may be 1,000 to 30,000. When the weight average molecular weight in terms of polystyrene of the olefin-based polymer is less than 1,000, there is a problem that a residual film rate decreases or heat resistance decreases during the development process when evaluating a positive photosensitive resin composition, and when it exceeds 30,000, the sensitivity of the positive photosensitive resin composition decreases Or a problem in which the developability of the pattern is poor may occur.
상기 포지티브형 감광성 수지 조성물 중, 상기 실록산계 중합체 및 올레핀계 중합체는 95:5 내지 10:90, 예를 들어 80:20 내지 40:60의 중량비로 제공될 수 있다. 상기 올레핀계 중합체의 함량비가 5 미만인 경우 포지티브 감광성 수지 조성물 평가 시 내화학성이 저하되거나 유연성이 떨어지는 문제가 있으며, 90 초과인 경우 현상속도가 느려지고 감도가 떨어지는 문제점이 발생할 수 있다. In the positive photosensitive resin composition, the siloxane-based polymer and the olefin-based polymer may be provided in a weight ratio of 95:5 to 10:90, for example, 80:20 to 40:60. When the content ratio of the olefin-based polymer is less than 5, there is a problem that chemical resistance is deteriorated or flexibility is poor when evaluating a positive photosensitive resin composition, and when it exceeds 90, a developing speed is slow and a sensitivity is deteriorated.
본 발명에서 사용되는 상기 1,2-퀴논디아지드 화합물은 감광성 화합물로서, 하기 화학식 4로 표시되는 페놀 화합물과 나프토퀴논디아지드술폰산 할로겐 화합물을 반응시켜 얻어진 것일 수 있다:The 1,2-quinonediazide compound used in the present invention is a photosensitive compound, and may be obtained by reacting a phenol compound represented by Formula 4 with a naphthoquinonediazide sulfonic acid halogen compound:
[화학식 4] [Formula 4]
Figure PCTKR2019018795-appb-img-000006
Figure PCTKR2019018795-appb-img-000006
상기 화학식 4에서, R 1 내지 R 6은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 4의 알킬기, 탄소수 1 내지 4의 알케닐기 또는 히드록시기이고, R 7 및 R 8은 각각 독립적으로 수소, 할로겐 또는 탄소수 1 내지 4의 알킬기이고, R 9는 수소 또는 탄소수 1 내지 4의 알킬기이다.In Formula 4, R 1 to R 6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxy group, and R 7 and R 8 are each independently hydrogen, halogen or carbon number It is an alkyl group of 1 to 4, and R 9 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
상기 1,2-퀴논디아지드 화합물은 페놀 화합물, 나프토퀴논디아지드술폰산할로겐 등을 약염기 하에서 반응시켜 제조될 수 있다. 상기 페놀 화합물과 나프토퀴논디아지드 폰산할로겐 화합물로 1,2-퀴논디아지드 화합물을 합성하는 경우, 이의 에스테르화도는 50 내지 85%일 수 있다. 상기 에스테르화도가 50% 미만인 경우에는 잔막율이 나빠질 수 있으며, 85% 초과인 경우에는 보관 안정성이 저하될 수 있다. The 1,2-quinonediazide compound may be prepared by reacting a phenol compound, naphthoquinonediazide sulfonate halogen, and the like under a weak base. When the 1,2-quinone diazide compound is synthesized from the phenol compound and the naphthoquinone diazide phonate halogen compound, the degree of esterification thereof may be 50 to 85%. When the esterification degree is less than 50%, the residual film rate may be deteriorated, and when it is more than 85%, storage stability may be deteriorated.
상기 1,2-퀴논디아지드 화합물은 1,2-퀴논디아지드 4-술폰산 에스테르, 1,2-퀴논디아지드 5-술폰산 에스테르, 1,2-퀴논디아지드 6-술폰산 에스테르 등을 포함하나, 이에 한정되는 것은 아니다. The 1,2-quinonediazide compound includes 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, and the like, It is not limited to this.
상기 1,2-퀴논디아지드 화합물은 아민 및/또는 할로겐 계열 불순물의 함량이 각각 500ppm 이하일 수 있다. 상기 불순물의 함량이 500ppm을 초과하는 경우에는 보관 안정성 및 베이크 산포가 저하될 수 있다. The 1,2-quinonediazide compound may have an amine and/or halogen-based impurity content of 500 ppm or less, respectively. When the content of the impurities exceeds 500ppm, storage stability and baking dispersion may be deteriorated.
상기 1,2-퀴논디아지드 화합물은, 상기 실록산계 중합체와 상기 올레핀계 중합체의 총중량 100 중량부에 대하여, 5 내지 50 중량부로 포함될 수 있다. 상기 1,2-퀴논디아지드 화합물의 함량이 5 중량부 미만인 경우에는 노광부와 비노광부의 용해도 차가 작아져 패턴 형성이 어려우며, 50 중량부 초과인 경우에는 단시간 동안 빛을 조사할 때 미반응 1,2-퀴논디아지드 화합물이 다량 잔존하여 현상액인 알칼리 수용액에 대한 용해도가 지나치게 낮아져 현상이 어려울 수 있다. The 1,2-quinonediazide compound may be included in 5 to 50 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer. When the content of the 1,2-quinone diazide compound is less than 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part becomes small, making pattern formation difficult, and when it exceeds 50 parts by weight, unreacted when irradiated with light for a short time 1 Due to the large amount of ,2-quinone diazide compound remaining, the solubility in an aqueous alkali solution as a developer may be too low, and development may be difficult.
본 발명에서 사용되는 상기 용매는 포지티브형 감광성 수지 조성물의 평탄성과 코팅 얼룩을 발생하지 않게 하여, 균일한 패턴 프로파일(pattern profile)을 형성할 수 있도록 한다.The solvent used in the present invention does not generate flatness and coating unevenness of the positive photosensitive resin composition, so that a uniform pattern profile can be formed.
상기 용매는 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르 프로피오네이트, 프로필렌글리콜에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 디프로필렌글리콜디메틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에테르, 트리에티렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디프로필렌글리콜에틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르 중 적어도 하나 이상을 포함할 수 있다. The solvent is propylene glycol methyl ether acetate, propylene glycol 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, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, di Ethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary 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 at least one of dipropylene glycol methyl hexyl ether.
상기 용매는 포지티브형 감광성 수지 조성물의 고형분의 함량이 10 내지 50 중량%가 되도록 포함될 수 있다. 상기 고형분의 함량이 10 중량% 미만인 경우에는 코팅 두께가 지나치게 얇게 되고 코팅 균일도가 저하될 수 있으며, 50 중량% 초과인 경우에는 코팅 두께가 지나치게 두꺼워지고 코팅 시 코팅 장비에 무리를 줄 수 있다. 상기 전체 조성물의 고형분의 함량이 10 내지 25 중량%인 경우, 슬릿 코팅기(Slit Coater)에서 사용되는 것이 용이하며, 25 내지 50 중량%인 경우 스핀 코팅기(Spin Coater)나 슬릿앤스핀 코팅기(Slit & Spin Coater)에서 사용되는 것이 용이하다.The solvent may be included so that the content of the solid content of the positive photosensitive resin composition is 10 to 50% by weight. If the content of the solid content is less than 10% by weight, the coating thickness may be too thin and the coating uniformity may be deteriorated. If it is more than 50% by weight, the coating thickness may be too thick and may impair coating equipment during coating. When the solid content of the total composition is 10 to 25% by weight, it is easy to be used in a slit coater, and when it is 25 to 50% by weight, a spin coater or a slit and spin coater Spin Coater).
