CN1983031A - Photosensitive resin composition for organic light emitting diodes - Google Patents
Photosensitive resin composition for organic light emitting diodes Download PDFInfo
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- CN1983031A CN1983031A CN 200610163334 CN200610163334A CN1983031A CN 1983031 A CN1983031 A CN 1983031A CN 200610163334 CN200610163334 CN 200610163334 CN 200610163334 A CN200610163334 A CN 200610163334A CN 1983031 A CN1983031 A CN 1983031A
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Abstract
The invention provides a photosensitive resin composition for organic light-emmiting diode(OLED), which has excellent performance such as sensitivity and low dielectric property, and particularly, which can simultaneously form patterns of insulator and isolator using a photosensitive resin composition to shorten the working procedure time, furthermore, the numerical aperture of panel is greatly improved, suitable for manufacture process of OLED. The photosensitive resin composition for OLED of the invention is characterised in that it comprises: a)novolak resins manufactured by step polymerization; b)1,2-diazidoquinone compound; c)photo-acid generator; d)cross linking agent of melamine; and e)solvent.
Description
Technical field
The present invention relates to Organic Light Emitting Diode (OLED, organic light emitting diodes) uses photosensitive polymer combination, more particularly, relate to following photosensitive polymer combination, its sensitivity, all excellent performances such as low dielectric property, particularly can utilize a kind of photosensitive polymer combination to form the pattern of insulator (insulator) and these two kinds of forms of isolated body (separator) simultaneously, can shorten activity time, moreover, also obviously improve the numerical aperture (aperture opening ratio) on the panel (panel) simultaneously, be suitable for OLED manufacturing process.
Background technology
Recently, in the manufacturing process of OLED, LCD, PDP etc., requirement can be shortened activity time, obtain the photoresist (photoresist) and the operation exploitation of excellent numerical aperture.
The insulator that uses in the existing OLED manufacturing process contains compositions such as PAC, bonding agent, solvent, described bonding agent mainly uses acrylic compounds, imines class, and isolated body uses the negative photoresist (negative photoresist) that contains compositions such as PAG, novolac resin (novolac resin), crosslinking chemical, solvent.But, when forming existing insulator and isolated body, there is the long problem of activity time owing to carrying out 2 steps (2-step) operation, when on insulator, carrying out isolated body arrangement (separator Align), there is the problem that causes numerical aperture to reduce in order to ensure arranging width (Align Margin).
Therefore, actual conditions now are for shortening applied insulator and the activity time of isolated body formation operation and the numerical aperture of guaranteeing excellence in the OLED manufacturing process, need further study.
Summary of the invention
The present invention proposes in order to solve above-mentioned existing technical matters, its purpose is to provide a kind of OLED photosensitive polymer combination, the oled substrate that contains the solidfied material of described photosensitive polymer combination, and the pattern formation method of having used the oled substrate of described photosensitive polymer combination, for described OLED photosensitive polymer combination, not only can form the pattern of insulator and these two kinds of forms of isolated body with a kind of photosensitive polymer combination simultaneously, thereby can shorten activity time, can also obviously improve simultaneously the numerical aperture on the panel, be suitable for OLED manufacturing process.
Another object of the present invention is to, provide a kind of OLED with photosensitive polymer combination, the oled substrate of solidfied material that comprises described photosensitive polymer combination and the pattern formation method of having used the oled substrate of described photosensitive polymer combination, all excellent performances such as the described OLED sensitivity of photosensitive polymer combination, low dielectric property, can shorten activity time, improve numerical aperture, thereby be suitable for OLED manufacturing process.
In order to achieve the above object, the invention provides a kind of OLED photosensitive polymer combination, this OLED is characterised in that with photosensitive polymer combination it contains:
A) pass through the novolac resin (novolac resin) that progressively polymerization is made;
B) 1,2-two nitrine naphtoquinone compounds;
C) photo-acid generator;
D) melamine class crosslinking chemical; And
E) solvent.
Preferably, OLED of the present invention uses in the photosensitive polymer combination, and the novolac resin that a) passes through progressively polymerization manufacturing with respect to 100 weight portions also contains:
The b of 5 weight portions～100 weight portions) 1,2-two nitrine naphtoquinone compounds;
The c of 1 weight portion～20 weight portions) photo-acid generator;
The d of 1 weight portion～30 weight portions) melamine class crosslinking chemical; And
Making the solid component content in the photosensitive polymer combination is the e of 10 weight %～50 weight %) solvent.
And, the invention provides the oled substrate of the solidfied material that comprises described photosensitive polymer combination.
In addition, the invention provides the pattern formation method of the oled substrate that has used described photosensitive polymer combination.
Photosensitive polymer combination of the present invention, all excellent performances such as its sensitivity, low dielectric property, the pattern that particularly can enough a kind of photosensitive polymer combinations forms insulator and these two kinds of forms of isolated body simultaneously, thereby can shorten activity time, moreover, can also obviously improve simultaneously the numerical aperture on the panel, have the effect that is suitable for OLED manufacturing process.
