CN117148676A - Negative photoresist composition for organic insulating film of liquid crystal display element - Google Patents

Negative photoresist composition for organic insulating film of liquid crystal display element Download PDF

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Publication number
CN117148676A
CN117148676A CN202311097310.5A CN202311097310A CN117148676A CN 117148676 A CN117148676 A CN 117148676A CN 202311097310 A CN202311097310 A CN 202311097310A CN 117148676 A CN117148676 A CN 117148676A
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Prior art keywords
insulating film
photoresist composition
negative photoresist
liquid crystal
crystal display
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Inventor
崔淑英
毕研刚
洪海哲
滕福爱
豆帆
颜俊雄
朱洪维
刘天用
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Yantai Shield Materials Technology Co ltd
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Yantai Shield Materials Technology Co ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of photoresist, and in particular relates to a negative photoresist composition for an organic insulating film of a liquid crystal display element, which comprises, by mass, 100 parts of a polymer with a free radical reactive group, 0.05-30 parts of a free radical polymerization initiator, 5-60 parts of an ethylenically unsaturated compound, 0.001-5 parts of a surfactant, 0.001-5 parts of an adhesion promoter and 45-2000 parts of a solvent, wherein the polymer with the free radical reactive group comprises polymers with structures shown in general formulas I and II. The invention adds the polymer with the structure shown in the general formulas I and II into the negative photoresist composition, so that the negative photoresist composition has the characteristics of high heat resistance, transparency and low electrical property, can be formed by developing with alkali developer, shortens the process, and has excellent adhesive force with metal, UV transmissivity, residual film rate and pattern stability.

Description

Negative photoresist composition for organic insulating film of liquid crystal display element
Technical Field
The invention relates to a negative photoresist composition for an organic insulating film of a liquid crystal display element, belonging to the technical field of photoresists.
Background
A liquid crystal display device (Liquid Crystal Display, LCD) is commonly used for devices such as televisions and graphic displays, and particularly each pixel is provided with a switching element such as a thin film transistor (Thin Film Transistor, TFT). An active matrix LCD has high-speed response characteristics and is suitable for a high number of pixels, and thus contributes to a display screen or the like that achieves high image quality, large size, and color, which are comparable to those of a Cathode Ray Tube (CRT).
In TFT-LCDs, as the demands for their size and resolution increase, the capacity increases, but the efficiency of the battery does not keep pace, so in order to solve the decrease in battery efficiency, a method of improving the transmittance of liquid crystals is often employed. The improvement of the transmittance of the liquid crystal can be achieved by greatly improving the aperture ratio of the liquid crystal panel, developing a highly transparent polarizing plate, or using a highly transparent color filter. The aperture ratio refers to the actual light transmittance of the pixel electrode area. In this method, a transparent Indium Tin Oxide (ITO) electrode is disposed on a TFT as a pixel electrode to increase a pixel electrode (pixel electrode) area. The mode is an epoch-making technology for improving the aperture opening ratio of the traditional TFT-LCD from 50-60% to about 80-85%, and can greatly reduce the reduction of the battery efficiency.
In the TFT-LCD, the organic insulating film plays an insulating role between the pixel electrode and the data line, and has a function of planarization with the lower layer. Such an insulating film layer has previously used benzocyclobutene to improve the aperture ratio. But benzocyclobutene is expensive and the method of manufacturing the contact hole has a problem in that a reactive ion etching (reactive ion etching, RIE) process using photoresist is necessary.
Disclosure of Invention
The present invention addresses the above-described drawbacks of the prior art by providing a negative photoresist composition for an organic insulating film of a liquid crystal display element, which has excellent storage stability and excellent adhesion to metal and pattern stability.