본 발명의 일 실시예에 따르면, 상기 포지티브형 감광성 수지조성물은 벤조트리아진계 및 벤조트리아졸계 중 적어도 하나 이상의 UV 흡광제를 추가로 포함할 수 있다. According to one embodiment of the present invention, the positive photosensitive resin composition may further include at least one UV absorber of benzotriazine-based and benzotriazole-based.
상기 UV 흡광제는 노광 시 발생하는 자외선 등의 파장으로 인하여 기대하지 못했던 미패턴부에의 난반사에 의한 중합 반응을 방지할 수 있다. The UV absorber can prevent a polymerization reaction due to diffuse reflection on the unpatterned portion, which was unexpected due to wavelengths of ultraviolet rays or the like generated during exposure.
상기 UV 흡광제는, 상기 실록산계 중합체 및 올레핀계 중합체의 총중량 100 중량부를 기준으로, 1 내지 20 중량부로 제공될 수 있다. 상기 UV 흡광제의 함량이 1 중량부 미만인 경우에는 UV 흡광 효율이 떨어지며, 20 중량부 초과인 경우에는 전체 조성물의 경화도가 저하되고 낮은 감도로 인해 정상적인 형상의 구현이 곤란해질 수 있다. 본 발명의 포지티브형 감광성 수지 조성물은 0.1 내지 0.2 ㎛의 밀리포아필터 등을 이용하여 여과한 후 사용하는 것이 좋다.The UV absorber may be provided in 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer. When the content of the UV absorber is less than 1 part by weight, the UV absorbing efficiency decreases, and when it exceeds 20 parts by weight, the curability of the entire composition is lowered and it may be difficult to implement a normal shape due to low sensitivity. The positive photosensitive resin composition of the present invention is preferably used after filtering using a millipore filter of 0.1 to 0.2 μm.
본 발명의 다른 일 양태는 상기 포지티브형 감광성 수지 조성물을 사용하는 디스플레이 소자의 패턴 형성 방법을 제공한다. Another aspect of the present invention provides a method for forming a pattern of a display device using the positive photosensitive resin composition.
상기 패턴 형성 방법은 디스플레이 제조 공정에서 절연막 및 뱅크, 화소정의막 패턴을 형성하는 방법에 있어서 공지된 방법에 의하여 수행될 수 있다. The pattern forming method may be performed by a known method in a method of forming an insulating layer, a bank, or a pixel defining layer pattern in a display manufacturing process.
구체적인 일 예로서, 상기 포지티브형 감광성 수지 조성물을 이용하여 디스플레이 소자의 패턴을 형성하는 방법은 다음과 같다. As a specific example, a method of forming a pattern of a display device using the positive photosensitive resin composition is as follows.
먼저, 본 발명의 일 실시예에 따른 포지티브형 감광성 수지 조성물을 스핀 코팅, 슬릿앤스핀 코팅, 슬릿 코팅, 롤 코팅 등으로 기판 표면에 도포하고, 진공 건조 후 프리베이크에 의해 용매를 제거하여 도포막을 형성한다. 이때, 상기 프리베이크는 100 내지 120 ℃의 온도에서 1 내지 3 분간 수행될 수 있다. 그 후, 미리 준비된 패턴에 따라 가시광선, 자외선, 원자외선, 전자선, 엑스선 등을 상기 형성된 도포막에 조사하고, 현상액으로 현상하여 불필요한 부분을 제거함으로써 소정의 패턴을 형성한다. First, the positive photosensitive resin composition according to an embodiment of the present invention is coated on a substrate surface with spin coating, slit & spin coating, slit coating, roll coating, etc., and then vacuum dried to remove the solvent by prebaking to form a coating film. Form. At this time, the pre-baking may be performed at a temperature of 100 to 120 ℃ for 1 to 3 minutes. After that, a predetermined pattern is formed by irradiating visible coating, ultraviolet rays, far ultraviolet rays, electron beams, X-rays or the like to the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.
상기 현상액은 알칼리 수용액을 사용할 수 있으며, 예를 들어, 수산화나트륨, 수산화칼륨, 탄산나트륨 등의 무기 알칼리류 에틸아민, n-프로필아민 등의 1급 아민류 디에틸아민, n-프로필아민 등의 2급 아민류 트리메틸아민, 메틸디에틸아민, 디메틸에틸아민, 트리에틸아민 등의 3급 아민류 디메틸에탄올아민, 메틸디에탄올아민, 트리에탄올아민 등의 알콜아민류 또는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드 등의 4급 암모늄염의 수용액 등을 사용할 수 있다. 이때, 상기 현상액은 알칼리성 화합물을 0.1 내지 5 중량부의 농도로 용해시켜 사용되며, 메탄올, 에탄올 등과 같은 수용성 유기용매 및 계면활성제를 적정량 첨가할 수 있다. As the developer, an aqueous alkali solution can be used, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate. Primary amines such as ethylamine, n-propylamine, diethylamine, and n-propylamine. Amines Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine Dimethylethanolamine, alcoholamines such as methyldiethanolamine, triethanolamine or tetramethylammonium hydroxide, tetraethylammonium hydroxide And quaternary ammonium salt aqueous solutions. At this time, the developer is used by dissolving the alkaline compound in a concentration of 0.1 to 5 parts by weight, and an appropriate amount of a water-soluble organic solvent and surfactant such as methanol and ethanol can be added.
상기와 같은 현상액으로 현상한 후 초순수로 30 내지 90 초간 세정하여 불필요한 부분을 제거하고 건조하여 패턴을 형성하고, 상기 형성된 패턴에 자외선 등의 빛을 조사한 후, 패턴을 오븐 등의 가열장치에 의해 150 내지 400 ℃의 온도에서 30 내지 90 분간 가열처리하여 최종 패턴을 수득할 수 있다.After developing with the developer as described above, washing is performed for 30 to 90 seconds with ultrapure water to remove unnecessary parts and drying to form a pattern, and after irradiating the formed pattern with ultraviolet light, the pattern is heated by an oven or other heating device. The final pattern may be obtained by heat treatment at a temperature of 400° C. for 30 to 90 minutes.
본 발명의 또 다른 일 양태는 상기 포지티브형 감광성 수지 조성물의 경화체를 포함하는 디스플레이 소자를 제공한다. Another aspect of the present invention provides a display device including a cured body of the positive photosensitive resin composition.