Description of drawings
Figure 1 shows that the formation pattern of the angle of forward pattern among the embodiment;
Figure 2 shows that the formation pattern of the angle of negative sense pattern among the embodiment.
Embodiment
Below, describe the present invention in detail.
OLED of the present invention is characterised in that with photosensitive polymer combination it contains: a) pass through the novolac resin that progressively polymerization is made; B) 1,2-two nitrine naphtoquinone compounds; C) photo-acid generator; D) melamine class crosslinking chemical; And e) solvent.
For the described novolac resin of a) making by polymerization progressively that uses among the present invention, it forms crosslinked combination in the presence of crosslinked combination, thereby is insoluble to alkaline-based developer; And before crosslinked combination, be solubility to alkaline-based developer, can form pattern.
Described novolac resin by progressively polymerization manufacturing can be made by making aldehyde and substituted phenol carry out condensation.Described aldehyde comprises formaldehyde etc., and substituted phenol comprises orthoresol, metacresol, paracresol, 2,4-xylenols, 2,5-xylenols, 3,4-xylenols, 3,5-xylenols, 2,3,5-pseudocuminol or their potpourri etc.
The polystyrene conversion weight-average molecular weight of described novolac resin by progressively polymerization manufacturing is preferably 3,000～30, and 000, more preferably 3,000～20,000.The weight-average molecular weight of the described novolac resin of making by polymerization progressively is less than 3,000 o'clock, has the declines such as development, residual film ratio of photosensitive polymer combination, or the problem that descends such as pattern development, thermotolerance; Greater than 30,000 o'clock, there is the problem that sensitivity descends or pattern development descends of photosensitive polymer combination.
The described b that uses among the present invention) 1,2-two nitrine naphtoquinone compounds use as photosensitive compounds in photosensitive polymer combination.
Described 1,2-two nitrine naphtoquinone compounds can use 1,2-two nitrine quinone 4-sulphonic acid esters, 1,2-two nitrine quinone 5-sulphonic acid esters or 1,2-two nitrine quinone 6-sulphonic acid esters etc.
Described two nitrine naphtoquinone compounds can be made by diazido naphthoquinone sulfonyl halogen compound and phenolic compound are reacted.
As described phenolic compound, can use 2,3, the 4-trihydroxybenzophenone, 2,4, the 6-trihydroxybenzophenone, 2,2 '-tetrahydroxybenzophenone, 4,4 '-tetrahydroxybenzophenone, 2,3,4,3 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone, 2,3,4,2 '-pentahydroxybenzophenone, 2,3,4,6 '-pentahydroxybenzophenone, 2,4,6,3 '-hexahydroxy benzophenone, 2,4,6,4 '-hexahydroxy benzophenone, 2,4,6,5 '-hexahydroxy benzophenone, 3,4,5,3 '-hexahydroxy benzophenone, 3,4,5,4 '-hexahydroxy benzophenone, 3,4,5,5 '-hexahydroxy benzophenone, two (2, the 4-dihydroxy phenyl) methane, two (p-hydroxybenzene) methane, three (p-hydroxybenzene) methane, 1,1,1-three (p-hydroxybenzene) ethane, two (2,3,4-trihydroxy phenyl) methane, 2,2-two (2,3,4-trihydroxy phenyl) propane, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-the 3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] biphenol, or two (2,5-dimethyl 4-hydroxy phenyl)-2-hydroxy phenyl methane etc., described compound can be used separately, or mix more than 2 kinds and use.
When adopting described phenolic compound and diazido naphthoquinone sulfonyl halogen compound to synthesize two nitrine naphtoquinone compounds, esterification degree is preferably 50%～90%.Described esterification degree was less than 50% o'clock, and the residual film ratio variation greater than 90% o'clock, has the problem that produces scum on pattern sometimes.
With respect to the novolac resin of a) making by polymerization progressively of 100 weight portions, described 1, the content of 2-two nitrine naphtoquinone compounds is preferably 5 weight portions～100 weight portions, more preferably 10 weight portions～50 weight portions.Its content is during less than 5 weight portions, poor solubility between exposure portion and the non-exposure portion reduces, be difficult to form pattern, if greater than 100 weight portions, then in the short irradiation light time, residual more unreacted 1,2-two nitrine naphtoquinone compounds, low excessively, there is the problem that is difficult to develop as the solubleness in the alkaline aqueous solution of developer solution.
The described c that uses among the present invention) photo-acid generator functions as follows: it forms acid by exposure or post exposure bake and spreads, cause a) novolac resin and the d that make by polymerization progressively) cross-linking reaction of melamine class crosslinking chemical, form pattern.
Described photo-acid generator can preferably use sulfosalt, salt compounded of iodine isoiony photo-acid generator, sulphonyl diazomethane class (sulfonyl diazomethane), N-sulphonyl oxygen imines (N-sulfonyloxyimide) class, benzoin sulfonate (ベ Application ゾ イ Application ス Le ホ ネ one foretells) class, nitrobenzyl Sulfonates, sulfone class, glyoxime class or triazines etc. so long as the compound that can utilize light to generate acid all can use.