The technical scheme for solving the technical problems is as follows:
a negative photoresist composition for an organic insulating film of a crystal display element comprises, in parts by mass, 100 parts of a polymer having a radical reactive group, 0.05 to 30 parts of a radical polymerization initiator, 5 to 60 parts of an ethylenically unsaturated compound, 0.001 to 5 parts of a surfactant, 0.001 to 5 parts of an adhesion promoter, and 45 to 2000 parts of a solvent;
the polymer with the free radical reactive group comprises polymers with structures shown in the following general formulas I and II;
the general formula I has the following structure:
wherein,
a, b, c, d are the mol ratio of each monomer, 0.ltoreq.a <1, 0.ltoreq.b <1, 0.ltoreq.c <1, 0.ltoreq.d <1, a+b+c+d=1;
x is a hydrogen atom or a methyl group;
Y 1 is an alkyl group having 1 to 15 carbon atoms, a hydroxyalkyl group or an epoxy resin;
Y 2 an olefinic group having a double bond and having 2 to 15 carbon atoms;
Y 3 is any one of the structures shown in structural formulas (I) to (VII):
in the structural formulae (I) to (VII), R 2 Is an olefin having 1 to 10 carbon atoms; r is R 3 Is a hydrocarbon compound having 1 to 10 carbon atoms; r is R 4 Is hydrogen or methyl;
the general formula II has the following structure:
wherein n is more than or equal to 1 and less than or equal to 3;
R 1 any one selected from alkyl group with 1-10 carbon atoms, olefin group with 2-10 carbon atoms or aryl-bearing alkyl group with 6-15 carbon atoms;
R 2 selected from alkyl groups having 1 to 6 carbon atoms.
Based on the technical scheme, the invention can also make the following improvements:
further, the average molecular weight of polystyrene equivalent is measured in the mobile phase by GPC (gel permeation chromatography) with tetrahydrofuran, and the average molecular weight of the polymer represented by the general formula I (the molecular weight in terms of polystyrene can be measured as average molecular weight) is 2000 to 50000, the dispersity is 1.0 to 5.0, and the acid value is 60 to 140KOHmg/g.
Further, the polymer represented by the general formula I can be synthesized by a three-step reaction:
step one, synthesizing acrylic polymer matrix resin;
introducing unsaturated groups into acrylic polymer matrix resin to obtain acrylic polymer resin;
step three, introducing an acid group into the acrylic polymer resin.
In the first step, synthesis is performed using a monomer containing both an epoxy group and a monomer containing an unsaturated bond. Wherein the monomer containing both epoxy group and unsaturated bond is one or two of allyl glycidyl ether, glycidyl (meth) acrylate and the like.
In the second step, an unsaturated group is introduced into the acrylic polymer matrix resin by a ring-opening reaction of an epoxy group.
In step three, the hydroxyl group produced by the reaction in step two is reacted with an acid by subjecting the polymer resin containing two unsaturated groups to an esterification reaction. Preferably, the acid is any one of anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous tetrahydrophthalic acid, and the like.
After the polymer shown in the general formula I is added into the negative photoresist composition, the formed pattern has no defect and has very excellent flatness. Wherein Y in the general formula I 1 Selected from alkyl, hydroxyalkyl or epoxy resins having 1 to 15 carbon atoms, which contributes to improved adhesion; y is Y 2 An alkenyl group having 2 to 15 carbon atoms and having a double bond of c=c, and having a characteristic of improving resolution by increasing a molecular weight after a reaction to ultraviolet light; y is Y 3 Unlike acrylic copolymer resins, for example, having an unsaturated aromatic group and a large amount of saturated ester ring structure, the structure improves the film residue ratio of the product compared to conventional binder resins, so that the product has excellent heat resistance.
Further, the average molecular weight of polystyrene equivalent is measured in the mobile phase using GPC (gel permeation chromatography) of tetrahydrofuran, and the average molecular weight of the polymer represented by the general formula II is 500 to 10000.
The polymer of formula II may include a silicone polymer, which is a hydrolyzed polymer of a hydrolyzed silane compound. The term "hydrolyzed polymer of a hydrolyzed silane compound" as used herein refers to some silane compounds that hydrolyze silane compounds, and is a hydrolytic polymerization reaction.
In the general formula II, R 1 Any one selected from an alkyl group having 1 to 10 carbon atoms, an olefin having 2 to 10 carbon atoms, and an alkyl group having 6 to 15 carbon atoms and having an aromatic group may be unsubstituted or a part or all of hydrogen atoms may be substituted. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-decyl, trifluoromethyl, 3-trifluoropropyl, 3-glycidoxypropyl, 2- (3, 4-epoxycyclohexyl) ethyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatopropyl, and the like. Alkylene groupExamples of (a) include vinyl, 3-acryloxypropyl, 3-methacryloxypropyl and the like. Examples of the aromatic group include phenyl, tolyl, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl, 2- (p-hydroxyphenyl) ethyl, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl and naphthyl.