본 발명의 일 실시예에 따르면, 상기 포지티브형 감광성 수지 조성물의 경화체는 디스플레이 소자에서의 절연막 및 평탄화막 중 적어도 하나 이상, 보다 구체적으로는 디스플레이 소자에서의 층간절연막, 보호절연막(Passivation), 게이트절연막, 평탄화막, 뱅크, 화소정의막 등에 유용하게 적용될 수 있다.According to an embodiment of the present invention, the cured body of the positive photosensitive resin composition is at least one or more of an insulating film and a planarizing film in a display device, more specifically, an interlayer insulating film, a protective insulating film (Passivation), a gate insulating film in a display device , It can be usefully applied to planarization films, banks, pixel definition films, and the like.
상기 포지티브형 감광성 수지 조성물은 감도, 내열변색성, 가스 배출, 수분흡습율 등의 성능이 우수할 뿐만 아니라, 특히 뛰어난 내열성을 가지고 있어, 상기 수지 조성물의 경화체의 내크랙성 및 내화학성이 향상되어 우수한 패널 신뢰성을 확보할 수 있다. The positive photosensitive resin composition not only has excellent performances such as sensitivity, heat discoloration resistance, gas discharge, and moisture absorption, but also has particularly excellent heat resistance, thereby improving crack resistance and chemical resistance of the cured body of the resin composition. Excellent panel reliability can be ensured.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아님은 자명하다.Hereinafter, a preferred embodiment is provided to help understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious that the scope of the present invention is not limited to the following embodiments.
실시예Example
제조예 1. 실록산계 공중합체의 제조Production Example 1. Preparation of siloxane copolymer
냉각관과 교반기를 구비한 플라스크에, 반응성 실란으로 각각 페닐트리에톡시실란 55 중량부, 테트라에톡시실란 20 중량부, 메틸트리에톡시실란 25 중량부를 넣고, 용매로 메탄올 100 중량부를 넣고, 질소치환한 후 완만히 교반하였다. 상기 반응용액에 추가로 초순수 50 중량부와 촉매로 옥살산을 4 중량부 투입 후 다시 완만히 교반하였다. 1 시간 후 상기 반응용액을 60 ℃까지 승온시켜 10 시간 동안 이 온도를 유지하여 중합 후, 상온으로 냉각시켜 반응을 종결하였다. 추가로 0 ℃이하로 급냉하여 반응물의 침전이 일어나도록 하여, 미반응 단량체 및 촉매가 함유된 상승액을 제거하였다. In a flask equipped with a cooling 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 silane, 100 parts by weight of methanol as a solvent, and nitrogen After substitution, the mixture was stirred gently. In addition to 50 parts by weight of ultrapure water and 4 parts by weight of oxalic acid as a catalyst, the mixture was stirred gently again. After 1 hour, the reaction solution was heated to 60°C to maintain this temperature for 10 hours, and after polymerization, the reaction was terminated by cooling to room temperature. It was further quenched to 0°C or lower to precipitate the reactants, thereby removing the rising solution containing unreacted monomers and catalysts.
미반응 단량체 및 촉매가 완벽하게 제거될 때까지 추가로 메탄올을 넣고 정제공정을 반복하였다. 정제공정 후, 진공 건조를 통하여 반응 중에 생성된 잔류 알코올계 용매 및 잔류수분을 제거하여, 실록산계 공중합체를 수득하였다. Purification was repeated by adding additional methanol until the unreacted monomer and catalyst were completely removed. After the purification process, the residual alcohol-based solvent and residual moisture generated during the reaction were removed through vacuum drying to obtain a siloxane-based copolymer.
GPC 분석은 Waters 2695, PDA 996 장치로 KF-803, KF-802, KF-801 컬럼을 이용하여, 테트라히드로푸란을 이동상으로 유량 1ml/min 조건에서 측정하여 폴리스타이렌 환산중량평균분자량(Mw)이 3,000인 실록산계 공중합체(A)를 제조하였다. 또한 실록산계 공중합체(A)가 Si NMR 분석을 통해 Q3+T3 비율이 전체 대비 50%임을 확인하였다. GPC analysis was carried out using a KF-803, KF-802, KF-801 column with a Waters 2695, PDA 996 device, and tetrahydrofuran was measured in a mobile phase at a flow rate of 1 ml/min. Phosphorus siloxane copolymer (A) was prepared. In addition, it was confirmed that the Q3+T3 ratio of the siloxane-based copolymer (A) was 50% compared to the total through Si NMR analysis.
제조예 2. 불소기를 포함한 실록산계 공중합체의 제조Production Example 2. Preparation of siloxane-based copolymer containing fluorine group
상기 합성예 1에서 메틸트리에톡시실란 대신 트리플로로프로필 트리메톡시실란을 사용한 것을 제외하고는 합성예 1과 동일한 방법으로 폴리스타이렌 환산중량평균분자량(Mw)이 3,000인 실록산계 공중합체(B)을 제조하였다.A siloxane-based copolymer (B) having a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 in the same manner as in Synthesis Example 1, except that in Example 1, trifluoropropyl trimethoxysilane was used instead of methyltriethoxysilane. Was prepared.
제조예 3. 1,2-퀴논디아지드 화합물의 제조Preparation Example 3 Preparation of 1,2-quinonediazide compound
하기 화학식으로 표시되는 페놀 화합물 1 몰 및 1,2-나프토퀴논디아지드-5-술폰산[클로라이드] 2 몰을 축합반응시켜, 에스테르화도가 67%인 1,2-나프토퀴논디아지드-5-술폰산 에스테르 화합물을 수득하였다.Condensation reaction of 1 mol of the phenol compound represented by the following formula and 2 mol of 1,2-naphthoquinone diazide-5-sulfonic acid [chloride], 1,2-naphthoquinone diazide-5 having an esterification degree of 67% -A sulfonic acid ester compound was obtained.
Figure PCTKR2019018795-appb-img-000007
Figure PCTKR2019018795-appb-img-000007
실시예 1. 포지티브형 감광성 수지 조성물 제조Example 1. Preparation of positive photosensitive resin composition
상기 제조예 1에서 수득한 실록산계 공중합체(A) 95 중량부, 폴리하이드록시스타이렌(PHS)와 스타이렌을 9:1의 몰비로 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체 5 중량부, 및 상기 제조예 3에서 수득한 1,2-나프토퀴논디아지드 화합물 25 중량부를 넣고, 고형분의 함량이 25 중량부가 되도록 프로필렌글리콜메틸에테르아세테이트로 혼합하여 용해시켰다. 이후, 0.1 ㎛의 밀리포아필터로 여과하여 포지티브형 감광성 수지 조성물을 수득하였다.95 parts by weight of the siloxane-based copolymer (A) obtained in Preparation Example 1, an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 in terms of a molar ratio of polyhydroxystyrene (PHS) and styrene of 9:1 5 25 parts by weight of the 1,2-naphthoquinone diazide compound obtained in Preparation Part 3, and the above Preparation Example 3 was added, and the mixture was dissolved with propylene glycol methyl ether acetate so that the content of solid content was 25 parts by weight. Then, it was filtered through a 0.1 μm millipore filter to obtain a positive photosensitive resin composition.
