CN102246095B - Positive photosensitive organic-inorganic hybrid insulating film composition - Google Patents

Positive photosensitive organic-inorganic hybrid insulating film composition Download PDF

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CN102246095B
CN102246095B CN200980149593.5A CN200980149593A CN102246095B CN 102246095 B CN102246095 B CN 102246095B CN 200980149593 A CN200980149593 A CN 200980149593A CN 102246095 B CN102246095 B CN 102246095B
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inorganic hybrid
photosensitive organic
positive photosensitive
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ether
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金柄郁
尹赫敏
金东明
丘冀赫
吕泰勋
尹柱豹
申洪大
崔守延
金珍善
李相勋
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Dongjin Semichem Co Ltd
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • G03F7/022—Quinonediazides
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/004—Photosensitive materials
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    • G—PHYSICS
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    • 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
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    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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    • 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

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Abstract

The present invention relates to a positive photosensitive organic-inorganic hybrid insulating film composition, and more particularly, to a positive photosensitive organic-inorganic hybrid insulating film composition containing an oligosiloxane compound obtained by hydrolyzing and polycondensing i) a reactive silane containing 1 to 3 phenyl groups represented by the following chemical formula 1 and ii) a silane monomer of a 4-functional reactive silane represented by the chemical formula 2 in the presence of a catalyst, the oligosiloxane compound having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 to 2,0000. According to the positive photosensitive organic-inorganic hybrid insulating film composition of the present invention, a double structure of the conventional SiNx passivation/acrylic photosensitive organic insulating film can be formed as one layer (layer), thereby simplifying the process and saving the production cost, and not only is excellent in performances such as sensitivity, resolution, process margin, transparency, thermal discoloration resistance, etc., but also it is possible to form a low dielectric constant insulating film, thereby reducing power consumption and eliminating afterimage, crosstalk, and shift phenomenon of threshold voltage. In addition, low outgassing due to excellent heat resistance is possible, and excellent panel reliability can be ensured. This makes it possible to be usefully applied to not only a passivation insulating film and a gate insulating film but also a planarization film in various displays.

Description

Positive photosensitive organic-inorganic hybrid insulator composition
Technical field
The present invention relates to positive photosensitive organic-inorganic hybrid insulator composition, relate in more detail the dual structure of existing SiNx passivation/acrylic acid series photonasty organic insulating film is formed to one deck (layer), thereby can bring the simplification of operation and the saving of producing cost, not only sensitivity, resolution, process margin, the transparency, the excellent performances such as heat-resisting discolouration, particularly make insulating film with low dielectric constant become possibility, thereby can reduce power consumption, and eliminate image retention, crosstalk, and the drift phenomenon of threshold voltage, in addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability, can in various displays, not only can usefully be applicable to passivation dielectric film thus, gate insulating film, but also can usefully be applicable to the positive photosensitive organic-inorganic hybrid insulator composition of planarization film etc.
Background technology
Recently, in TFT type liquid crystal display cells or integrated circuit component, in order to make to insulate between the distribution of interlayer configuration and to improve aperture opening ratio and use the duplex film being formed by SiNx passivating film and acrylic acid series photonasty organic insulating film.In the situation of SiNx film, by CVD operation, obtain, in the situation of acrylic acid series photonasty organic insulating film, by light (Photo) operation, obtained, so the productive capacity problem that activity time causes is serious.
In dielectric film in the past, while forming the SiNx film being formed by above-mentioned CVD separately, there is the problem of the aperture opening ratio reduction of display, according to the maximization of display, on production line, the shared area of evaporation coating device is also quite large, thereby equipment enlarging is brought to very large burden.In addition, while forming separately the acrylic acid series photonasty organic insulating film by existing smooth operation, cause image retention, crosstalk, the drift phenomenon of threshold voltage value etc. is bad to the electricity of display.Known causes electric leakage as the shortcoming on the film of the weakness of organic substance is its reason.
Thus, to take organic and inorganic hybrid technology, be recently need to greatly increasing of the basis individual layer dielectric film that only just can form by light operation, this technological development is carried out actively.
Summary of the invention
The technical matters solving
In order to solve the problem of above-mentioned prior art, the object of the present invention is to provide positive photosensitive organic-inorganic hybrid insulator composition, utilize the pattern formation method of its display device, and the display device of the solidfied material that contains positive photosensitive organic-inorganic hybrid insulator composition with the form of dielectric film, above-mentioned positive photosensitive organic-inorganic hybrid insulator composition forms one deck (layer) by the dual structure of existing SiNx passivation/acrylic acid series photonasty organic insulating film, thereby can bring the simplification of operation and the saving of producing cost, not only sensitivity, resolution, process margin, the transparency, the excellent performances such as heat-resisting discolouration, particularly make insulating film with low dielectric constant become possibility, thereby can reduce power consumption, and eliminate image retention, crosstalk, and the drift phenomenon of threshold voltage, in addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability, can in various displays, not only can usefully be applicable to passivation dielectric film thus, gate insulating film, but also can usefully be applicable to planarization film etc.
The technical scheme of dealing with problems
In order to achieve the above object, the invention provides a kind of positive photosensitive organic-inorganic hybrid insulator composition, it is characterized in that, contain a) oligosiloxane compound, this oligosiloxane compound is to make i) reactive silane that contains 1-3 phenyl, the ii that by following Chemical formula 1, are represented) 4 functional response's property silane of being represented by following Chemical formula 2 are hydrolyzed and polycondensation and obtaining under catalyzer exists, the polystyrene conversion weight-average molecular weight Mw of this oligosiloxane compound is 1,000 to 2,0000; B) 1,2-quinone di-azido compound; And c) solvent:
[Chemical formula 1]
(R 1)nSi(R 2) 4-n
In above-mentioned Chemical formula 1, R 1for phenyl, R 2be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another, the integer that n is 1-3,
[Chemical formula 2]
Si(R 3) 4。
Preferably, above-mentioned positive photosensitive organic-inorganic hybrid insulator composition contains a) above-mentioned oligosiloxane compound 100 weight portions; B) above-mentioned 1,2-quinone di-azido compound 5 to 50 weight portions; And c) solvent, making solid component content is 10-50 % by weight.
