WO2010068027A2 - Composition d'isolant hybride organique-inorganique photosensible positif - Google Patents

Composition d'isolant hybride organique-inorganique photosensible positif Download PDF

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Publication number
WO2010068027A2
WO2010068027A2 PCT/KR2009/007337 KR2009007337W WO2010068027A2 WO 2010068027 A2 WO2010068027 A2 WO 2010068027A2 KR 2009007337 W KR2009007337 W KR 2009007337W WO 2010068027 A2 WO2010068027 A2 WO 2010068027A2
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Prior art keywords
insulating film
inorganic hybrid
photosensitive organic
weight
group
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PCT/KR2009/007337
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English (en)
Korean (ko)
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WO2010068027A3 (fr
Inventor
김병욱
윤혁민
김동명
구기혁
여태훈
윤주표
신홍대
최수연
김진선
이상훈
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주식회사 동진쎄미켐
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Priority to CN200980149593.5A priority Critical patent/CN102246095B/zh
Priority to JP2011540603A priority patent/JP6018383B2/ja
Publication of WO2010068027A2 publication Critical patent/WO2010068027A2/fr
Publication of WO2010068027A3 publication Critical patent/WO2010068027A3/fr

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    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a positive photosensitive organic-inorganic hybrid insulating film composition, and more specifically, to form a dual structure of the existing SiNx Passivation / acrylic photosensitive organic insulating film as a single layer (layer) can bring about process simplification and production cost reduction In addition, it has excellent performances such as sensitivity, resolution, process margin, transparency, and heat dissipation resistance, and in particular, enables a low dielectric constant insulating film to reduce power consumption, eliminating afterimages, crosstalk, and shift of threshold voltage.
  • a double film made of SiNx passivation and an acrylic photosensitive organic insulating film is used for TFT type liquid crystal display device or integrated circuit device to insulate the wirings arranged between layers and to improve the aperture ratio. Since SiNx film is made through CVD process and acrylic photosensitive organic insulating film is made by photo process, production capacity problem according to process time is serious.
  • the opening ratio of the display is lowered, and as the size of the display increases, the area occupied by the deposition equipment in the production line is also significant, which acts as a large burden on the large facility.
  • the acrylic photosensitive organic insulating film is formed by the existing photo process alone, it causes electrical defects such as afterimage, crosstalk, and shift of threshold voltage. This is known to be caused by current leakage due to defects on the film, which is a disadvantage of organic materials.
  • the present invention can form a dual structure of the existing SiNx Passivation / acrylic photosensitive organic insulating film as a single layer (layer), which can bring about process simplification and production cost reduction, sensitivity, resolution, In addition to excellent performance margins, transparency, heat dissipation resistance, and the like, it is possible to lower the power consumption by enabling a low dielectric constant insulating film, and to eliminate afterimages, crosstalk, and shift of threshold voltage. By enabling low outgassing due to excellent heat resistance, excellent panel reliability can be secured.
  • positive type photosensitive organic-inorganic hybrid insulating film composition which can be usefully applied to not only passivation insulating film and gate insulating film but also planarizing film in various displays.
  • Pattern formation method of display element using the same, and positive type Light-oil- is an object of the present invention to provide a display device comprising a cured product of the insulating inorganic hybrid composition in an insulating film.
  • a positive photosensitive organic-inorganic hybrid insulating film composition a) i) a reactive silane comprising 1-3 phenyl groups represented by the following formula (1), ii) a hydrolysis of a tetrafunctional reactive silane represented by the following formula (2) under a catalyst And siloxane oligomeric compounds having a polystyrene reduced weight average molecular weight (Mw) obtained by condensation polymerization of 1,000 to 2,0000; b) 1,2-quinonediazide compounds; And c) a solvent, wherein the positive type photosensitive organic-inorganic hybrid insulating film composition is provided.
  • a reactive silane comprising 1-3 phenyl groups represented by the following formula (1), ii) a hydrolysis of a tetrafunctional reactive silane represented by the following formula (2) under a catalyst And siloxane oligomeric compounds having a polystyrene reduced weight average molecular weight (Mw) obtained by condensation polymerization of 1,000 to 2,0000; b)
  • R 1 is a phenyl group
  • R 2 is each independently alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy
  • n is an integer of 1-3
  • the positive photosensitive organic-inorganic hybrid insulating film composition Preferably the positive photosensitive organic-inorganic hybrid insulating film composition
  • the present invention provides a method of forming a pattern of a display device, characterized in that using the positive photosensitive organic-inorganic hybrid insulating film composition.