Specifically, described sulfosalt is the salt of sulfonium cation and sulfonate (sulfonic acid anion), described sulfonium cation comprises trisphenol sulfonium (foretelling リ Off エ ノ one Le ス Le ホ ニ ウ system), (4-tert-butoxy phenyl) diphenyl sulfonium, two (4-tert-butoxy phenyl) phenyl sulfonium, 4-aminomethyl phenyl diphenyl sulfonium, three (4-aminomethyl phenyl sulfoniums), 4-tert-butyl-phenyl diphenyl sulfonium, three (4-tert-butyl-phenyl) sulfonium, three (4-tert-butoxy phenyl) sulfonium, (3-tert-butoxy phenyl) diphenyl sulfonium, two (3-tert-butoxy phenyl) phenyl sulfonium, three (3-tert-butoxy phenyl) sulfonium, (3,4-two tert-butoxy phenyl) diphenyl sulfonium, two (3,4-two tert-butoxy phenyl) phenyl sulfonium, three (3,4-two tert-butoxy phenyl) sulfonium, diphenyl (4-sulphur Phenoxyphenyl) sulfonium, (4-tert-butoxycarbonyl methoxyphenyl) diphenyl sulfonium, three (4-tert-butoxycarbonyl methoxyphenyl) sulfonium, (4-tert-butoxy phenyl) two (4-dimethylaminophenyl) sulfonium, three (4-dimethylaminophenyl) sulfonium,-2-naphthyl diphenyl sulfonium, dimethyl-2-naphthyl sulfonium, 4-hydroxy phenyl dimethyl sulfonium, 40 methoxyphenyl dimethyl sulfoniums, trimethylsulfonium, the diphenyl methyl sulfonium, methyl-2 oxopropyl phenyl sulfonium, 2-oxo cyclohexyl ring hexyl methyl sulfonium, three naphthyl sulfoniums, or the tribenzyl sulfonium etc., described sulfonate comprises trifluoro-methanyl sulfonate, nine fluorine butane sulfonate, 17 perfluoroctanesulfonic acid salt, 2,2,2-HFC-143a sulfonate, phenyl-pentafluoride sulfonate, 4-trifluoromethyl benzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camsilate, Perfluorooctane sulfonate, dodecyl benzene sulfonate, butane sulfonate, or methane sulfonates etc.
Described salt compounded of iodine is the salt of iodine kation and sulfonate (sulfonic acid anion), described iodine kation comprises diphenyl iodine, two (4-tert-butyl-phenyl) iodine, 4-tert-butoxy phenyl iodine, or 4-methoxyphenyl phenyl-iodide etc., described sulfonate comprises trifluoro-methanyl sulfonate, nine fluorine butane sulfonate, 17 perfluoroctanesulfonic acid salt, 2,2,2-HFC-143a sulfonate, phenyl-pentafluoride sulfonate, 4-trifluoromethyl benzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camsilate, Perfluorooctane sulfonate, dodecyl benzene sulfonate, butane sulfonate, or methane sulfonates etc.
Described sulphonyl diazomethane class photo-acid generator comprises two (ethylsulfonyl) diazomethane; two (1-methyl-propyl sulfonyl) diazomethane; two (2-methyl-propyl sulfonyl) diazomethane; two (1; 1-dimethyl ethyl sulfonyl) diazomethane; two (cyclohexyl sulfonyl) diazomethane; two (perfluor isopropyl sulfonyl) diazomethane; two (phenyl sulfonyl) diazomethane; two (4-aminomethyl phenyl sulfonyl) diazomethane; two (2,4-3,5-dimethylphenyl sulfonyl) diazomethane; two (2-naphthyl sulfonyl) diazomethane; 4-aminomethyl phenyl sulfonyl benzoyl diazomethane; tert-butyl group carbonyl-4-aminomethyl phenyl sulfonyl diazomethane; 2-naphthyl sulfonyl benzoyl diazomethane; 4-aminomethyl phenyl sulfonyl-2-naphthalene formyl diazomethane; methyl sulphonyl benzoyl diazomethane; or tert-butoxycarbonyl-disulfonyl basic weight n-formyl sarcolysine alkane and sulfonyl carbonyl diazomethanes such as 4-aminomethyl phenyl sulphonyl diazomethane.
Described N-sulphonyl oxygen imines class photo-acid generator comprises succinimide, benzene-naphthalene diimide, phthalimide, the cyclohexyl diimide, 5-norborene-2, the 3-diimide, or 7-oxabicyclo [2,2,1]-5-heptene-2, imines skeleton and trifluoro-methanyl sulfonates such as 3-diimide, nine fluorine butane sulfonate, 17 perfluoroctanesulfonic acid salt, 2,2,2-HFC-143a sulfonate, phenyl-pentafluoride sulfonate, 4-trifluoromethyl benzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camsilate, Perfluorooctane sulfonate, dodecyl benzene sulfonate, butane sulfonate, or the compound of methane sulfonates etc.