The pattern formation method that the invention provides in addition a kind of display device, is characterized in that, utilizes above-mentioned positive photosensitive organic-inorganic hybrid insulator composition.
The invention provides in addition a kind of display device, it is characterized in that, the solidfied material that contains above-mentioned positive photosensitive organic-inorganic hybrid insulator composition.
Preferably, the solidfied material of above-mentioned positive photosensitive organic-inorganic hybrid insulator composition is applicable to passivation dielectric film, gate insulating film or planarization film.
Beneficial effect
Positive photosensitive organic-inorganic hybrid insulator composition according to the present invention forms one deck (layer) by the dual structure of existing SiNx passivation/acrylic acid series photonasty organic insulating film, thereby can bring the simplification of operation and the saving of producing cost, not only sensitivity, resolution, process margin, the transparency, the excellent performances such as heat-resisting discolouration, particularly make insulating film with low dielectric constant become possibility, thereby can reduce power consumption, and eliminate image retention, crosstalk, and the drift phenomenon of threshold voltage, in addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability, can in various displays, not only can usefully be applicable to passivation dielectric film thus, gate insulating film, but also can usefully be applicable to planarization film etc.
Embodiment
The invention is characterized in, in positive photosensitive organic-inorganic hybrid insulator composition, contain a) oligosiloxane compound, this oligosiloxane compound is to make i) reactive silane that contains 1-3 phenyl, the ii that by following Chemical formula 1, are represented) 4 functional response's property silane of being represented by following Chemical formula 2 are hydrolyzed and polycondensation and obtaining under catalyzer exists, the polystyrene conversion weight-average molecular weight (Mw) of this oligosiloxane compound is 1,000 to 2,0000; B) 1,2-quinone di-azido compound; And c) solvent.
[Chemical formula 1]
(R 1)nSi(R 2) 4-n
In above-mentioned Chemical formula 1, R 1for phenyl, R 2be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another, the integer that n is 1-3,
[Chemical formula 2]
Si(R 3) 4
In above-mentioned Chemical formula 2, R 3be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another.
Preferably, above-mentioned positive photosensitive organic-inorganic hybrid insulator composition contains: a) above-mentioned oligosiloxane compound 100 weight portions; B) above-mentioned 1,2-quinone di-azido compound 5 to 50 weight portions; And c) solvent, making solid component content is 10-50 % by weight.
Above-mentioned oligosiloxane compound a) using in the present invention is a kind of like this bonding agent: it not only can solve the image retention that becomes at present problem for the existing duplex film consisting of SiNx passivating film and acrylic acid series photonasty organic insulating film is replaced with to monofilm, crosstalks, the problem of the drift phenomenon of threshold voltage and so on, and make to become possibility due to the low outgas that excellent thermotolerance is brought, thereby can guarantee excellent panel reliability.
Above-mentioned oligosiloxane compound a) can be by by a) i) reactive silane that contains 1-3 phenyl and the ii that by above-mentioned Chemical formula 1, are represented) silane monomer of 4 functional response's property silane of being represented by above-mentioned Chemical formula 2 obtains by hydrolysis and polycondensation under acid catalyst or base catalyst exist.
For above-mentioned a) i of the present invention) reactive silane that contains 1-3 phenyl that represented by above-mentioned Chemical formula 1 has: phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three butoxy silanes, phenyl methyl dimethoxy silane, phenyl triacetoxysilane, phenyl triple phenoxyl silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, diphenyl hexichol TMOS, triphenyl methoxy silane, triphenyl Ethoxysilane etc., can use separately, or two or more is mixed and is used.
Above-mentioned a) i) reactive silane that contains 1-3 phenyl being represented by above-mentioned Chemical formula 1 preferably contains 50-90 weight portion with respect to whole total monomers.When its content is less than 50 weight portion, when film forms, may crack (Crack), while surpassing 90 weight portion, when polymerization, reactive decline, may be difficult to control molecular weight.
For above-mentioned a) ii of the present invention) 4 functional response's property silane of being represented by above-mentioned Chemical formula 2 have tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, tetrem acyloxy silane etc., can use separately, or two or more is mixed and is used.
Above-mentioned a) ii) the 4 functional response's property silane that represented by above-mentioned Chemical formula 2 preferably contain 10-50 weight portion with respect to whole total monomers.When its content is less than 10 weight portion, when the pattern of photonasty organic and inorganic dielectric film composition forms, the decreased solubility to aqueous alkali, may occur bad, while surpassing 50 weight portion, may be excessive to the dissolubility of aqueous alkali.
In addition, for oligosiloxane compound a) of the present invention, except above-mentioned i) and silane monomer ii) can also further contain iii) reactive silane that represented by following chemical formula 3, under acid catalyst or base catalyst exist, be hydrolyzed and polycondensation.
[chemical formula 3]
(R 4)nSi(R 5) 4-n
In above-mentioned chemical formula 3, R 4be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another, R 5be alkyl, aryl, epoxy radicals, vinyl, hexenyl, acryloyl group, methacryl or the allyl of hydrogen, carbon number 1-10 independently of one another, the integer that n is 1-3.