In the general formula II, R 2 Selected from alkyl groups having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, butyl, etc. Among them, methyl and ethyl are preferable from the viewpoint of easy hydrolysis.
From the viewpoint of the progress of the hydrolytic condensation reaction, n is preferably 1 to 3.
In the case where n=1, the polymer represented by the general formula ii may be vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrioxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, m-styryltriethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxyethyltriethoxysilane, methacryloxytripropoxysilane, acryloxytripropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylpropoxysilane, 2-acryloxyethyltriethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, or the like.
In the case where n=2, the polymer represented by the general formula ii may be a dialkoxysilane compound such as vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, and phenyltrifluoropropyldimethoxysilane.
In the case where n=3, the polymer represented by the general formula ii may be a monoalkoxysilane compound such as allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-oxopropyl dimethylmethoxysilane, 3-acryloxypropyl dimethylmethoxysilane, 3-methacryloxypropyl diphenylmethoxysilane, 3-acryloxypropyl diphenylmethoxysilane, 3',3 "-oxypropylmethoxysilane triacrylate, 3',3" -oxypropylmethoxysilane triacrylate, and dimethyltrifluoropropyl methoxysilane.
Among these polymers represented by the general formula II, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane are preferable. Among these hydrolyzable silane compounds, trifunctional silane and tetrafunctional silane are preferably used from the viewpoint of improving the surface hardness of the cured film.
The conditions for hydrolysis and condensation of the polymer represented by the above formula II are that at least a part of the hydrolyzable silane compound is hydrolyzed to hydrolyze hydrolyzable groups (-OR) 2 ) Converted to silanol to cause a condensation reaction.
Further, the polymer shown in the general formula II is preferably purified by any one of reverse osmosis membrane treatment, ion exchange treatment, distillation and the like; the water is used in an amount of 0.1 to 3mol. By purifying the polymer represented by the general formula II with purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved, and the reaction rates of hydrolysis and condensation can be optimized.
The solvent used for hydrolytic condensation may be the same as the negative photoresist composition of the present invention. Preferred examples of the solvent for hydrolytic condensation include any of ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, propionate and the like.
The catalyst used for hydrolytic condensation is preferably any one of an acid catalyst, a base catalyst, a basic ion exchange resin, a hydroxide, a carbonate, an alkoxide, and the like. The amount of the catalyst to be used is preferably 0.2mol or less, more preferably 0.0001mol to 0.1mol.
The reaction temperature of the polymer represented by the general formula II in the hydrolytic condensation is preferably 40℃to 150℃and more preferably 50℃to 100℃and the reaction time is preferably 30 minutes to 24 hours and more preferably 1 hour to 12 hours. The reaction temperature and the reaction time can be most effectively subjected to a hydrolytic condensation reaction in which water and the resulting alcohol in the reactants can be removed by adding a dehydrating agent and vacuum distillation at a temperature lower than 40 ℃.
Further, the radical polymerization initiator is any one or a combination of two or more of an oxime compound, an acetophenone compound and a biimidazole compound.
The acyloxym compound is preferably selected from the group consisting of ethyl ketone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-amino oxazol-3-yl ] -1- (O-acetyloxime), 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-yl ] octane-1-oxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-methyloxime-O-benzoate, 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9H-amino oxazol-3-yl ] ethane-1-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-oxazol-3-yl ] -1- (O-acetyloxime), any one of ethaneone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-furan-3-yl ] -1- (O-acetyl oxime), and ethaneone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime).
The acetophenone compound is preferably an alpha-aminoketone compound or an alpha-hydroxyketone compound. The alpha-aminoketone compound comprises any one of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-ketone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) -butane-1-ketone or 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-ketone; the α -hydroxyketone compound is preferably any one of 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-dipropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, or 1-hydroxycyclohexyl phenyl ketone.
The bisimidazole compound is preferably any one of 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -bisimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biazole, or 2,2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biazole.