실시예 2. 포지티브형 감광성 수지 조성물 제조Example 2. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 90 중량부와 올레핀계 공중합체 10 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 1, 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.
실시예 3. 포지티브형 감광성 수지 조성물 제조Example 3. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 80 중량부와 올레핀계 공중합체 20 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 1, a positive-type 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.
실시예 4. 포지티브형 감광성 수지 조성물 제조Example 4. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 70 중량부와 올레핀계 공중합체 30 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 1, 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.
실시예 5. 포지티브형 감광성 수지 조성물 제조Example 5. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 50 중량부와 올레핀계 공중합체 50 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 1, a positive type 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.
실시예 6. 포지티브형 감광성 수지 조성물 제조Example 6. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 30 중량부와 올레핀계 공중합체 70 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 1, a positive-type 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.
실시예 7. 포지티브형 감광성 수지 조성물 제조Example 7. Preparation of positive photosensitive resin composition
상기 실시예 1에서 실록산계 공중합체 10 중량부와 올레핀계 공중합체 90 중량부를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 1, a positive-type 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.
실시예 8. 포지티브형 감광성 수지 조성물 제조Example 8. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 1,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 1,000 was used.
실시예 9. 포지티브형 감광성 수지 조성물 제조Example 9. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 5,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.A positive type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 5,000 in Example 5 was used.
실시예 10. 포지티브형 감광성 수지 조성물 제조Example 10. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 8,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 8,000 was used.
실시예 11. 포지티브형 감광성 수지 조성물 제조Example 11. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 15,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 15,000 was used.
실시예 12. 포지티브형 감광성 수지 조성물 제조Example 12. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 20,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 20,000 was used.
실시예 13. 포지티브형 감광성 수지 조성물 제조 Example 13. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 30,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. A positive type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 30,000 in Example 5 was used.
실시예 14. 포지티브형 감광성 수지 조성물 제조Example 14. Preparation of positive photosensitive resin composition
상기 실시예 5에서 폴리하이드록시스타이렌(PHS)과 스타이렌이 9.5:0.5의 몰비로 중합되고 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 5, except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 9.5:0.5 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
실시예 15. 포지티브형 감광성 수지 조성물 제조Example 15. Preparation of positive photosensitive resin composition
상기 실시예 5에서 폴리하이드록시스타이렌(PHS)과 스타이렌이 8:2의 몰비로 중합되고 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 5, except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 8:2 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
실시예 16. 포지티브형 감광성 수지 조성물 제조Example 16. Preparation of positive photosensitive resin composition
상기 실시예 5에서 폴리하이드록시스타이렌(PHS)과 스타이렌이 7:3의 몰비로 중합되고 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 5, except that polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 7:3 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, and Example 5 and In the same manner, a positive photosensitive resin composition was prepared.
실시예 17. 포지티브형 감광성 수지 조성물 제조Example 17. Preparation of positive photosensitive resin composition
상기 실시예 5에서 UV 흡광제로 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸에스터 10 중량부를 더 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. Except that 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester was further used as the UV absorber in Example 5, In the same manner as in Example 5, a positive photosensitive resin composition was prepared.
실시예 18. 포지티브형 감광성 수지 조성물 제조Example 18. Preparation of positive photosensitive resin composition
상기 실시예 6에서 UV 흡광제로 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터 10 중량부를 더 사용한 것을 제외하고는 상기 실시예 6과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.Except that in Example 6, 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester was further used as a UV absorber. A positive type photosensitive resin composition was prepared in the same manner as in Example 6.
실시예 19. 포지티브형 감광성 수지 조성물 제조Example 19. Preparation of positive photosensitive resin composition
상기 실시예 4에서 UV 흡광제로 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터 10 중량부를 사용한 것을 제외하고는 상기 실시예 4와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 4, except for using 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoate octyl ester as a UV absorber. A positive type photosensitive resin composition was prepared in the same manner as in Example 4.
실시예 20. 포지티브형 감광성 수지 조성물 제조Example 20. Preparation of positive photosensitive resin composition
상기 실시예 3에서 UV 흡광제로 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터 10 중량부를 사용한 것을 제외하고는 상기 실시예 3과 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다.In Example 3, except for using 10 parts by weight of 3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoate octyl ester as a UV absorber A positive photosensitive resin composition was prepared in the same manner as in Example 3.
실시예 21. 포지티브형 감광성 수지 조성물 제조Example 21. Preparation of positive photosensitive resin composition
상기 실시예 17에서 UV 흡광제 5 중량부를 사용한 것을 제외하고는 상기 실시예 17과 동일한 방법으로 제조하였다.It was prepared in the same manner as in Example 17, except that 5 parts by weight of UV absorber in Example 17.
실시예 22. 포지티브형 감광성 수지 조성물 제조Example 22. Preparation of positive photosensitive resin composition
상기 실시예 17에서 UV 흡광제 20 중량부를 사용한 것을 제외하고는 상기 실시예 17과 동일한 방법으로 제조하였다.It was prepared in the same manner as in Example 17, except that 20 parts by weight of UV absorber in Example 17.
실시예 23. 포지티브형 감광성 수지 조성물 제조Example 23. Preparation of positive photosensitive resin composition
상기 실시예 2에서 실록산계 공중합체 97 중량부와 올레핀계 공중합체 3 중량부를 사용한 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 2, 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.
실시예 24. 포지티브형 감광성 수지 조성물 제조Example 24. Preparation of positive photosensitive resin composition
상기 실시예 2에서 실록산계 공중합체 5 중량부와 올레핀계 공중합체 95 중량부를 사용한 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 2, a positive-type 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.
실시예 25. 포지티브형 감광성 수지 조성물 제조Example 25. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 500인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 500 was used.
실시예 26. 포지티브형 감광성 수지 조성물 제조 Example 26. Preparation of positive photosensitive resin composition
상기 실시예 5에서 환산중량평균분자량(Mw) 40,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, a positive-type photosensitive resin composition was prepared in the same manner as in Example 5, except that an olefin-based copolymer having a weight average molecular weight (Mw) of 40,000 was used.
실시예 27. 포지티브형 감광성 수지 조성물 제조Example 27. Preparation of positive photosensitive resin composition
상기 실시예 5에서 올레핀계 공중합체를 올레핀계 공중합체를 폴리하이드록시스타이렌(PHS)으로만 중합되고 하기 화학식으로 표시되는 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, the olefin-based copolymer was polymerized with only hydroxy-styrene (PHS), and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 represented by the following formula was used. In the same manner as in Example 5, a positive photosensitive resin composition was prepared.
실시예 28. 포지티브형 감광성 수지 조성물 제조Example 28. Preparation of positive photosensitive resin composition
상기 실시예 5에서 올레핀계 공중합체를 폴리하이드록시스타이렌(PHS)과 스타이렌이 6.5:4.5의 몰비로 중합되고 환산중량평균분자량(Mw) 10,000인 올레핀계 공중합체를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 5, except that the olefin-based copolymer of polyhydroxystyrene (PHS) and styrene were polymerized in a molar ratio of 6.5:4.5 and an olefin-based copolymer having a weight average molecular weight (Mw) of 10,000 was used, In the same manner as in Example 5, a positive photosensitive resin composition was prepared.