The object lesson of the reactive silane above-mentioned iii) being represented by above-mentioned chemical formula 3 has: trimethoxy silane, triethoxysilane, trimethylethoxysilane, triethylbenzene TMOS, trimethyl methoxy silane, methyltrimethoxy silane, methyl triethoxysilane, methyl triple phenoxyl silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyltriacetoxysilane, methyl triacetoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, chloropropylmethyldimethoxysilane, chlorine isobutyl methyl dimethoxysilane, trifluoro propyl trimethoxy silane, trifluoro propyl methyl dimethoxysilane, isobutyl trimethoxy silane, isobutyl triethoxy silane, normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, n-butylmethyldimethoxyforane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, n-octyl trimethoxy silane, decyl trimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl ethyl dimethoxy silane, dicyclopentyl dimethoxyl silane, tert-butyl group ethyl dimethoxy silane, tert-butyl group propyl group dimethoxy silane, Dicyclohexyldimethoxysilane, isooctyltrimethoxysi,ane, n-octyl triethoxysilane, glycidoxypropyltrime,hoxysilane, glycidoxy propyl-triethoxysilicane, glycidoxy propyl group methyl dimethoxysilane, glycidoxy propyl group diethoxy silane, epoxy radicals cyclohexyl ethyl trimethoxy silane, methacryloxypropyl trimethoxy silane, acryloxy propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, methyl ethylene dimethoxy silane, aryl trimethoxy silane, hexenyl trimethoxy silanes etc., can be used separately, or two or more is mixed and is used.
Use above-mentioned iii) when the reactive silane that represented by above-mentioned chemical formula 3 or their potpourri, consumption is preferably 10 to 50 weight portions of all total silane monomers.Consumption is in above-mentioned scope time, and sensitivity and developability can be better.
Can be by above-mentioned monomer is carried out to bulk polymerization or solution polymerization under the existence of water and acid catalyst or base catalyst for oligosiloxane compound a) of positive photosensitive organic-inorganic hybrid insulator composition of the present invention, and obtain through the process of hydrolysis and polycondensation etc.
While carrying out above-mentioned polymerization, operable acid catalyst has hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid etc., base catalyst has ammonium, organic amine and alkyl ammonium hydroxide salt etc., can use separately, or two or more mixing is used simultaneously or step by step.
It is 1,000 to 2,0000 that oligosiloxane compound a) finally obtaining preferably adopts the polystyrene conversion weight-average molecular weight (Mw) of GPC.Above-mentioned polystyrene conversion weight-average molecular weight is less than at 1,000 o'clock, the decline such as developability, residual film ratio while exist evaluating positive photosensitive organic-inorganic hybrid insulator, or cause the bad problems such as pin hole (Pin-Hole) while forming film; Surpass at 20,000 o'clock, exist the sensitivity of positive photosensitive organic-inorganic hybrid insulator to decline, or the problem of the developability variation of pattern.
In addition, positive photosensitive organic-inorganic hybrid insulator composition of the present invention contains b) 1,2-quinone di-azido compound, for above-mentioned b of the present invention) 1,2-quinone di-azido compound is used as photosensitive compounds.Above-mentioned b) 1,2-quinone di-azido compound can be used the phenolic compounds that represented by following chemical formula 4 and naphthoquinones two nitrine sulfuryl halides reactions and the product that obtains.
In above-mentioned chemical formula 4, R 1to R 6be alkyl, alkenyl or the hydroxyl of hydrogen, halogen, carbon number 1-4 independently of one another, R 7and R 8be the alkyl of hydrogen, halogen, carbon number 1-4 independently of one another, R 9alkyl for hydrogen or carbon number 1-4.
Preferably, above-mentioned 1,2-quinone di-azido compound can be used 1,2-quinone, two nitrine 4-sulphonic acid esters, 1,2-quinone two nitrine 5-sulphonic acid esters or 1,2-quinone, two nitrine 6-sulphonic acid esters etc.
As concrete example, above-mentioned quinone di-azido compound can react the phenolic compounds of naphthoquinones two nitrine sulfuryl halides and following chemical formula and manufacture under weak base.
Figure BPA00001387926500071
Figure BPA00001387926500091
Figure BPA00001387926500101
Figure BPA00001387926500111
Figure BPA00001387926500131
Above-mentioned phenolic compounds can be used separately, or two or more is mixed and is used.
During with above-mentioned phenolic compounds and the synthetic quinone di-azido compound of naphthoquinones two nitrine sulfuryl halides, esterification degree is preferably 50 to 85%.When above-mentioned esterification degree is less than 50%, residual film ratio possible deviation, while surpassing 85%, storage stability may reduce.
Above-mentioned b) 1,2-quinone di-azido compound preferably contains 5 to 50 weight portions with respect to oligosiloxane compound 100 weight portions a).When its content is less than 5 weight portion, the difference of the solubleness of exposure portion and non-exposure portion diminishes, and is difficult to form pattern; While surpassing 50 weight portion, there is the short irradiation light time, a large amount of remaining unreacteds 1,2-quinone di-azido compound, thus too low for the solubleness of the aqueous alkali as developer solution, be difficult to the problem of developing.
In addition, positive photosensitive organic-inorganic hybrid insulator composition of the present invention contains c) solvent, above-mentioned c) solvent make dielectric film smooth and be not coated with spot, thereby can form the pattern contour (pattern profile) of homogeneous.