As described benzoin Sulfonates photo-acid generator, can enumerate benzoin toluene sulfonate, benzoin mesylate or benzoin butane sulfonate etc.
Described nitrobenzyl Sulfonates photo-acid generator comprises 2,4-dinitro benzyl sulfonate, 2-nitrobenzyl sulfonate or 2,6-dinitro benzyl sulfonate etc., described sulfonate comprises trifluoro-methanyl sulfonate, nine fluorine butane sulfonate, 17 perfluoroctanesulfonic acid salt, 2,2,2-HFC-143a sulfonate, phenyl-pentafluoride sulfonate, 4-trifluoromethyl benzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camsilate, Perfluorooctane sulfonate, dodecyl benzene sulfonate, butane sulfonate or methane sulfonates etc.And, can also use the compound that the nitro of benzyl side is substituted by trifluoromethyl.
Described sulfone class photo-acid generator comprises two (phenyl sulfonyl) methane, two (4-aminomethyl phenyl sulfonyl) methane, two (2-naphthyl sulfonyl) methane, 2; 2-two (phenyl sulfonyl) propane, 2; 2-two (4-aminomethyl phenyl sulfonyl) propane, 2; 2-two (2-naphthyl sulfonyl) propane, 2-methyl-2-(p-toluenesulfonyl) acetone (acetone; プ ロ ピ オ ネ ノ Application), 2-(cyclohexyl-carbonyl)-2-(p-toluenesulfonyl) propane or 2,4-dimethyl-2-(p-toluenesulfonyl) pentane-3-ketone etc.
Described glyoxime class photo-acid generator comprises two-adjacent (p-toluenesulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (p-toluenesulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (p-toluenesulfonyl)-α-dicyclohexyl glyoxime; two-adjacent (p-toluenesulfonyl)-2; 3-pentane diketone glyoxime; two-adjacent (p-toluenesulfonyl)-2-methyl-3; 4-pentane diketone glyoxime; two-adjacent (normal butane sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (normal butane sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (normal butane sulfonyl)-α-dicyclohexyl glyoxime; two-adjacent (normal butane sulfonyl)-2; 3-pentane diketone glyoxime; two-adjacent (normal butane sulfonyl)-2-methyl-3; 4-pentane diketone glyoxime; two-adjacent (methane sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (trifluoromethane sulfonyl group)-alpha-alpha-dimethyl glyoxime; two-adjacent (1; 1,1-HFC-143a sulfonyl)-the alpha-alpha-dimethyl glyoxime; two-adjacent (uncle's butane sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (PFO sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (cyclohexyl sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (benzenesulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (to the fluorobenzene sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (to the tert-butyl benzene sulfonyl)-alpha-alpha-dimethyl glyoxime; two-adjacent (dimethylbenzene sulfonyl)-alpha-alpha-dimethyl glyoxime; or two-adjacent (camphor sulfonyl)-alpha-alpha-dimethyl glyoxime etc.
Described triazines photo-acid generator comprises PDM-triazine, WS-triazine, PDM-triazine, dimethoxy-triazine, MP-triazine, TFE-triazine or TME-triazine (three and chemical company) etc.
With respect to the novolac resin that a) passes through progressively polymerization manufacturing of 100 weight portions, the content of described photo-acid generator is preferably 1 weight portion～20 weight portions, more preferably 1 weight portion～10 weight portions.Its content is during less than 1 weight portion, the problem that exists sensitivity (photospeed) to descend; During greater than 20 weight portions, the problem that exists gas leakage (outgassing) and storage stability to descend.
The described d that uses among the present invention) the melamine class crosslinking chemical plays and a) forms by the novolac resin of progressively polymerization manufacturing the effect of cross-linked structure.
As described melamine class crosslinking chemical, can use condensation product or the hydroxymethyl urea alkyl ether that obtains by alcohol, the melamine methylol alkyl ether etc. of condensation product, melamine and the formaldehyde of urea and formaldehyde.
Specifically, as the condensation product of described urea and formaldehyde, can use monomethylol urea, dihydroxymethyl urea etc.As the condensation product of described melamine and formaldehyde, can use hexamethylolmelamine, in addition, can also use the part condensation product of melamine and formaldehyde.
And, described hydroxymethyl urea alkyl ether be make urea and formaldehyde condensation product methylol partly or entirely react the material that obtains with alcohols, as concrete example, can use monomethyl urea methyl ether, dimethyl urea methyl ether etc.Described melamine methylol alkyl ether be make melamine and formaldehyde condensation product methylol partly or entirely react the material that obtains with alcohols, as concrete example, can use hexamethylolmelamine pregnancy ether, hexamethylolmelamine six butyl ether etc.And, the hydrogen atom of amino that also can use the hydrogen atom of the amino of melamine to be substituted by compound, the melamine of the structure of methylol and methoxy is substituted by the compound etc. of the structure of butoxymethyl and methoxy, especially preferably uses the melamine methylol alkyl ether.