비교예 1. 포지티브형 감광성 수지 조성물 제조Comparative Example 1. Preparation of positive photosensitive resin composition
상기 실시예 5에서 실록산계 공중합체를 상기 제조예 2에서 제조한 실록산계 공중합체(B)를 사용한 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. 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 in Example 5.
비교예 2. 포지티브형 감광성 수지 조성물 제조 Comparative Example 2. Preparation of positive photosensitive resin composition
상기 실시예 2에서 실록산계 공중합체 100 중량부를 사용하고 올레핀계 공중합체는 사용하지 않는 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 2, a positive photosensitive resin composition was prepared in the same manner as in Example 2, except that 100 parts by weight of the siloxane-based copolymer was used and no olefin-based copolymer was used.
비교예 3. 포지티브형 감광성 수지 조성물 제조Comparative Example 3. Preparation of positive photosensitive resin composition
상기 실시예 2에서 실록산계 공중합체는 사용하지 않고 올레핀계 공중합체 100 중량부를 사용한 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 포지티브형 감광성 수지 조성물을 제조하였다. In Example 2, a positive type 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 without using the siloxane-based copolymer.
실험예 1. 포지티브형 감광성 수지 조성물의 물성 측정Experimental Example 1. Measurement of physical properties of positive photosensitive resin composition
상기 실시예 1 내지 28 및 비교예 1 내지 3에 대하여, 감도, 스컴(Scum), 해상도, 내열변색성, 내열성, 크랙, 내화학성, 접착력 등의 물성을 측정하여 그 결과를 하기 표 1에 나타내었다.For Examples 1 to 28 and Comparative Examples 1 to 3, properties such as sensitivity, scum, resolution, heat discoloration, heat resistance, cracking, chemical resistance, and adhesion were measured, and the results are shown in Table 1 below. Did.
1.1. 샘플의 준비1.1. Sample preparation
이를 위하여, 글래스(glass) 기판 상에 스핀 코팅기를 사용하여 상기 실시예 1 내지 22 및 비교예 1 내지 9에서 수득한 포지티브형 감광성 수지 조성물을 각각 도포한 후, 진공 건조 시키고, 100 ℃로 2 분간 핫플레이트 상에서 프리베이크하여 두께가 4.0 ㎛인 막을 형성하였다. To this end, the positive type photosensitive resin compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 9 were respectively coated on a glass substrate using a spin coater, followed by vacuum drying and 100° C. for 2 minutes. It was prebaked on a hot plate to form a film having a thickness of 4.0 μm.
1.2. 감도1.2. Sensitivity
상기 실험예 1.1.에서 형성된 막에 소정 패턴 마스크(pattern mask)를 사용하여 광대역(Broadband)에서의 강도가 20 ㎽/㎠인 자외선을 5 ㎛ 컨택홀(Contact Hole) CD 형성기준 투여량(Dose)을 조사한 후, 테트라메틸 암모늄히드록시드 2.38 중량%의 수용액으로 23 ℃에서 1분간 현상하고, 초순수로 1분간 세정하였다. Using a predetermined pattern mask on the film formed in Experimental Example 1.1., the ultraviolet rays having a strength of 20 ㎽/㎠ in broadband are 5 μm contact hole CD formation reference dose (Dose) After irradiating, it was developed for 1 minute at 23°C with an aqueous solution of 2.38% by weight of tetramethyl ammonium hydroxide, and washed with ultrapure water for 1 minute.
그후, 상기에서 현상된 패턴에 광대역에서의 강도가 20 ㎽/㎠인 자외선을 500 mJ/cm2로 조사하고, 오븐 속에서 230 ℃로 60 분간 경화시켜 두께가 3.5 ㎛이고, 컨택홀 CD가 5 ㎛인 패턴 막을 수득하였다. Thereafter, the pattern developed in the above was irradiated with ultraviolet light having a strength of 20 ㎽/cm 2 at a broadband of 500 mJ/cm 2, and cured in an oven at 230° C. for 60 minutes to have a thickness of 3.5 μm and a contact hole CD of 5 μm. A phosphorus pattern film was obtained.
1.3. 스컴1.3. Scum
상기 실험예 1.2.에서 감도 측정 시 형성된 패턴 내부를 SEM으로 관찰하여 Line & Space 및 컨택홀에 잔사가 존재하는지 확인하였다. 현상 잔사가 존재하는 경우에는 X, 현상잔사가 패턴 경계부에만 존재하는 경우에는 △현상잔사가 존재하지 않는 경우 O로 표기하였다. In Experimental Example 1.2., the inside of the pattern formed during the sensitivity measurement was observed by SEM to check whether residues exist in Line & Space and contact holes. It is denoted as X when the development residue is present, and △ when the development residue is present only at the pattern boundary, and when the development residue is not present.
1.4. 해상도1.4. resolution
상기 실험예 1.2.에서 감도 측정 시 형성된 컨택홀 패턴의 최소 크기로 측정하였다.In Experimental Example 1.2., it was measured to the minimum size of the contact hole pattern formed when measuring sensitivity.
1.5. 내열변색성1.5. Heat discoloration resistance
상기 실험예 1.2.에서 감도 측정 시 형성된 측정 기판을 300 ℃의 오븐에서 60분 동안 추가 경화하여 경화 전후 400 nm 투과율 변화에 의해 내열변색성을 평가하였다. 이때 변화율이 3% 미만인 경우를 ◎3 ~ 5%인 경우를 ○5 ~ 10%인 경우를 △10% 를 넘는 경우를 X로 표기하였다.The measurement substrate formed during the sensitivity measurement in Experimental Example 1.2. was further cured in an oven at 300° C. for 60 minutes to evaluate heat discoloration resistance by 400 nm transmittance change before and after curing. At this time, when the rate of change was less than 3%, ◎3 to 5%, ○5 to 10%, and △10% or more were indicated by X.
1.6. 내열성1.6. Heat resistance
내열성은 TGA를 이용하여 측정하였다. 상기 실험예 1.2.에서 감도 측정 시 형성된 패턴막을 샘플링 한 후, TGA를 이용하여 상온에서 900 ℃까지 분당 10 ℃씩 승온하였다. 열분해 온도(Td)가 450℃이상인 경우를 ○열분해 온도(Td)가 350~400 ℃인 경우를 △열분해 온도(Td)가 350℃미만인 경우를 X로 표기하였다. Heat resistance was measured using TGA. After sampling the pattern film formed during the sensitivity measurement in Experimental Example 1.2., the temperature was raised by 10° C. per minute from room temperature to 900° C. using TGA. The case where the thermal decomposition temperature (Td) is 450°C or higher ○ The case where the thermal decomposition temperature (Td) is 350 to 400°C △ The case where the thermal decomposition temperature (Td) is less than 350°C is denoted by X.