  • the present invention also provides a display device comprising a cured body of the positive photosensitive organic-inorganic hybrid insulating film composition.
  • the cured product of the positive photosensitive organic-inorganic hybrid insulating film composition is applied as a passivation insulating film, a gate insulating film, or a planarizing film.
  • the positive type photosensitive organic-inorganic hybrid insulating film composition according to the present invention can form a dual structure of a conventional SiNx Passivation / acrylic photosensitive organic insulating film as one layer, which can bring about process simplification and reduction of production cost.
  • a conventional SiNx Passivation / acrylic photosensitive organic insulating film as one layer, which can bring about process simplification and reduction of production cost.
  • By enabling low outgassing due to its excellent heat resistance it is possible to secure excellent panel reliability. Through this, it can be usefully applied not only to passivation insulation film and gate insulation film but also to planarization film.
  • the present invention provides a positive photosensitive organic-inorganic hybrid insulating film composition
  • a positive photosensitive organic-inorganic hybrid insulating film composition comprising: a) i) a reactive silane comprising 1-3 phenyl groups represented by the following Chemical Formula 1, and ii) a tetrafunctional reactive silane represented by the following Chemical Formula 2; Siloxane oligomer compounds having a polystyrene reduced weight average molecular weight (Mw) obtained by hydrolysis and condensation polymerization under a range from 1,000 to 2,0000; b) 1,2-quinonediazide compounds; And c) a solvent.
  • Mw polystyrene reduced weight average molecular weight
  • R 1 is a phenyl group
  • R 2 is each independently alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy
  • n is an integer of 1-3
  • R 3 in Formula 2 are each independently an alkoxy group, phenoxy, or acetoxy group having 1 to 4 carbon atoms.
  • the positive photosensitive organic-inorganic hybrid insulating film composition comprises a) 100 parts by weight of the siloxane oligomer compound; b) 5 to 50 parts by weight of the 1,2-quinonediazide compound; And c) the solvent so that the solids content is 10-50% by weight.
  • the siloxane oligomer compound of a) used in the present invention can solve problems such as afterimage, crosstalk, and shift of threshold voltage, which have previously been a problem in order to replace the conventional double layer composed of SiNx passivation and acrylic photosensitive organic insulating layer with a single layer. It is a binder that can secure excellent panel reliability by enabling low outgassing due to excellent heat resistance.
  • the siloxane oligomer compound of a) comprises a) i) a reactive silane comprising 1-3 phenyl groups represented by Formula 1, and ii) a silane monomer of the tetrafunctional reactive silane represented by Formula 2 as an acid or base catalyst. Under hydrolysis and condensation polymerization.
  • the reactive silane comprising 1-3 phenyl groups represented by the formula (1) used in the present invention is phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenylmethyldimethoxysilane , Phenyltriacetoxysilane, phenyltriphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and the like. It can mix and use species.
  • A) i) Reactive silane comprising 1-3 phenyl groups represented by Formula 1 is preferably included in 50-90 parts by weight based on the total monomers. If the content is less than 50 parts by weight cracks (crack) may occur when forming the film, if it exceeds 90 parts by weight it may be difficult to control the molecular weight due to the reactivity during the polymerization.
  • the a) ii) tetrafunctional reactive silane represented by the formula (2) used in the present invention includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and the like. Or it can mix and use 2 or more types.
  • the tetrafunctional reactive silane represented by Formula 2 is preferably included in an amount of 10-50 parts by weight based on the total monomers. If the content is less than 10 parts by weight of the photosensitive organic-inorganic insulating film composition may form a poor solubility in the aqueous alkali solution when the pattern is formed, if it exceeds 50 parts by weight may be too large solubility in the aqueous alkali solution. .
  • siloxane oligomer compound of a) used in the present invention may be hydrolyzed and condensation-polymerized under an acid or base catalyst, in addition to the silane monomers of i) and ii), and iii) a reactive silane represented by the following general formula (3). have.
  • R 4 is each independently an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy
  • R 5 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, an epoxy group, a vinyl, hexenyl group, or acryl.
  • Group, a methacryl group, or an allyl group, n is an integer of 1-3.