Above-mentioned c) solvent can be by methyl alcohol, ethanol, benzylalcohol, the alcohols such as hexanol, ethylene glycol monomethyl ether acetate, the ethylene glycol alkyl ether acetate esters such as ethyl cellosolve acetate, ethylene glycol monomethyl ether propionic ester, the ethylene glycol alkyl ether propionic acid esters such as ethylene glycol ethyl ether propionic ester, ethylene glycol monomethyl ether, the ethylene glycol monoalkyl ether classes such as ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, the diethylene glycol alkyl ethers such as diglycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, the propylene glycol alkyl ether acetic acid ester classes such as propylene glycol propyl ether acetic acid esters, propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, the propylene glycol alkyl ether propionic acid esters such as propylene glycol propyl ether propionic ester, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, the propylene-glycol monoalky lether classes such as propandiol butyl ether, dipropylene glycol dimethyl ether, the dipropylene glycol alkyl ethers such as dipropylene glycol diethyl ether, butylene glycol monomethyl ether, the butylene glycol monomethyl ether classes such as butylene glycol list ether, dibutylene glycol dimethyl ether, the dibutylene glycol alkyl ethers such as dibutylene glycol diethyl ether etc. are used separately or two or more are mixed and is used.
Above-mentioned c) solvent is preferably so that the solid component content of positive photosensitive organic-inorganic hybrid insulator composition becomes the mode of 10 to 50 % by weight contains.When solid component content is less than 10 % by weight, the problem that exists coating thickness attenuation, coating uniformity coefficient to reduce; While surpassing 50 % by weight, while there is coating thickness thickening, coating, to apparatus for coating, bring the problem of infringement.The solid component content of above-mentioned whole compositions is 10 during to 20 % by weight, easily in slit coater, use, 20 during to 50 % by weight, easily in slit coater or crack rotary coating machine (Slit & Spin Coater), uses.
The positive photosensitive organic-inorganic hybrid insulator composition of the present invention consisting of mentioned component can further contain d as required) plastifier, e) epoxy resin, f) the nitrogenous crosslinking chemical and the g that contain silane alcohol base) surfactant.
Above-mentioned d) plastifier can regulate the degree of crosslinking of dielectric film, and after curing process, it is maintained does not have (Crack) of crackle membrane property, and maintains high sensitivity characteristic.
Above-mentioned plastifier can be by phthalic ester systems such as dioctyl phthalate, diisononyl phthalates, the adipate systems such as hexanedioic acid dioctyl ester, the phosphate systems such as tricresyl phosphate, 2,2,4-trimethyl-1, the mono isobutyrate systems such as 3-pentanediol mono isobutyrate etc. are used separately, or two or more is mixed and is used.
Above-mentioned plastifier preferably contains 5-20 weight portion with respect to oligosiloxane compound 100 weight portions a), and its content in above-mentioned scope time, easily regulates degree of crosslinking, excellent heat resistance, and the generation of flue gas in operation (Fume) is few, therefore favourable.
Above-mentioned e) epoxy resin plays the effect of the thermotolerance, bonding force etc. that improve the pattern obtained by photonasty organic and inorganic mix insulation film composition.
Above-mentioned epoxy resin can be used the above-mentioned epoxy resin bisphenol A type epoxy resin of glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hetero ring type, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, cyclic aliphatic epoxy resin etc. separately, or two or more is mixed and is used, particularly preferably use bisphenol A type epoxy resin, cresols phenolic resin varnish type epoxy resin or glycidyl ester type epoxy resin.
With respect to above-mentioned oligosiloxane compound 100 weight portions a), preferably contain above-mentioned epoxy resin 0.5 to 10 weight portion, in the time of in above-mentioned scope, thermotolerance, bonding force, storage-stable are all excellent, and also having in addition an advantage is not worry separating out mutually from positive photosensitive organic-inorganic hybrid insulator composition of the present invention.
In addition, above-mentioned f) the nitrogenous crosslinking chemical that contains silane alcohol base plays the effect of the bonding force that improves the pattern being obtained by photonasty organic and inorganic mix insulation film composition, becomes cross-linked structure and increases degree of crosslinking with resin-shaped.As so nitrogenous crosslinking chemical, can utilize the condensation product of condensation product, melamine and the formaldehyde of iodine and formaldehyde, the methylol iodine alkyl ether being obtained by alcohols, melamine methylol alkyl ether etc.Preferably, as the above-mentioned nitrogenous crosslinking chemical that contains silane alcohol base, preferably the compound being represented by following chemical formula 5, chemical formula 6, chemical formula 7, chemical formula 8, chemical formula 9, Chemical formula 10, Chemical formula 11, Chemical formula 12 is used separately, or two or more is mixed and is used.
Figure BPA00001387926500151
In above-mentioned chemical formula 5, R 1, R 3and R 5be independently of one another-CH 2o (CH 2) ncH 3, n is 0 to 3 integer, R 2, R 4and R 6be hydrogen atom ,-(CH independently of one another or simultaneously 2) OH or-CH 2o (CH 2) mCH 3, m is 0 to 3 integer.
[chemical formula 6]
Figure BPA00001387926500161
In above-mentioned chemical formula 6, R 1, R 3be independently of one another-CH 2o (CH 2) nCH 3, n is 0 to 3 integer, R 2, R 4be hydrogen atom ,-(CH independently of one another or simultaneously 2) OH or-CH 2o (CH 2) mCH 3, m is 0 to 3 integer, R 5alkyl or phenyl for carbon number 1-3.)
Figure BPA00001387926500162
Figure BPA00001387926500171
In above-mentioned chemical formula 7 to 12, R is hydrogen atom ,-(CH independently of one another or simultaneously 2) OH or-CH 2o (CH 2) mCH 3, the integer that m is 0-3, at least more than one is alkanol.
Above-mentioned f) the nitrogenous crosslinking chemical that contains silane alcohol base plays the effect of the cementability of raising and substrate, with respect to above-mentioned oligosiloxane compound 100 weight portions a), preferably contains 0.5 to 10 weight portion.
Or KP341 (trade name: etc. above-mentioned g) surfactant can be used NONIN HS 240, polyoxyethylene nonylplenyl ether, F171, F172, F173 (trade name: large Japanese ink company), FC430, FC431 (trade name: Sumitomo 3M company) chemical industrial company of SHIN-ETSU HANTOTAI).