With respect to the novolac resin that a) passes through progressively polymerization manufacturing of 100 weight portions, the content of described melamine class crosslinking chemical is preferably 1 weight portion～30 weight portions, more preferably 1 weight portion～20 weight portions.Its content is during less than 1 weight portion, the problem that exists sensitivity to descend; During greater than 30 weight portions, the problem that exists storage stability to descend.
The described e that uses among the present invention) solvent functions as follows: it is used to form uniform pattern contour (pattem profile), thereby realizes the flatness of insulator and isolated body, and makes it not produce the coating spot.
Described solvent can use alcohols such as methyl alcohol, ethanol, benzyl alcohol, hexanol; Ethylene glycol alkyl ether acetate esters such as Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate; Ethylene glycol alkyl ether propionic acid esters such as Ethylene Glycol Methyl ether propionic ester, glycol ethyl ether propionic ester; Ethylene glycol monoalkyl ether classes such as Ethylene Glycol Methyl ether, glycol ethyl ether; Diglycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diglycol methyl ethyl ether; Propylene glycol alkyl ether acetic acid ester classes such as methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters; Propylene glycol alkyl ether propionic acid esters such as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester; Propylene-glycol monoalky lether classes such as methyl proxitol, propylene glycol ethylether, propylene glycol propyl ether, propylene glycol butyl ether; Dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; Butylene glycol monomethyl ether classes such as butylene glycol monomethyl ether, butylene glycol list ether; Or dibutylene glycol alkyl ethers such as dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether etc.
The content of described solvent is preferably the amount that the solid component content that makes all photosensitive polymer combinations reaches 10 weight %～50 weight %, more preferably makes the solid component content of all photosensitive polymer combinations reach the amount of 15 weight %～40 weight %.The solid component content of described all compositions is during less than 10 weight %, the coating thickness attenuation, and the problem that exists the coating flatness to descend, during greater than 50 weight %, coating thickness thickens, and when having coating apparatus for coating is applied the problem of burden.
Can in containing the photosensitive polymer combination of the present invention of described composition, append f as required) surfactant.
And described surfactant plays the coating that improves photosensitive composite, the effect of development.
Described surfactant can use NONIN HS 240, polyoxyethylene nonylplenyl ether, F171, F172, F173 (trade name: Dainippon Ink. ﹠ Chemicals Inc makes), FC430, FC431 (trade name: 3M Co., Ltd. in Sumitomo makes) or KP341 (trade name: Shin-Etsu Chemial Co., Ltd makes) etc.
The described novolac resin that a) passes through progressively polymerization manufacturing with respect to 100 weight portions, the content of described surfactant is preferably 0.0001 weight portion～2 weight portions, its content is in described scope the time, and is more excellent aspect the coating that improves photosensitive composite, development.
Contain in the photosensitive polymer combination of the present invention of described composition, solid component concentration is preferably 10 weight portions～50 weight portions, uses after the composition that preferably will have a solid constituent of described scope filters with Mi Libo (millipore) filtering membrane etc. of 0.1 μ m～0.2 μ m.
And, the pattern formation method that the invention provides the oled substrate of the solidfied material that contains described photosensitive polymer combination and used the oled substrate of described photosensitive polymer combination.
The pattern formation method of oled substrate of the present invention is characterised in that, forms simultaneously in insulator and the method for patterning of isolated body with the formation oled substrate at the usability photosensitive resin composition, uses described photosensitive polymer combination.
As concrete example, it is as follows to use described photosensitive polymer combination to form the method for patterning of oled substrate.
At first, utilize spraying process, rolling method, spin-coating method etc. to be coated with photosensitive polymer combination of the present invention, remove by prebake and desolvate, form coated film at substrate surface.At this moment, described prebake was preferably implemented 1 minute～15 minutes under 80 ℃～120 ℃ temperature.
Afterwards, visible light, ultraviolet ray, far ultraviolet, electronics line, X line etc. are arrived the coated film of described formation by pre-prepd patterned illumination, implement post exposure bake (PEB) and flood exposure (Flood Exposure) as required afterwards, develop with developer solution, remove unwanted part, thereby form predetermined pattern.
For above-mentioned developer solution, preferably use alkaline aqueous solution, specifically, can use inorganic bases such as NaOH, potassium hydroxide, sodium carbonate; Primary amine such as ethamine, n-propylamine class; Secondary amine such as diethylamine, n-propylamine class; Tertiary amines such as Trimethylamine, methyl-diethyl-amine, dimethyl amine, triethylamine; Alkanol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; Or the aqueous solution of quaternary ammonium salts such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide etc.At this moment, above-mentioned developer solution can dissolve alkali compounds with the concentration of 0.1 weight %～10 weight % and use, and can also suitably add such as water-miscible organic solvent and surfactants such as methyl alcohol, ethanol.
And, after developing with described developer solution, with ultrapure water washing 30 seconds～90 seconds, remove unwanted part, carry out drying, form pattern, utilize heating arrangement such as baking oven pattern to be carried out 30 minutes～90 minutes heat treated, thereby can access final pattern 130 ℃～250 ℃ temperature.