  • Specific examples of the reactive silane represented by Formula 3 include trimethoxysilane, triethoxysilane, trimethylethoxysilane, triethylphenoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, and methyltriethoxy Silane, methyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, propyltrimethoxysilane, propyl tree Ethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloropropylmethyldimethoxysilane, chloroisobutyl
  • the amount of use is preferably 10 to 50 parts by weight of the total silane monomers.
  • the amount of use is within the above range, the sensitivity and developability may be further improved.
  • the oligomeric siloxane compound of a) used in the positive type photosensitive organic-inorganic hybrid insulating film composition of the present invention can bulk or solution polymerize the above monomers under water, an acid or a base catalyst, and undergo hydrolysis and condensation polymerization. Obtained through a process or the like.
  • Acid catalysts that can be used during the polymerization include hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, and the like. It may be used alone or in combination of two or more kinds at the same time.
  • the oligomer siloxane compound of a) finally obtained has a polystyrene reduced weight average molecular weight (Mw) of 1,000-20,000 via GPC.
  • Mw polystyrene reduced weight average molecular weight
  • the polystyrene reduced weight average molecular weight is less than 1,000, there is a problem that developability, residual film ratio, etc. are lowered when evaluating a positive type photosensitive organic-inorganic hybrid insulating film, or defects such as pinholes are formed during film formation. In the case of exceeding, the sensitivity of the positive photosensitive organic-inorganic hybrid insulating film is lowered or the developability of the pattern is inferior.
  • the positive photosensitive organic-inorganic hybrid insulating film composition of the present invention includes b) 1,2-quinonediazide compound, and the 1,2-quinonediazide compound of b) used in the present invention is a photosensitive compound.
  • the b) 1,2-quinonediazide compound may be one obtained by reacting a phenol compound represented by the following formula (4) with a naphthoquinone diazide 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 or a hydroxyl group
  • R 7 and R 8 are each independently hydrogen, a halogen or an alkyl group having 1 to 4 carbon atoms.
  • R 9 is hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • the 1,2-quinonediazide compound is 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, or the like. Can be used.
  • the quinone diazide compound may be prepared by reacting a naphthoquinone diazide sulfonic acid halogen compound with a phenol compound represented by the following formula under a weak base.
  • the said phenolic compound can be used individually or in mixture of 2 or more types.
  • the esterification degree is preferably 50 to 85%.
  • the esterification degree is less than 50%, the residual film rate may be worse, and when the esterification degree is greater than 85%, storage stability may be lowered.
  • the b) 1,2-quinonediazide compound is preferably included in an amount of 5 to 50 parts by weight based on 100 parts by weight of the siloxane oligomer compound of a). If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed parts is small, and if it exceeds 50 parts by weight, a large amount of unreacted 1,2-quinonediazide compound is produced when irradiated with light for a short time. There is a problem that the development is difficult because the solubility in the alkali aqueous solution remaining as a developer is too low.
  • the positive photosensitive organic-inorganic hybrid insulating film composition of the present invention includes c) a solvent, wherein the solvent of c) does not generate flatness and coating stain of the insulating film to form a uniform pattern profile. do.
  • the solvent of c) is ethylene glycol alkyl ether acetates such as alcohols such as methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate and ethylene glycol ethyl ether.
  • alcohols such as methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate and ethylene glycol ethyl ether.
  • Ethylene glycol alkyl ether propionates such as propionate
  • Ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether
  • Diethylene glycol alkyl ethers such as diethylene glycol methyl ethyl ether
  • propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate
  • Propylene glycol alkyl ether propionates propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene such as propylene glycol methyl ether propionate, propylene glycol ethyl ether
  • the solvent of c) is preferably included so that the solid content of the positive photosensitive organic-inorganic hybrid insulating film composition is 10 to 50% by weight. If the solid content is less than 10% by weight, there is a problem that the coating thickness is thin, and coating uniformity is lowered. If the solid content is more than 50% by weight, the coating thickness becomes thick, and the coating equipment may be unreasonable during coating. have. If the solids content of the total composition is 10 to 20% by weight, it is easy to use in the Slit Coater, if it is 20 to 50% by weight it is easy to use in the Spin Coater or Slit & Spin Coater.
  • the positive photosensitive organic-inorganic hybrid insulating film composition of the present invention comprising the above components may further contain d) a plasticizer, e) an epoxy resin, f) a nitrogen-containing crosslinking agent containing an alkanol group, and g) a surfactant, if necessary. It may include.