With respect to above-mentioned oligosiloxane compound 100 weight portions a), above-mentioned surfactant preferably contains 0.0001 to 2 weight portion, and its content is in above-mentioned scope time, more useful to the raising of the coating of photosensitive composite or developability.
It is 10 to 50 % by weight that above-mentioned positive photosensitive organic-inorganic hybrid insulator composition of the present invention preferably makes solid component concentration, after the filtrations such as millipore filter with 0.1～0.2 μ m, uses.
In addition, the invention provides in order to the pattern formation method of the display device that is feature with above-mentioned positive photosensitive organic-inorganic hybrid insulator composition and take the display device that the solidfied material that contains above-mentioned positive photosensitive organic-inorganic hybrid insulator composition is feature, according to pattern formation method of the present invention, in display operation, form in the method for insulating film pattern, except using above-mentioned positive photosensitive organic-inorganic hybrid insulator composition and utilizing light operation, other operation can be suitable for known method certainly.
As concrete example, utilize above-mentioned positive photosensitive organic-inorganic hybrid insulator to form the method for pattern of display device as follows.
First, utilize spin coating, crack rotary coating, slot coated, roller coat etc., positive photosensitive organic-inorganic hybrid insulator of the present invention is coated on to substrate surface, by prebake, remove desolventizing, formation is filmed.Now, above-mentioned prebake is preferably implemented 1～3 minute at the temperature of 100～120 ℃.
Then, according to pre-prepd pattern, luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc. are radiated to filming of above-mentioned formation, with developer solution, develop, remove unnecessary part, form the pattern of regulation.
Above-mentioned developer solution is preferably used aqueous alkali, specifically can use the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, the primary amine such as ethamine, n-propylamine class, the secondary amine such as diethylamine, n-propylamine class, the tertiary amines such as trimethylamine, methyl-diethyl-amine, dimethyl amine, triethylamine, the aqueous solution of the quaternary ammonium salts such as the alcaminess such as dimethylethanolamine, methyldiethanolamine, triethanolamine or Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide etc.Now, above-mentioned developer solution is alkali compounds is dissolved to the concentration of 0.1 to 10 weight portion and uses, and can also suitably add water-miscible organic solvent and the surfactants such as methyl alcohol, ethanol.
In addition, after developing with developer solution described above, with ultrapure water, clean 30～90 seconds, remove unnecessary part, and dry, form pattern, after the light such as patterned illumination ultraviolet ray of above-mentioned formation, utilize the heating arrangements such as baking oven, by pattern heat treated 30～90 minutes at the temperature of 150～400 ℃, can obtain final pattern.
According to the pattern formation method of display of the present invention, by utilizing 1 painting process to form dielectric film, the dual structure of existing SiNx passivation/acrylic acid series photonasty organic insulating film is formed to one deck (layer), thereby can bring the simplification of operation and the saving of producing cost, not only sensitivity, resolution, process margin, the transparency, the excellent performances such as heat-resisting discolouration, particularly make insulating film with low dielectric constant become possibility, thereby can reduce power consumption, and eliminate image retention, crosstalk, and the drift phenomenon of threshold voltage, in addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability, can in various displays, not only can usefully be applicable to passivation dielectric film thus, gate insulating film, but also can usefully be applicable to planarization film etc.
Below, enumerate preferred embodiment, but following embodiment is only illustration the present invention in order to help understand the present invention, scope of the present invention is not limited to following embodiment.
Synthesis example
Synthesis example 1 (manufacture of oligosiloxane compound (A))
In possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 55 weight portions, tetraethoxysilane 20 weight portions, triethoxysilane 25 weight portions, add ethanol 100 weight portions as solvent, after nitrogen replacement, stir lentamente.In above-mentioned reaction solution, further drop into after ultrapure water 40 weight portions and oxalic acid 3 weight portions as catalyzer, again stir lentamente.After 1 hour, make above-mentioned reaction solution be warming up to 60 ℃, make this temperature maintain 10 hours, carry out, after solution polymerization, being cooled to normal temperature, finish reaction.Further, below quenching to 0 ℃, make to produce the precipitation of reactant.In addition, remove after the supernatant that contains unreacted silane, by vacuum drying (Vacume Drying), except solvent and the residual moisture of the alcohols producing in dereaction.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 4000.
Synthesis example 2 (manufacture of oligosiloxane compound (B))
In possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 55 weight portions, tetraethoxysilane 20 weight portions, triethoxysilane 25 weight portions, do not put into solvent, after nitrogen replacement, stir lentamente.In above-mentioned reaction solution, further drop into after ultrapure water 40 weight portions and nitric acid 2 weight portions as catalyzer, again stir lentamente.After 1 hour, make above-mentioned reaction solution be warming up to 60 ℃, make this temperature maintain 10 hours, carry out, after bulk polymerization, being cooled to normal temperature, finish reaction.Further, below quenching to 0 ℃, make to produce the precipitation of reactant.In addition, remove after the supernatant that contains unreacted silane, by vacuum drying, remove solvent and the residual moisture of the alcohols producing in dereaction.Finally, gpc analysis result, oligosiloxane compound solution a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 8000.
Synthesis example 3 (manufacture of oligosiloxane compound (C))
In above-mentioned synthesis example 1, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively dimethoxydiphenylsilane 60 weight portions, tetraphenoxy-silicane alkane 20 weight portions, vinyltriethoxysilane 20 weight portions, in addition, according to the method identical with above-mentioned synthesis example 1, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 3000.
Synthesis example 4 (manufacture of oligosiloxane compound (D))
In above-mentioned synthesis example 1, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively triphenyl methoxy silane 50 weight portions, tetramethoxy-silicane 40 weight portions, glycidoxy propyl-triethoxysilicane 10 weight portions, in addition, according to the method identical with above-mentioned synthesis example 1, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 6000.