1.7. 크랙 1.7. crack
상기 실험예 1.2.에서 감도 평가기판을 육안 검사 및 현미경 100배 배율에서 관찰하여, 크랙이 관찰되는 경우 X, 크랙이 코팅 테두리 부에서만 관찰되는 경우 △크랙이 관찰되지 않는 경우 O로 표기하였다. In the experimental example 1.2., the sensitivity evaluation board was observed by visual inspection and a microscope at 100 times magnification, and X was observed when cracks were observed and △ when cracks were observed only at the coating edge, △ when no cracks were observed.
1.8. 내화학성1.8. Chemical resistance
상기 실험예 1.2.에서 감도 평가기판을 40 ℃NMP에 120 초 동안 침지하고, 침지 전후의 경화막 두께 변화율을 측정하여 0 내지 300 Å미만은 O, 300~600 Å은 △600 Å이상은 X로 표기하였다. In the experimental example 1.2., the sensitivity evaluation substrate was immersed in 40° C. NMP for 120 seconds, and the rate of change in the thickness of the cured film before and after immersion was measured. Notation.
1.9. 접착력1.9. Adhesion
상기 실험예 1.2.에서 감도 측정 시와 동일한 방법으로, 패턴막을 형성하되 10 ㎛ 선폭 및 슬릿폭이 1:1인 경우를 기준으로 베이크 온도에 따른 접착력을 비교하였다. 이때, 프리베이크 90 내지 100 ℃에서 접착력이 확보되는 경우를 O, 프리베이크 105 내지 115 ℃에서 접착력이 확보되는 경우를 △프리베이크 120 ℃이상에서 접착력이 확보되거나 그렇지 않은 경우를 X로 표기하였다.In the same manner as in the sensitivity measurement in Experimental Example 1.2., a pattern film was formed, but the adhesive strength according to the baking temperature was compared based on the case where the 10 µm line width and slit width were 1:1. At this time, the case where the adhesion is secured at 90 to 100° C. pre-baking, the case where the adhesion is secured at 105 to 115° C. pre-baking, or the case where the adhesion is secured at 120° C. or higher, or not, is designated as X.
구분division 분자량/화합물Molecular weight/compound 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6
실록산계 중합체Siloxane polymer 함량(중량부)Content (parts by weight) 9595 9090 8080 7070 5050 3030
분자량Molecular Weight 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000
올레핀계 중합체Olefin polymer 함량(중량부)Content (parts by weight) 55 1010 2020 3030 5050 7070
분자량Molecular Weight 10,00010,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000
PHSPHS 99 99 99 99 99 99
스타이렌Styrene 1One 1One 1One 1One 1One 1One
감광제Photosensitizer 1,2-퀴논디아지드 화합물1,2-quinonediazide compounds 2525 2525 2525 2525 2525 2525
UV 흡광제UV absorber 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester -- -- -- -- -- --
용액내 고형분 함량Solid content in solution 2525 2525 2525 2525 2525 2525
감도(mJ/cm 2)Sensitivity (mJ/cm 2 ) 8080 9090 8585 9090 9090 9090
스컴(㎛)Scum (㎛) ○○ ○○ ○○ ○○ ○○ ○○
해상도(㎛)Resolution (㎛) 33 22 22 22 22 22
내열 변색성Heat discoloration resistance ○○ ○○ ○○ ○○ ○○ ○○
내열성Heat resistance ○○ ○○ ○○ ○○ ○○ ○○
내크랙성Crack resistance ○○ ○○ ○○ ○○ ○○ ○○
내화학성Chemical resistance ○○ ○○ ○○ ○○ ○○ ○○
접착력Adhesion ○○ ○○ ○○ ○○ ○○ ○○
구분division 분자량/화합물Molecular weight/compound 실시예 7Example 7 실시예 8Example 8 실시예 9Example 9 실시예 10Example 10 실시예 11Example 11 실시예 12Example 12
실록산계 중합체Siloxane polymer 함량(중량부)Content (parts by weight) 9595 5050 5050 5050 5050 5050
분자량Molecular Weight 3,0003,000 3,0003,000 5,0005,000 8,0008,000 15,00015,000 20,00020,000
올레핀계 중합체Olefin polymer 함량(중량부)Content (parts by weight) 55 5050 5050 5050 5050 5050
분자량Molecular Weight 10,00010,000 1,0001,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000
PHSPHS 99 99 99 99 99 99
스타이렌Styrene 1One 1One 1One 1One 1One 1One
감광제Photosensitizer 1,2-퀴논디아지드 화합물1,2-quinonediazide compounds 2525 2525 2525 2525 2525 2525
UV 흡광제UV absorber 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester -- -- -- -- -- --
용액내 고형분 함량Solid content in solution 2525 2525 2525 2525 2525 2525
감도(mJ/cm 2)Sensitivity (mJ/cm 2 ) 9595 7575 8080 8585 9595 100100
스컴(㎛)Scum (㎛) ○○ ○○ ○○ ○○ ○○ ○○
해상도(㎛)Resolution (㎛) 22 22 22 22 22 22
내열 변색성Heat discoloration resistance ○○ ○○ ◎◎ ○○ ○○ ○○
내열성Heat resistance ○○ ○○ ○○ ○○ ○○ ○○
내크랙성Crack resistance ○○ ○○ ○○ ○○ ○○ ○○
내화학성Chemical resistance ○○ ○○ ○○ ○○ ○○ ○○
접착력Adhesion ○○ ○○ ○○ ○○ ○○ ○○
구분division 분자량/화합물Molecular weight/compound 실시예 13Example 13 실시예 14Example 14 실시예 15Example 15 실시예 16Example 16 실시예 17Example 17 실시예 18Example 18
실록산계 중합체Siloxane polymer 함량(중량부)Content (parts by weight) 5050 5050 5050 1010 5050 3030
분자량Molecular Weight 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000
올레핀계 중합체Olefin polymer 함량(중량부)Content (parts by weight) 5050 5050 5050 9090 5050 7070
분자량Molecular Weight 30,00030,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000
PHSPHS 99 9.59.5 88 77 99 99
스타이렌Styrene 1One 0.50.5 22 33 1One 1One
감광제Photosensitizer 1,2-퀴논디아지드 화합물1,2-quinonediazide compounds 2525 2525 2525 2525 2525 2525
UV 흡광제UV absorber 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester -- -- -- -- 1010 1010
용액내 고형분 함량Solid content in solution 2525 2525 2525 2525 2525 2525
감도(mJ/cm 2)Sensitivity (mJ/cm 2 ) 100100 8585 9090 9595 9595 9595
스컴(㎛)Scum (㎛) ○○ ○○ ○○ ○○ ○○ ○○
해상도(㎛)Resolution (㎛) 22 22 22 22 22 22
내열 변색성Heat discoloration resistance ○○ ○○ ○○ ○○ ◎◎ ◎◎
내열성Heat resistance ○○ ○○ ○○ ○○ ○○ ○○
내크랙성Crack resistance ○○ ○○ ○○ ○○ ○○ ○○
내화학성Chemical resistance ○○ ○○ ○○ ○○ ○○ ○○
접착력Adhesion ○○ ○○ ○○ ○○ ○○ ○○
구분division 분자량/화합물Molecular weight/compound 실시예 19Example 19 실시예 20Example 20 실시예 21Example 21 실시예 22Example 22 실시예 23Example 23 실시예 24Example 24
실록산계 중합체Siloxane polymer 함량(중량부)Content (parts by weight) 7070 8080 5050 5050 9797 55