  • the plasticizer of d) maintains film characteristics without cracks and maintains high sensitivity after the curing process by adjusting the crosslinking density of the insulating film.
  • the said plasticizer is phthalate type, such as dioctyl phthalate and diisononyl phthalate, adipate type, such as dioctyl adipate, and phosphate type, such as tricresyl phosphate, 2,2,4-trimethyl-1,3-pentanediol mono Monoisobutyrate systems, such as isobutyrate, etc. can be used individually or in mixture of 2 or more types.
  • the plasticizer may be included in an amount of 5-20 parts by weight based on 100 parts by weight of the siloxane oligomer compound of a), and when the content is within the above range, the control of crosslinking density is easy, heat resistance is excellent, and generation of fumes during the process is performed. This is advantageous to write down.
  • the epoxy resin of e serves to improve heat resistance, adhesion, and the like of the pattern obtained from the photosensitive organic-inorganic hybrid insulating film composition.
  • the epoxy resins include glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins such as bisphenol A type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, and cycloaliphatic compounds.
  • An epoxy resin etc. can be used individually or in mixture of 2 or more types, It is preferable to use a bisphenol-A epoxy resin, a cresol novolak-type epoxy resin, or a glycidyl ester type epoxy resin especially.
  • the epoxy resin is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the siloxane oligomer compound of a).
  • the epoxy resin is in the above range, heat resistance, adhesive strength, and storage stability are excellent at the same time. -There is an advantage that there is no fear of precipitation on the inorganic hybrid insulating film composition.
  • the nitrogen-containing crosslinking agent containing the alkanol group of f) serves to improve the adhesion of the pattern obtained from the photosensitive organic-inorganic hybrid insulating film composition, and forms a crosslinking structure with the resin to increase the degree of crosslinking.
  • nitrogen-containing crosslinking agents condensation products of urea and formaldehyde, condensation products of melamine and formaldehyde, methylol urea alkyl ethers obtained from alcohols, methylol melamine alkyl ethers and the like can be used.
  • the nitrogen-containing crosslinking agent including the alkanol group is a compound represented by the following formula (5), (6), (7), (8), (9), (10), (11), (12) It is good to use.
  • R 1, R 3 , and R 5 are each independently —CH 2 O (CH 2 ) n CH 3 , n is an integer of 0 to 3, and R 2 , R 4 , and R 6 are Each independently or simultaneously is a hydrogen atom, or m is an integer of 0 to 3 as-(CH 2 ) OH or -CH 2 O (CH 2 ) mCH 3 .
  • R 1 , R 3 are each independently —CH 2 O (CH 2 ) nCH 3 , n is an integer of 0 to 3, and R 2 , R 4 are each independently or simultaneously a hydrogen atom, or — (CH 2 ) OH or -CH 2 O (CH 2 ) mCH 3 , m is an integer from 0 to 3, R 5 is an alkyl or phenyl group having 1 to 3 carbon atoms.
  • each R is independently or simultaneously a hydrogen atom, or-(CH 2 ) OH or -CH 2 O (CH 2 ) mCH 3 as m is an integer of 0-3, at least one or more alkanes It's coming
  • the nitrogen-containing crosslinking agent containing the alkanol group of f) serves to improve adhesion to the substrate, and is preferably included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the siloxane oligomer compound of a).
  • the surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Trim Corporation), or KP341 (brand name) : Sinwol Chemical Co., Ltd.).
  • the surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the siloxane oligomer compound of a), and when the content is within the above range, it is more preferable in improving the coating property and developability of the photosensitive composition.
  • the positive photosensitive organic-inorganic hybrid insulating film composition of the present invention as described above may be used after filtering with a Millipore filter of 0.1 to 0.2 ⁇ m with a solid content concentration of 10 to 50 wt%.
  • the present invention is a display device pattern forming method characterized in that using the positive photosensitive organic-inorganic hybrid insulating film composition and the cured body of the positive photosensitive organic-inorganic hybrid insulating film composition
  • a pattern forming method according to the present invention is a method of forming an insulating film pattern in a display process, except that a process other than using a photo process using the positive photosensitive organic-inorganic hybrid insulating film composition is performed.
  • known methods can be applied.
  • a method of forming a pattern of a display device using the positive photosensitive organic-inorganic hybrid insulating film is as follows.