Synthesis example 5 (manufacture of oligosiloxane compound (E))
In above-mentioned synthesis example 1, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively triphenyl methoxy silane 50 weight portions, four butoxy silane 25 weight portions, n-hexyl trimethoxy silane 25 weight portions, in addition, according to the method identical with above-mentioned synthesis example 1, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 4000.
Synthesis example 6 (manufacture of oligosiloxane compound (F))
In above-mentioned synthesis example 2, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively triphenyl methoxy silane 50 weight portions, four butoxy silane 25 weight portions, n-hexyl trimethoxy silane 25 weight portions, in addition, according to the method identical with above-mentioned synthesis example 2, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 8000.
Synthesis example 7 (manufacture of oligosiloxane compound (G))
In above-mentioned synthesis example 2, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 90 weight portions, tetraethoxysilane 5 weight portions, n-hexyl trimethoxy silane 5 weight portions, in addition, according to the method identical with above-mentioned synthesis example 2, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 7000.
Synthesis example 8 (manufacture of oligosiloxane compound (H))
In above-mentioned synthesis example 2, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 50 weight portions, tetraethoxysilane 15 weight portions, n-hexyl trimethoxy silane 35 weight portions, in addition, according to the method identical with above-mentioned synthesis example 2, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 10000.
Synthesis example 9 (manufacture of oligosiloxane compound (I))
In above-mentioned synthesis example 2, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 70 weight portions, tetraethoxysilane 30 weight portions, in addition, according to the method identical with above-mentioned synthesis example 2, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 1500.
Compare synthesis example 1 (manufacture of oligosiloxane compound (J))
In above-mentioned synthesis example 1, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 40 weight portions, tetraethoxysilane 15 weight portions, n-hexyl trimethoxy silane 45 weight portions, in addition, according to the method identical with above-mentioned synthesis example 1, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 10000.
Compare synthesis example 2 (manufacture of oligosiloxane compound (K))
In above-mentioned synthesis example 1, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 95 weight portions, n-hexyl trimethoxy silane 5 weight portions, in addition, according to the method identical with above-mentioned synthesis example 1, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 1000.
Compare synthesis example 3 (manufacture of oligosiloxane compound (L))
In above-mentioned synthesis example 2, in possessing the flask of condenser pipe and stirrer, as reactive silane, put into respectively phenyl triethoxysilane 20 weight portions, tetraethoxysilane 70 weight portions, n-hexyl trimethoxy silane 10 weight portions, in addition, according to the method identical with above-mentioned synthesis example 2, implement.Finally, gpc analysis result, oligosiloxane compound a) that to have manufactured polystyrene conversion weight-average molecular weight (MW) be 12000.
Synthesis example 10 (manufacture of 1,2-quinone di-azido compound (A))
Make to carry out condensation reaction by 2 moles of 1 mole of the phenolic compounds of following chemical formulation and 1,2-naphthoquinones, two nitrine-5-sulphonyl [chloride], to have manufactured esterification degree be 67% 1,2-naphthoquinones two nitrine-5-sulfonate compound.
Figure BPA00001387926500221
Synthesis example 11 (manufacture of 1,2-quinone di-azido compound (B))
Make to carry out condensation reaction by 2 moles of 1 mole of the phenolic compounds of following chemical formulation and 1,2-naphthoquinones, two nitrine-5-sulphonyl [chloride], to have manufactured esterification degree be 67% 1,2-naphthoquinones two nitrine-5-sulfonate compound.
Figure BPA00001387926500222
Synthesis example 12 (manufacture of 1,2-quinone di-azido compound (C))
Make to carry out condensation reaction by 2 moles of 1 mole of the phenolic compounds of following chemical formulation and 1,2-naphthoquinones, two nitrine-5-sulphonyl [chloride], to have manufactured esterification degree be 67% 1,2-naphthoquinones two nitrine-5-sulfonate compound.
Embodiment
Embodiment 1 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
Put into 1 of oligosiloxane compound (A) 100 weight portions of above-mentioned synthesis example 1 manufacture, 10 manufactures of above-mentioned synthesis example, 2-naphthalene quinone di-azido compound (A) 25 weight portions and as dioctyl phthalate 15 weight portions of plastifier, mix, dissolve with propylene glycol methyl ether acetate and after making solid component content be 20 weight portions, with the millipore filter of 0.1 μ m, filter, manufactured positive light sensitivity organic and inorganic blend compositions.
Embodiment 2 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (B) that replaces oligosiloxane compound (A) the use synthesis example 2 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 3 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (C) that replaces oligosiloxane compound (A) the use synthesis example 3 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 4 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (D) that replaces oligosiloxane compound (A) the use synthesis example 4 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 5 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (E) that replaces oligosiloxane compound (A) the use synthesis example 5 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 6 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (F) that replaces oligosiloxane compound (A) the use synthesis example 6 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 7 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (G) that replaces oligosiloxane compound (A) the use synthesis example 7 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 8 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (H) that replaces oligosiloxane compound (A) the use synthesis example 8 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 9 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
The oligosiloxane compound (I) that replaces oligosiloxane compound (A) the use synthesis example 9 of synthesis example 1 in above-described embodiment 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 10 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
In above-described embodiment 1, replace 1 of synthesis example 10,2-naphthoquinones two nitrine-5-sulfonate compound (A) is used 1 of synthesis example 11,2-naphthoquinones two nitrine-5-sulfonate compound (B), in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 11 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
In above-described embodiment 1, replace 1 of synthesis example 10,2-naphthoquinones two nitrine-5-sulfonate compound (A) is used 1 of synthesis example 12,2-naphthoquinones two nitrine-5-sulfonate compound (C), in addition, according to the method manufacture identical with above-described embodiment 1.