Based on all excellent performances such as the sensitivity of photosensitive polymer combination of the present invention, low dielectric properties, the pattern that particularly can enough a kind of photosensitive polymer combinations forms insulator and these two kinds of forms of isolated body simultaneously, not only can shorten activity time, can also obviously improve simultaneously the numerical aperture on the panel, be adapted at using in the OLED manufacturing process.
Below, in order to help understanding of the present invention, preferred embodiment is shown, but following embodiment example of the present invention only, scope of the present invention is not limited to following embodiment.
[embodiment]
Embodiment 1
(manufacturing novolac resin)
In overhead type stirring machine (overhead mixer), add 45g metacresol, 55g paracresol, 65g formaldehyde and 0.5g oxalic acid, stir, make uniform homogeneous blend.In 95 ℃ of described uniform homogeneous blends of heating, kept this temperature 4 hours.Reflux condenser is replaced with distilling apparatus, the temperature of uniform homogeneous blend is controlled at 110 ℃ of distillations 2 hours.Carry out vacuum distillation in 2 hours in 180 ℃, residual monomer is removed in distillation, at room temperature with the novolac resin cooling of fusion.Afterwards, utilize GPC to measure weight-average molecular weight, obtain weight-average molecular weight and be 3500 novolac resin.At this moment, weight-average molecular weight is to use the polystyrene conversion mean molecular weight that GPC measures.
(making 1,2-two nitrine naphtoquinone compounds)
Make 1 mole 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] and biphenol and 2 moles 1,2-diazido naphthoquinone-5-sulfonic acid [chloride] carries out condensation reaction, make 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] biphenol 1,2-diazido naphthoquinone-5-sulphonic acid ester.
(manufacturing photosensitive polymer combination)
With 4 of the above-mentioned novolac resin of making by polymerization progressively of 100 weight portions, the above-mentioned manufacturing of 30 weight portions, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] biphenol 1,2-diazido naphthoquinone-5-sulphonic acid ester, 3 weight portions mix as the triazines TME-triazine (TME-Triazine) of photo-acid generator and the 5 weight portions hexamethylolmelamine as melamine crosslinkers.Afterwards, said mixture is dissolved with the dipropylene glycol dimethyl ether, so that solid component content is 20 weight %, the Mi Libo filtering membrane with 0.2 μ m filters then, makes photosensitive polymer combination.
Embodiment 2
In described embodiment 1, during the polymerization novolac resin,, use 70g metacresol and 30g xylenols to substitute 45g metacresol and 55g paracresol, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1 as monomer.
Embodiment 3
In described embodiment 1 during the polymerization novolac resin, as monomer, use 35g metacresol, 40g paracresol and 25g xylenols to substitute 45g metacresol and 55g paracresol, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Embodiment 4
In described embodiment 1 during the polymerization novolac resin, as monomer, use 40g metacresol, 40g paracresol and 20g pseudocuminol to substitute 45g metacresol and 55g paracresol, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Embodiment 5
When in described embodiment 1, making photosensitive polymer combination, use sulfosalt class trisphenol sulfonium and (4-tert-butoxy phenyl) diphenyl sulfonium to substitute triazines TME-triazine as photo-acid generator, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Embodiment 6
When in described embodiment 1, making photosensitive polymer combination, two (4-tert-butyl-phenyl) iodine of use salt compounded of iodine class substitute the triazines TME-triazine (TME-Triazine) as photo-acid generator, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Embodiment 7
When in described embodiment 1, making photosensitive polymer combination; use two (ethylsulfonyl) diazomethane substitutes the triazines TME-triazine as photo-acid generator; in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Embodiment 8
When in described embodiment 1, making photosensitive polymer combination, use nitrobenzyl Sulfonates 2,4-dinitro benzyl sulfonate substitutes the triazines TME-triazine as photo-acid generator, in addition, adopts the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Comparative example 1
When in described embodiment 1, making photosensitive polymer combination, do not use triazines TME-triazine, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1 as photo-acid generator.
Comparative example 2
When in described embodiment 1, making photosensitive polymer combination, do not use 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] biphenol 1,2-diazido naphthoquinone-5-sulphonic acid ester, in addition, adopt the method manufacturing photosensitive polymer combination identical with described embodiment 1.
Use the photosensitive polymer combination of making in described embodiment 1～8 and the comparative example 1～2, adopt method as described below to estimate after the rerum natura, it be the results are shown in following table 1.
I) axial sensitivity
Use spin coater at evaporation after the photosensitive polymer combination of making in the described embodiment 1～8 of coating and the comparative example 1～2 on the 370mm of ITO * 470mm glass substrate, in 110 ℃ of preliminary dryings 2 minutes on hot plate, forming thickness is the film of 2.0 μ m.With the intensity of 435nm is 20mW/cm
2The ultraviolet ray amount of removing exposure doses (Dose to Clear) with 50 μ m segregation pattern (Isolate Pattern) CD benchmark expose to the film of described formation by appointed pattern mask (pattem mask), developed for 90 seconds in 23 ℃ with the tetramethylammonium hydroxide aqueous solution of 2.38 weight % then, afterwards with ultrapure water washing 1 minute.Subsequently with the pattern of described development in baking oven in 140 ℃ of heating 60 minutes, it is solidified, obtain the pattern film that thickness is 1.5 μ m.