  • the positive photosensitive organic-inorganic hybrid insulating film of the present invention is applied to the surface of the substrate by spin coating, slit and spin coating, slit coating, roll coating, and the like, and the solvent is removed by prebaking to form a coating film.
  • the prebaking is preferably carried out for 1 to 3 minutes at a temperature of 100 ⁇ 120 °C.
  • a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like on the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.
  • an aqueous alkali solution for the developing solution.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and primary amines such as n-propylamine and secondary amines such as diethylamine and n-propylamine Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like.
  • the aqueous solution of the quaternary ammonium salt, etc. can be used.
  • the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10 parts by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.
  • the pattern is applied to a heating apparatus such as an oven.
  • a heating apparatus such as an oven.
  • the pattern forming method of the display according to the present invention forms a double layer of a conventional SiNx Passivation / acrylic photosensitive organic insulating layer as a single layer by forming an insulating layer using a single photo process, resulting in process simplification and production cost reduction.
  • a conventional SiNx Passivation / acrylic photosensitive organic insulating layer As a single layer by forming an insulating layer using a single photo process, resulting in process simplification and production cost reduction.
  • Synthesis Example 2 Except that in Synthesis Example 2, 90 parts by weight of phenyltriethoxysilane, 5 parts by weight of tetraethoxysilane, and 5 parts by weight of n-hexyltrimethoxysilane were added as reactive silane into the flask equipped with a cooling tube and a stirrer. It carried out in the same manner as in Synthesis example 2. Finally, as a result of GPC analysis, a) siloxane oligomer compound having a polystyrene equivalent weight average molecular weight (MW) of 7000 was prepared.
  • MW polystyrene equivalent weight average molecular weight
  • Synthesis Example 2 was carried out in the same manner as in Synthesis Example 2, except that 70 parts by weight of phenyltriethoxysilane and 30 parts by weight of tetraethoxysilane were added to the flask having the cooling tube and the stirrer as reactive silanes, respectively. Finally, as a result of GPC analysis, a) siloxane oligomer compound having a polystyrene reduced weight average molecular weight (MW) of 1500 was prepared.
  • MW polystyrene reduced weight average molecular weight
  • Example 1 (Preparation of positive type photosensitive organic-inorganic hybrid insulating film composition )
  • Example 1 Except for using the siloxane oligomer compound (B) of Synthesis Example 2 instead of the siloxane oligomer compound (A) of Synthesis Example 1 in Example 1 was prepared in the same manner as in Example 1.
  • the photosensitive resin composition was manufactured by the same method as Example 1, except that dioctyl adipate was used instead of dioctylphthalate as a plasticizer when the photosensitive resin composition was prepared in Example 1.
  • Example 1 In Example 1 except that 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was used in place of dioctylphthalate as a plasticizer in the preparation of the photosensitive resin composition, in the same manner as in Example 1. To prepare a photosensitive resin composition.
  • a photosensitive resin composition was prepared in the same manner as in Example 1, except that dioctylphthalate was not used as a plasticizer when preparing the photosensitive resin composition in Example 1.
  • a photosensitive resin composition was prepared in the same manner as in Example 1, except that diethylene glycol methylethyl ether was used instead of propylene glycol methyl ether acetate as a solvent when preparing the photosensitive resin composition in Example 1.
  • Examples 1 to 15 and Comparative Examples 1 to 3 physical properties such as sensitivity, resolution, process margin, transmittance, heat discoloration resistance, insulation, and heat resistance were measured and shown in Table 1 below.
  • Table 1 After applying the positive photosensitive organic-inorganic hybrid insulating film composition prepared in Examples 1 to 15 and Comparative Examples 1 to 3 using a spin coater on a glass substrate, and free on a hot plate for 2 minutes at 100 °C It was baked to form a film having a thickness of 3.6 mu m.
  • the developed pattern was irradiated with 500 mJ / cm 2 of ultraviolet light having an intensity of 20 mA / cm 2 at 435 nm and cured at 230 ° C. for 60 minutes in an oven to obtain a pattern film having a thickness of 3.0 ⁇ m.
  • Heat discoloration resistance The heat discoloration resistance is determined by the 400 nm transmittance change of the pattern film before and after curing by curing for 40 minutes in an oven at 300 ° C in addition to the measurement substrate for evaluating the transparency of the above d). Evaluated. (Circle) and the case where the change rate at this time are less than 5%, (triangle
  • Insulation-Insulation was determined based on the dielectric constant.