Embodiment 12 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
While manufacturing photosensitive polymer combination in above-described embodiment 1, as plastifier, replace dioctyl phthalate to use hexanedioic acid dioctyl ester, in addition, according to the method identical with above-described embodiment 1, implement, manufacture photosensitive polymer combination.
Embodiment 13 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
While manufacturing photosensitive polymer combination in above-described embodiment 1, as plastifier, replace dioctyl phthalate to use 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate, in addition, according to the method identical with above-described embodiment 1, implement, manufacture photosensitive polymer combination.
Embodiment 14 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
While manufacturing photosensitive polymer combination in above-described embodiment 1, as plastifier, do not use dioctyl phthalate, in addition, according to the method identical with above-described embodiment 1, implement, manufacture photosensitive polymer combination.
Embodiment 15 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
While manufacturing photosensitive polymer combination in above-described embodiment 1, as solvent, replace propylene glycol methyl ether acetate to use diglycol methyl ethyl ether, in addition, according to the method identical with above-described embodiment 1, implement, manufacture photosensitive polymer combination.
Comparative example 1 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
In above-described embodiment 1, replace the oligosiloxane compound (A) of synthesis example 1 to use the relatively oligosiloxane compound (J) of synthesis example 1, in addition, according to the method manufacture identical with above-described embodiment 1.
Comparative example 2 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
In above-described embodiment 1, replace the oligosiloxane compound (A) of synthesis example 1 to use the relatively oligosiloxane compound (K) of synthesis example 2, in addition, according to the method manufacture identical with above-described embodiment 1.
Comparative example 3 (manufacture of positive photosensitive organic-inorganic hybrid insulator composition)
In above-described embodiment 1, replace the oligosiloxane compound (A) of synthesis example 1 to use the relatively oligosiloxane compound (L) of synthesis example 3, in addition, according to the method manufacture identical with above-described embodiment 1.
To physical property such as above-described embodiment 1 to 15 and comparative example 1 to 3 mensuration sensitivity, resolution, process margin, transmissivity, heat-resisting discolouration, insulativity, thermotolerances, and be illustrated in following table 1.After the positive photosensitive organic-inorganic hybrid insulator composition that use spin coating instrument is manufactured be coated with above-described embodiment 1 to 15 and comparative example 1 to 3 on glass (glass) substrate in, with 100 ℃ of prebakes 2 minutes on hot plate, forming thickness is the film of 3.6 μ m.
One) sensitivity: the intensity under 435nm that is 1: 1 CD benchmark Dose amount of 10 μ m Line & Space to film use predetermined pattern mask (pattern mask) illumination sensitivity as above-mentioned formation is 20mW/cm 2ultraviolet ray after, by the aqueous solution of Tetramethylammonium hydroxide 2.38 % by weight, at 23 ℃, develop after 1 minute, with ultrapure water, clean 1 minute.
Then, to the intensity under the patterned illumination 435nm of above-mentioned development, be 20mW/cm 2ultraviolet 500mJ/cm 2, in baking oven, with 230 ℃, solidify 60 minutes, thereby obtained thickness, be the pattern film of 3.0 μ m.
Two) minimum value of pattern (Pattern) film forming during sensitivity determination resolution: with above-mentioned one) is measured.
Three) during sensitivity determination process margin: according to above-mentioned), identical method forms pattern (Pattern) film, with 1: 1 CD benchmark of 10 μ m Line & Space, measures the CD rate of change before and after solidifying.Now, the information slip that is 0～10% by rate of change is shown zero, and 10～20% information slip is shown to △, the information slip that surpasses 20% is shown *.
Four) pattern (Pattern) film that forms during transparent: the evaluation of the transparency is by above-mentioned) sensitivity determination, utilizes the transmissivity of the 400nm of spectrophotometric determination pattern film.By transmissivity now, be that more than 90% information slip is shown zero, 85～90% information slip is shown to △, be less than 80% information slip to be shown *.
Five) the mensuration substrate when transparency heat-resisting discolouration: by above-mentioned four) is evaluated further solidifies 40 minutes in the baking oven of 300 ℃, by the 400nm transmission change of pattern (Pattern) film before and after solidifying, evaluates heat-resisting discolouration.Rate of change is now less than to 5% information slip and is shown zero, 5～10% information slip is shown to △, the information slip that surpasses 10% is shown *.
Six) insulativity: take specific inductive capacity as benchmark judgement insulativity.Specific inductive capacity is the static capacity of measuring capacitor, by following formula, obtains.Forming between the upper and lower metal electrode of pattern with gold of 1cm2 area, according to above-mentioned one) sensitivity determination time identical formation method form after positive photosensitive organic-inorganic hybrid insulator, the element consisting of MIM (Metal/Insulator/Metal) structure is measured to static capacity by electric impedance analyzer, by following formula, calculate specific inductive capacity separately.
C (static capacity)=ε 0(permittivity of vacuum) * ε r(dielectric film is than specific inductive capacity) * A (useful area)/d (dielectric film thickness)
To measure above-mentioned specific inductive capacity, 2.5～2.8 information slip is shown to zero, 2.8～3.2 information slip and is shown △, 3.2 information slip is shown *.
Seven) thermotolerance: utilize TGA to measure thermotolerance.To above-mentioned one) sensitivity determination time after pattern (Pattern) film that forms samples, utilize TGA from normal temperature, to be warming up to 900 ℃ with 10 ℃ of per minutes.5 % by weight weightless temperatures are surpassed to the information slip of 350 ℃, and to be shown zero, 5 % by weight weightless temperature be that the information slip of 300-350 ℃ is shown △, 5 % by weight weightless temperatures are less than the information slip of 300 ℃ and are shown *.