II) negative sense sensitivity
Use spin coater at evaporation after the photosensitive polymer combination of making in the described embodiment 1～8 of coating and the comparative example 1～2 on the 370mm of ITO * 470mm glass substrate, in 110 ℃ of preliminary dryings 2 minutes on hot plate, forming thickness is the film of 5.0 μ m.With the intensity of 435nm is 20mW/cm
2Ultraviolet ray expose to the film of described formation with the amount of 25 μ m segregation pattern CD datum quantities (Dose) by pattern mask, in 110 ℃ of post exposure bakes (PEB) that on hot plate, carried out for 90 seconds.Developed for 100 seconds in 23 ℃ with the tetramethylammonium hydroxide aqueous solution of 2.38 weight % then, afterwards with ultrapure water washing 1 minute.Then with the pattern of described development in baking oven in 140 ℃ of heating 60 minutes, it is solidified, obtain the pattern film that thickness is 4.0 μ m.
III) angle of forward pattern
The angle (angle) of edge (edge) portion of the pattern that forms is (referring to the θ of Fig. 1 among the described figure (1)
1) be that 10 degree～30 are expressed as zero when spending, be expressed as when above less than 10 degree or 30 degree *.Usually, angle hour produces leakage current (Leakage Current) sometimes; When angle is big, existing problems aspect the homogeneity (Uniformity) when the evaporation organic membrane.
IV) angle of negative sense pattern
Anti-conical surface angle (Reversal the TaperAngle) (θ of following Fig. 2 of the edge part of the pattern that forms among the described figure (2)
2) be that 50 degree～70 are expressed as zero when spending, be expressed as when above less than 50 degree or 70 degree *.Usually, angle hour is having problems aspect bonding (Adhesion) sometimes; When angle is big, existing problems aspect the separation (Separation) when the evaporation organic membrane.
V) numerical aperture
When making oled panel, have on 370mm * 470mm glass substrate of ITO when forming insulator and isolated body, will remove insulator and isolated body and remaining ito surface is long-pending estimates as numerical aperture (%) with 25 μ m standard at interval at evaporation.
At first, in two step operations, use the photosensitive polymer combination of making in the comparative example 1, utilize described I) method form insulator, use the photosensitive polymer combination of making in the comparative example 2, utilize described II) method form isolated body.In the single step operation, after the photosensitive polymer combination of making in coating embodiment 1～8, in 110 ℃ of preliminary dryings 2 minutes on hot plate, forming thickness is the film of 6.0 μ m.Use and specify the forward pattern mask that the intensity of 435nm is 20mW/cm
2The ultraviolet ray amount of removing exposure dose with 50 μ m segregation pattern CD benchmark expose to formed film, then with the tetramethylammonium hydroxide aqueous solution of 2.38 weight % after 23 ℃ were developed for 90 seconds, with ultrapure water washing 1 minute, formation forward pattern.Arrange the negative sense pattern mask afterwards, the intensity with 435nm is 20mW/cm then
2Ultraviolet ray with the amount irradiation of 25 μ m segregation pattern CD datum quantities (Dose), in 110 ℃ of post exposure bakes (PEB) that on hot plate, carried out for 90 seconds.Afterwards, remove mask, flood exposure is set at 100mJ/sqcm, after 23 ℃ were developed for 100 seconds, washed 1 minute with ultrapure water with the tetramethylammonium hydroxide aqueous solution of 2.38 weight %.With the pattern of described development in baking oven in 140 ℃ of heating 60 minutes, it is solidified, form insulator that thickness is 1.5 μ m and the isolated body of 4.0 μ m simultaneously.
VI) specific inductive capacity
By described I) the middle pattern that forms, measure specific inductive capacity.Specific inductive capacity is by trying to achieve according to following calculating formula after the static capacity of measuring capacitor.At first, thin dielectric film is coated with into certain thickness, then, measures electrostatic capacitance by the impedance analysis device, according to following calculating formula, calculate specific inductive capacity separately, specific inductive capacity is 3.8 to be expressed as zero when following, greater than be expressed as in 3.8 o'clock *.
[calculating formula]
In the aforementioned calculation formula, ε 0 is a permittivity of vacuum, ε r be thin dielectric film than specific inductive capacity, A is a useful area, d is the thin dielectric film thickness.