분자량Molecular Weight 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000
올레핀계 중합체Olefin polymer 함량(중량부)Content (parts by weight) 3030 2020 5050 5050 33 9595
분자량Molecular Weight 10,00010,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000
PHSPHS 99 99 99 99 99 99
스타이렌Styrene 1One 1One 1One 1One 1One 1One
감광제Photosensitizer 1,2-퀴논디아지드 화합물1,2-quinonediazide compounds 2525 2525 2525 2525 2525 2525
UV 흡광제UV absorber 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester -- -- 55 2020 -- --
용액내 고형분 함량Solid content in solution 2525 2525 2525 2525 2525 2525
감도(mJ/cm 2)Sensitivity (mJ/cm 2 ) 9595 9090 9595 100100 7575 9595
스컴(㎛)Scum (㎛) ○○ ○○ ○○ ○○ ○○ ○○
해상도(㎛)Resolution (㎛) 22 22 22 22 33 22
내열 변색성Heat discoloration resistance ◎◎ ◎◎ ◎◎ ◎◎ ○○ ○○
내열성Heat resistance ○○ ○○ ○○ ○○ ○○ △△
내크랙성Crack resistance ○○ ○○ ○○ ○○ △△ ○○
내화학성Chemical resistance ○○ ○○ ○○ ○○ △△ ○○
접착력Adhesion ○○ ○○ ○○ ○○ ○○ ○○
분자량/화합물Molecular weight/compound 실시예 25Example 25 실시예 26Example 26 실시예 27Example 27 실시예 28Example 28 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
실록산계 중합체Siloxane polymer 함량(중량부)Content (parts by weight) 5050 5050 5050 5050 50 ( B) 50 ( B) -- 100100
분자량Molecular Weight 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000 3,0003,000
올레핀계 중합체Olefin polymer 함량(중량부)Content (parts by weight) 5050 5050 5050 5050 5050 100100 --
분자량Molecular Weight 500500 40,00040,000 10,00010,000 10,00010,000 10,00010,000 10,00010,000
PHSPHS 99 99 1010 6.56.5 99 99
스타이렌Styrene 1One 1One 00 4.54.5 1One 1One
감광제Photosensitizer 1,2-퀴논디아지드 화합물1,2-quinonediazide compounds 2525 2525 2525 2525 2525 2525 2525
UV 흡광제UV absorber 3-(2H-벤조트리아졸릴)-5-(1,1-디메틸에틸)-4-히드록시-벤젠프로파논산 옥틸 에스터3-(2H-benzotriazolyl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid octyl ester -- -- -- -- -- --
용액내 고형분 함량Solid content in solution 2525 2525 2525 2525 2525 2525 2525
감도(mJ/cm 2)Sensitivity (mJ/cm 2 ) 7070 105105 8585 100100 100100 110110 105105
스컴(㎛)Scum (㎛) ○○ △△ ○○ ○○ △△ ○○ △△
해상도(㎛)Resolution (㎛) 33 33 22 44 44 22 44
내열 변색성Heat discoloration resistance ○○ ○○ ○○ ○○ ○○ ○○ ○○
내열성Heat resistance △△ ○○ ○○ ○○ △△ XX XX
내크랙성Crack resistance △△ ○○ ○○ △△ △△ ○○ △△
내화학성Chemical resistance △△ ○○ ○○ △△ △△ ○○ △△
접착력Adhesion △△ ○○ △△ ○○ ○○ ○○ ○○
상기 표 1을 통하여, 본 발명에 따라 실시예 1 내지 28에서 제조한 포지티브형 감광성 수지 조성물은 해상도, 감도, 스컴, 변색성, 내열성, 내크랙성 등의 특성이 우수하였다. Through Table 1, the positive photosensitive resin compositions prepared in Examples 1 to 28 according to the present invention were excellent in properties such as resolution, sensitivity, scum, discoloration, heat resistance, and crack resistance.
반면, 비교예 1 및 2와 같이 어느 하나의 레진이 사용될 경우, 특성이 현저히 저하되는 것을 알 수 있으며, 실록산 레진에 F가 치환된 경우에도 특성이 저하됨을 알 수 있었다. On the other hand, when any one resin is used as in Comparative Examples 1 and 2, it can be seen that the properties are significantly lowered, and it can be seen that even when F is substituted for the siloxane resin, the properties are lowered.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다. The above description of the present invention is for illustration only, and a person having ordinary knowledge in the technical field to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본 발명의 범위는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is indicated by the following claims, and all modifications or variations derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

Claims (14)

1종 이상의 하기 화학식 1로 표시되는 반응성 실란을 중합하여 얻어진 실록산계 중합체; A siloxane-based polymer obtained by polymerizing at least one reactive silane represented by Formula 1 below;
하기 화학식 2로 표시되는 반복단위를 포함하거나 하기 화학식 2 및 3으로 표시되는 반복단위를 포함하는 올레핀계 중합체; An olefin-based polymer comprising a repeating unit represented by the following Chemical Formula 2 or a repeating unit represented by the following Chemical Formulas 2 and 3;
1,2-퀴논디아지드 화합물; 및 1,2-quinonediazide compounds; And
용매를 포함하는 포지티브형 감광성 수지 조성물: Positive photosensitive resin composition comprising a solvent:
[화학식 1] [Formula 1]
Si(R 1) i(R 2) 4-i Si(R 1 ) i (R 2 ) 4-i
상기 화학식 1에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시기 또는 아세톡시기이고, i는 0 내지 3의 정수이다.In Chemical Formula 1, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group. , i is an integer from 0 to 3.
[화학식 2] [Formula 2]
Figure PCTKR2019018795-appb-img-000008
Figure PCTKR2019018795-appb-img-000008
[화학식 3][Formula 3]
Figure PCTKR2019018795-appb-img-000009
Figure PCTKR2019018795-appb-img-000009
제1항에 있어서, According to claim 1,
상기 반응성 실란은 1종 이상의 하기 화학식 1-1로 표시되는 반응성 실란; 및 1종 이상의 하기 화학식 1-2로 표시되는 4관능 반응성 실란을 포함하는 포지티브형 감광성 수지 조성물. 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 Formulas 1-2.
[화학식 1-1][Formula 1-1]
(R 1) nSi(R 2) 4-n (R 1 ) n Si(R 2 ) 4-n
[화학식 1-2][Formula 1-2]
Si(R 3) 4 Si(R 3 ) 4
상기 화학식 1-1 및 화학식 1-2에서, R 1은 서로 독립적으로 탄소수 1 내지 10의 알킬기 또는 탄소수 6 내지 15의 아릴기이고, R 2는 서로 독립적으로 히드록시기, 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기이고, 상기 R 3은 서로 독립적으로 탄소수 1 내지 4의 알콕시기, 페녹시, 또는 아세톡시기중 어느 하나이고, n은 1 내지 3의 자연수이다.In Formula 1-1 and Formula 1-2, R 1 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R 2 is independently a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, It is a phenoxy or acetoxy group, and R 3 is independently an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3 carbon atoms.