Table 1
Figure BPA00001387926500271
Known by above-mentioned table 1, the performances such as the sensitivity of the positive photosensitive organic-inorganic hybrid insulator composition of manufacturing in embodiment 1 to 15 according to the present invention, resolution, process margin, the transparency, heat-resisting discolouration are all excellent, particularly insulativity is than comparative example 1 to 3 excellence, thereby can reduce power consumption, can eliminate image retention, crosstalk, the drift phenomenon of threshold voltage.In addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability.Knownly in utilizing its various display operations, can be suitable for positive photosensitive organic-inorganic hybrid insulator.
In industry, utilize possibility
Positive photosensitive organic-inorganic hybrid insulator composition according to the present invention forms one deck (layer) by the dual structure of existing SiNx passivation/acrylic acid series photonasty organic insulating film, thereby can bring the simplification of operation and the saving of producing cost, not only sensitivity, resolution, process margin, the transparency, the excellent performances such as heat-resisting discolouration, particularly make insulating film with low dielectric constant become possibility, thereby can reduce power consumption, and eliminate image retention, crosstalk, and the drift phenomenon of threshold voltage, in addition, make the low outgas that excellent thermotolerance is brought become possibility, thereby can guarantee excellent panel reliability, can in various displays, not only can usefully be applicable to passivation dielectric film thus, gate insulating film, but also can usefully be applicable to planarization film etc.

Claims (12)

1. a positive photosensitive organic-inorganic hybrid insulator composition, it is characterized in that, contain a) oligosiloxane compound 100 weight portions, this oligosiloxane compound is that making with respect to whole total silane monomers is the i of 50-90 weight portion) reactive silane that contains 1-3 phenyl that represented by following Chemical formula 1, with respect to whole total silane monomers, being the ii of 10-50 weight portion) 4 functional response's property silane of being represented by following Chemical formula 2 are hydrolyzed under catalyzer exists and polycondensation obtains, the polystyrene conversion weight-average molecular weight Mw of this oligosiloxane compound is 1, 000 to 2, 0000, b) 1,2-quinone di-azido compound 5 to 50 weight portions, and c) making solid component content is the solvent of 10-50 % by weight,
[Chemical formula 1]
(R 1)nSi(R 2) 4-n
In described Chemical formula 1, R 1for phenyl, R 2be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another, the integer that n is 1-3,
[Chemical formula 2]
Si(R 3) 4
In described Chemical formula 2, R 3be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another.
2. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, it is the iii of 10-50 weight portion that the reactive silane that forms described a) oligosiloxane compound further contains with respect to all total silane monomers) reactive silane that represented by following chemical formula 3, here, all total silane monomers add up to 100 weight portions
[chemical formula 3]
(R 4)nSi(R 5) 4-n
In described chemical formula 3, R 4be alkoxy, phenoxy group or the acetoxyl group of carbon number 1-4 independently of one another, R 5be alkyl, aryl, epoxy radicals, vinyl, hexenyl, acryloyl group, methacryl or the allyl of hydrogen, carbon number 1-10 independently of one another, the integer that n is 1-3.
3. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, described b) 1,2-quinone di-azido compound reacts the phenolic compounds being represented by following chemical formula 4 and naphthoquinones two nitrine sulfuryl halides to obtain,
[chemical formula 4]
Figure FDA00003293606300021
In described chemical formula 4, R 1to R 6be alkyl, alkenyl or the hydroxyl of hydrogen, halogen, carbon number 1-4 independently of one another, R 7and R 8be the alkyl of hydrogen, halogen, carbon number 1-4 independently of one another, R 9alkyl for hydrogen or carbon number 1-4.
4. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, described b) 1,2-quinone di-azido compound is choosing free 1,2-quinone two nitrine 4-sulphonic acid esters, 1, in the group that 2-quinone two nitrine 5-sulphonic acid esters and 1,2-quinone two nitrine 6-sulphonic acid esters form more than a kind.
5. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, described c) solvent is for selecting free methyl alcohol, ethanol, benzylalcohol, hexanol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether propionic ester, ethylene glycol ethyl ether propionic ester, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diglycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol list ether, in the group that dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether form more than a kind.
6. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, described positive photosensitive organic-inorganic hybrid insulator composition also contains and selects free dioctyl phthalate, diisononyl phthalate, dioctyl adipate, tricresyl phosphate and 2,2,4-trimethyl-1, a kind of above d in the group that 3-pentanediol mono isobutyrate forms) plastifier.
7. positive photosensitive organic-inorganic hybrid insulator composition according to claim 1, wherein, described positive photosensitive organic-inorganic hybrid insulator composition also contain select free d) plastifier 5-20 weight portion, e) epoxy resin 0.5-10 weight portion, f) the nitrogenous crosslinking chemical 0.5-10 weight portion and the h that contain silane alcohol base) a kind of above adjuvant in the group that forms of surfactant 0.0001-2 weight portion.
8. a pattern formation method for display device, is characterized in that, right to use requires the positive photosensitive organic-inorganic hybrid insulator composition described in any one in 1 to 7.
9. the pattern formation method of display device according to claim 8, wherein, using described positive photosensitive organic-inorganic hybrid insulator composition as TFT-LCD, the passivation dielectric film of OLED or O-TFT utilizes.
10. the pattern formation method of display device according to claim 8, wherein, using described positive photosensitive organic-inorganic hybrid insulator composition as TFT-LCD, the gate insulating film of OLED or O-TFT utilizes.
The pattern formation method of 11. display devices according to claim 8, wherein, using described positive photosensitive organic-inorganic hybrid insulator composition as TFT-LCD, the planarization film of OLED or O-TFT utilizes.
12. 1 kinds of display devices, is characterized in that, the solidfied material that contains the positive photosensitive organic-inorganic hybrid insulator composition described in any one in claim 1 to 7.
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