[table 1]
| Classification | Axial sensitivity (mJ/cm 2) | Negative sense sensitivity (mJ/cm 2) | The forward pattern angles | The negative sense pattern angles | Numerical aperture (%) | Specific inductive capacity |
| Embodiment 1 | 250 | 27 | ○ | ○ | 70 | ○ |
| Embodiment 2 | 245 | 27 | ○ | ○ | 72 | ○ |
| Embodiment 3 | 255 | 26 | ○ | ○ | 71 | ○ |
| Embodiment 4 | 260 | 26 | ○ | ○ | 70 | ○ |
| Embodiment 5 | 255 | 28 | ○ | ○ | 70 | ○ |
| Embodiment 6 | 250 | 28 | ○ | ○ | 71 | ○ |
| Embodiment 7 | 260 | 29 | ○ | ○ | 70 | ○ |
| Embodiment 8 | 260 | 28 | ○ | ○ | 72 | ○ |
| Comparative example 1 | 255 | Do not form pattern | ○ | × | 55 | ○ |
| Comparative example 2 | Do not form pattern | 28 | × | ○ | 55 | ○ |
Shown in above-mentioned table 1, can confirm that the sensitivity of the photosensitive polymer combination of embodiment 1～8 constructed in accordance, low dielectric property etc. are all excellent, particularly can use a kind of photosensitive polymer combination to form the pattern of two kinds of forms, thus, can shorten activity time.And, to compare with comparative example 1～2, numerical aperture is obviously excellent, by this result as can be known, when being applied to OLED manufacturing process based on photosensitive polymer combination of the present invention, can access more excellent result.
In contrast, under the situation of comparative example 1,2, only can realize a kind of pattern of form respectively, have following shortcoming: activity time is long, and when forming isolated body, operation profit (margin) descends, cause the decline of numerical aperture thus, so be difficult to be applied in the OLED operation.
Claims (10)
1. OLED photosensitive polymer combination, this OLED is characterised in that with photosensitive polymer combination it contains:
A) pass through the novolac resin that progressively polymerization is made;
B) 1,2-two nitrine naphtoquinone compounds;
C) photo-acid generator;
D) melamine class crosslinking chemical; And
E) solvent.
2. OLED photosensitive polymer combination according to claim 1 is characterized in that, uses in the photosensitive polymer combination at described OLED, the novolac resin that a) passes through progressively polymerization manufacturing with respect to 100 weight portions, contain:
The b of 5 weight portions～100 weight portions) 1,2-two nitrine naphtoquinone compounds;
The c of 1 weight portion～20 weight portions) photo-acid generator;
The d of 1 weight portion～30 weight portions) melamine class crosslinking chemical; And
Making the solid component content in the photosensitive polymer combination is the e of 10 weight %～50 weight %) solvent.
3. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described a) the novolac resin by progressively polymerization manufacturing carries out condensation by aldehyde and phenol and makes, described aldehyde is formaldehyde etc., described phenol is selected from by orthoresol, metacresol, paracresol, 2,4-xylenols, 2,5-xylenols, 3,4-xylenols, 3,5-xylenols, 2,3, in the group that 5-pseudocuminol and their potpourri are formed more than a kind.
4. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described a) the polystyrene conversion weight-average molecular weight of the novolac resin by progressively polymerization manufacturing is 3,000～30,000.
5. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described b) 1,2-two nitrine naphtoquinone compounds are selected from by 1,2-two nitrine quinone 4-sulphonic acid esters, 1,2-two nitrine quinone 5-sulphonic acid esters and 1, more than one in the group that 2-two nitrine quinone 6-sulphonic acid esters are formed.
6. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described c) photo-acid generator is selected from more than one in the group of being made up of sulfosalt, salt compounded of iodine, sulphonyl diazomethane class photo-acid generator, N-sulphonyl oxygen imines class photo-acid generator, benzoin Sulfonates photo-acid generator, nitrobenzyl Sulfonates photo-acid generator, sulfone class photo-acid generator, glyoxime class photo-acid generator and triazines photo-acid generator.
7. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described d) the melamine class crosslinking chemical is selected from more than one in the group of being made up of following substances: the condensation product of the condensation product of urea and formaldehyde, melamine and formaldehyde, hydroxymethyl urea alkyl ether and melamine methylol alkyl ether.
8. OLED photosensitive polymer combination according to claim 1 is characterized in that,
Described e) solvent is selected from more than one in the group of being made up of following substances: alcohols such as methyl alcohol, ethanol, benzyl alcohol, hexanol; Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, Ethylene Glycol Methyl ether propionic ester, the glycol ethyl ether propionic ester, Ethylene Glycol Methyl ether, glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, the methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, methyl proxitol, the propylene glycol ethylether, the propylene glycol propyl ether, propylene glycol butyl ether, the dipropylene glycol dimethyl ether, the dipropylene glycol diethyl ether, the butylene glycol monomethyl ether, butylene glycol list ether, the dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether.
9. oled substrate, wherein, described oled substrate contains the solidfied material of any described photosensitive polymer combination of claim 1～8.
10. the pattern formation method of an oled substrate, wherein, described pattern formation method is used any described photosensitive polymer combination of claim 1～9.
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| JP2014071373A (en) * | 2012-09-28 | 2014-04-21 | Asahi Kasei E-Materials Corp | Photosensitive resin composition |
| JP6649433B2 (en) * | 2018-05-31 | 2020-02-19 | 旭化成株式会社 | Photosensitive resin composition |
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