제2항에 있어서,According to claim 2,
상기 실록산계 공중합체는 상기 화학식 1-1로 표시되는 반응성 실란 및 상기 화학식 1-2로 표시되는 4관능 반응성 실란이 2:8 내지 8:2의 중량비로 가수 분해 및 축합 중합한 포지티브형 감광성 수지 조성물. The siloxane-based copolymer is a positive photosensitive resin obtained by hydrolysis and condensation polymerization of a reactive silane represented by Chemical Formula 1-1 and a tetrafunctional reactive silane represented by Chemical Formula 1-2 in a weight ratio of 2:8 to 8:2. Composition.
제1항에 있어서, According to claim 1,
상기 올레핀계 중합체에서, 상기 화학식 2 및 3으로 표시되는 반복단위는 99:1 내지 60:40의 비로 제공되는 포지티브형 감광성 수지 조성물. In the olefin-based polymer, the repeating units represented by Chemical Formulas 2 and 3 are positive photosensitive resin compositions provided in a ratio of 99:1 to 60:40.
제1항에 있어서,According to claim 1,
상기 실록산계 중합체는 Si NMR 분석 결과 중 (Q3+T3)의 비율이 전체 실리콘 중 40% 이상인 포지티브형 감광성 수지 조성물.The siloxane-based polymer is a positive photosensitive resin composition in which the proportion of (Q3+T3) in Si NMR analysis results is 40% or more of the total silicone.
제1항에 있어서, According to claim 1,
상기 실록산계 중합체의 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 20,000이고, 상기 올레핀계 중합체의 폴리스티렌 환산중량평균분자량(Mw)은 1,000 내지 30,000인 포지티브형 감광성 수지 조성물.The siloxane polymer has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 20,000, and the olefin-based polymer has a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 30,000.
제1항에 있어서, According to claim 1,
상기 실록산계 중합체 및 올레핀계 중합체는 95:5 내지 10:90의 중량비로 제공되는 포지티브형 감광성 수지 조성물. The siloxane-based polymer and the olefin-based polymer are positive photosensitive resin compositions provided in a weight ratio of 95:5 to 10:90.
제1항에 있어서, According to claim 1,
상기 1,2-퀴논디아지드 화합물은 하기 화학식 4로 표시되는 페놀 화합물과 나프토퀴논디아지드술폰산 할로겐 화합물을 반응시켜 얻어진 포지티브형 감광성 수지조성물: The 1,2-quinone diazide compound is a positive photosensitive resin composition obtained by reacting a phenol compound represented by the following Chemical Formula 4 with a naphthoquinone diazide sulfonic acid halogen compound:
[화학식 4] [Formula 4]
Figure PCTKR2019018795-appb-img-000010
Figure PCTKR2019018795-appb-img-000010
상기 화학식 4에서, R 1 내지 R 6은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 4의 알킬기, 탄소수 1 내지 4의 알케닐기 또는 히드록시기이고, R 7 및 R 8은 각각 독립적으로 수소, 할로겐 또는 탄소수 1 내지 4의 알킬기이고, R 9는 수소 또는 탄소수 1 내지 4의 알킬기이다. In Formula 4, R 1 to R 6 are each independently hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms or a hydroxy group, and R 7 and R 8 are each independently hydrogen, halogen or carbon number It is an alkyl group of 1 to 4, and R 9 is hydrogen or an alkyl group of 1 to 4 carbon atoms.
제1항에 있어서, According to claim 1,
상기 용매는 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 프로필렌글리콜메틸에테르프로피오네이트, 프로필렌글리콜에틸에테르프로피오네이트, 프로필렌글리콜프로필에테르 프로피오네이트, 프로필렌글리콜에테르, 프로필렌글리콜에틸에테르, 프로필렌글리콜프로필에테르, 프로필렌글리콜부틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 디프로필렌글리콜디메틸에테르, 디부틸렌글리콜디메틸에테르, 및 디부틸렌글리콜디에틸에테르, 디에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜부틸에테르, 트리에티렌글리콜디메틸에테르, 트리에틸렌글리콜부틸메틸에테르, 디에틸렌글리콜터셔리부틸에테르, 테트라에틸렌글리콜디메틸에테르, 디프로필렌글리콜에틸에테르, 디에틸렌글리콜에틸헥실에테르, 디에틸렌글리콜메틸헥실에테르, 디프로필렌글리콜부틸메틸에테르, 디프로필렌글리콜에틸헥실에테르 및 디프로필렌글리콜메틸헥실에테르 중 적어도 하나 이상을 포함하는 포지티브형 감광성 수지 조성물. The solvent is propylene glycol methyl ether acetate, propylene glycol 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, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, di Ethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol ethyl ether, diethylene glycol ethyl A positive photosensitive resin composition comprising at least one of hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether.
제1항에 있어서, 상기 실록산계 중합체 및 올레핀계 중합체의 총중량 100 중량부를 기준으로, 상기 1,2-퀴논디아지드 화합물은 5 내지 50 중량부로 포함하고, According to claim 1, Based on the total weight of 100 parts by weight of the siloxane-based polymer and the olefin-based polymer, the 1,2-quinonediazide compound comprises 5 to 50 parts by weight,
상기 용매는 고형분의 함량이 10 내지 50 중량%가 되도록 포함하는 포지티브형 감광성 수지 조성물. The solvent is a positive photosensitive resin composition comprising a content of solid content of 10 to 50% by weight.
제1항에 있어서, According to claim 1,
벤조트리아진계 및 벤조트리아졸계 중 적어도 하나 이상의 UV 흡광제를 추가로 포함하는 포지티브형 감광성 수지 조성물. A positive photosensitive resin composition further comprising at least one UV absorber of benzotriazine-based and benzotriazole-based.
제7항에 있어서,The method of claim 7,
상기 UV 흡광제는, 상기 실록산계 중합체 및 올레핀계 중합체의 총중량 100 중량부를 기준으로, 1 내지 20 중량부로 제공되는 포지티브형 감광성 수지 조성물. The UV absorber is a positive photosensitive resin composition provided in 1 to 20 parts by weight based on 100 parts by weight of the total weight of the siloxane-based polymer and the olefin-based polymer.
제1항 내지 제12항 중 어느 한 항의 포지티브형 감광성 수지 조성물을 사용하는 디스플레이 소자의 패턴 형성 방법. The pattern formation method of the display element using the positive photosensitive resin composition of any one of Claims 1-12.
제1항 내지 제12항 중 어느 한 항의 포지티브형 감광성 수지 조성물의 경화체를 포함하는 디스플레이 소자.A display device comprising a cured product of the positive photosensitive resin composition of claim 1.
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