  • the dielectric constant was obtained by measuring the capacitance of the capacitor and the following equation.
  • the positive photosensitive organic-inorganic hybrid insulating film was formed in the same manner as in the above-described sensitivity measurement between the upper and lower metal electrodes patterned with gold of 1 cm2, and then formed into a MIM (Metal / Insulator / Metal) structure.
  • the capacitance of the device was measured through an impedance analyzer, and the dielectric constant was calculated by the following equation.
  • C (capacitance) ⁇ 0 (vacuum dielectric constant) * ⁇ r (dielectric dielectric constant) * A (effective area) / d (dielectric dielectric thickness)
  • the dielectric constant was measured, and the case of 2.5 to 2.8 was represented by ⁇ , and the case of 2.8 to 3.2 was represented by ⁇ and 3.2 or more.
  • the positive photosensitive organic-inorganic hybrid insulating film composition prepared in Examples 1 to 15 according to the present invention was excellent in the performance, such as sensitivity, resolution, process margin, transparency, heat discoloration resistance, in particular insulation Compared with Comparative Examples 1 to 3, the power consumption can be reduced, and afterimage, crosstalk, and shift of threshold voltage can be eliminated. In addition, it was possible to secure excellent panel reliability by enabling low outgassing due to excellent heat resistance. It can be seen that a positive photosensitive organic-inorganic hybrid insulating film is applicable to various display processes.
  • the positive type photosensitive organic-inorganic hybrid insulating film composition according to the present invention can form a dual structure of a conventional SiNx Passivation / acrylic photosensitive organic insulating film as one layer, which can bring about process simplification and reduction of production cost.
  • a conventional SiNx Passivation / acrylic photosensitive organic insulating film as one layer, which can bring about process simplification and reduction of production cost.
  • By enabling low outgassing due to its excellent heat resistance it is possible to secure excellent panel reliability. Through this, it can be usefully applied not only to passivation insulation film and gate insulation film but also to planarization film.

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  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne une composition d'isolant hybride organique-inorganique photosensible positif comprenant : i) un silane réactif contenant 1 à 3 groupes phényles représenté par la formule chimique (1) ; et ii) un oligomère de siloxane qui est obtenu par hydrolyse et polymérisation par condensation d'un monomère de silane tétra-fonctionnel représenté par la formule chimique (2) en présence d'un catalyseur et qui possède un poids moléculaire moyen (converti par rapport au polystyrène) de 1000 à 20 000. La composition d'isolant hybride organique-inorganique photosensible positif de la présente invention simplifie le procédé et réduit les coûts du fait de la formation d'une double structure constituée d'une monocouche de passivation en SiNx/isolant organique acrylique photosensible, améliore la sensibilité, la résolution, la marge du procédé, la transparence et l'anti-thermochromisme, réduit la consommation d'électricité du fait de l'obtention d'un isolant ayant une constante diélectrique basse, et élimine la rémanence d'une image, la diaphonie et le phénomène de décalage d'une tension seuil. En outre, la composition peut accroître la fiabilité d'un panneau en permettant un faible dégazage du fait d'une résistance thermique élevée. Par conséquent, la composition peut être appliquée à un isolant de passivation, un isolant de grille et un isolant de plaque de divers dispositifs d'affichage.
PCT/KR2009/007337 2008-12-10 2009-12-09 Composition d'isolant hybride organique-inorganique photosensible positif WO2010068027A2 (fr)

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CN200980149593.5A CN102246095B (zh) 2008-12-10 2009-12-09 正型感光性有机-无机混合绝缘膜组合物
JP2011540603A JP6018383B2 (ja) 2008-12-10 2009-12-09 ポジティブ型感光性有機・無機ハイブリッド絶縁膜組成物

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KR10-2008-0125285 2008-12-10
KR1020080125285A KR20100066808A (ko) 2008-12-10 2008-12-10 포지티브형 감광성 유-무기 하이브리드 절연막 조성물

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JP2012511740A (ja) 2012-05-24
KR20100066808A (ko) 2010-06-18
JP6018383B2 (ja) 2016-11-02
CN102246095A (zh) 2011-11-16
TWI519897B (zh) 2016-02-01
TW201028794A (en) 2010-08-01
CN102246095B (zh) 2014-04-02

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