When a bisimidazole compound is selected as the radical polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group may be added as the amino sensitizer. The amino sensitizer is preferably either 4,4 '-bis (dimethylamino) benzophenone or 4,4' -bis (diethylamino) benzophenone or a combination of both.
When the biimidazole compound and the amino sensitizer are used in combination, a thiol compound may be added as a hydrogen radical donor. The biimidazole compound generates imidazole free radicals under the action of an amino sensitizer, so that the polymerization initiating capability is improved. By adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical from the thiol compound is donated to an imidazole radical, and not only is the imidazole radical converted to neutral imidazole, but also a component of a sulfur radical having a high polymerization initiation ability is generated, and therefore, a hardened film having high frictional resistance can be formed even at a low irradiation dose.
The thiol compound is preferably an aromatic thiol compound or an aliphatic mono-thiol compound,
the aromatic thiol compound is preferably any one of 2-mercaptobenzothiazole, 2-mercaptobenzoxazole or 2-mercapto-5-methoxybenzothiazole; the aliphatic monothiol compound is preferably 3-mercaptopropionic acid or any one of methyl 3-mercaptopropionate, pentaerythritol tetrakis (mercaptoacetate) or pentaerythritol tetrakis (3-mercaptopropionate).
When the biimidazole compound and the amino sensitizer are used in combination, the use amount ratio (mass ratio) of the amino sensitizer to the biimidazole compound is preferably 0.1 to 50, more preferably 1 to 20. By increasing the mass ratio of the amino sensitizer to the bisimidazole compound from 0.1 to 50, the curing reactivity of the polymer can be improved, and the abrasion resistance of the obtained cured film can be improved.
Further, the ethylenically unsaturated compound is any one or a combination of two or more of monofunctional acrylate, difunctional acrylate and trifunctional acrylate.
By adding an ethylenically unsaturated compound to the composition, photosensitivity of the composition is improved and sublimation is reduced, and a cured film formed from the composition is further improved in terms of abrasion resistance and transparency.
The monofunctional acrylate is preferably any one of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω -carboxyl polycaprolactone monoacrylate.
The difunctional acrylate is preferably any one of ethylene glycol di (meth) acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate and 1, 9-nonanediol dimethacrylate.
The trifunctional acrylate is preferably any one of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or pentaerythritol trimethacrylate.
The ethylenically unsaturated compound may also be selected from more functional acrylates, such as any of pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and ethylene oxide modified dipentaerythritol hexaacrylate.
The surfactant is one or a combination of two or more of fluorine-based surfactant, silicone-based surfactant and nonionic surfactant.
Further, the adhesion promoter is any one or a mixture of two or more of trimethoxy silicon-based benzoic acid, gamma-methacrylic acid oxypropyl trimethoxy silane, vinyl triacetoxy silane, vinyl trimethoxy silane, gamma-isocyanate propyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl triethoxy silane, N-phenylaminopropyl trimethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane. The adhesion promoter may improve adhesion to the substrate.
Further, the solvent of the present invention includes a high boiling point solvent having a boiling point of 110 ℃ or more and a low boiling point solvent lower than 110 ℃ at atmospheric pressure.
The high boiling point solvent may have a boiling point of at least 110 ℃, preferably 110 ℃ to 250 ℃, more preferably 110 ℃ to 210 ℃ at atmospheric pressure. The content of the high boiling point solvent in the solvent of the present invention may be preferably 5% to 60%, more preferably 10% to 50%, and still more preferably 15% to 40% (based on the total weight of the solvent). Within the above range, a highly flat film can be produced in the process of forming a coating film. The high boiling point solvent is selected from the group consisting of gamma-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, dipropylene glycol methyl ether acetate, N-dimethylformamide, N-methylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl diethyl ether, dihexyl ether, ethylacetone, isopiponone, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate, propylene carbonate and benzyl acetate. Preferably, in terms of developing performance, it may be one or more of γ -butyrolactone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
The low boiling point solvent is compatible with but does not react with the above-mentioned photosensitive resin composition components and has a boiling point of less than 110 ℃, preferably a boiling point of 100 ℃, and examples of the low boiling point solvent include one or more of propylene glycol monomethyl ether acetate, cyclohexanone, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol N-propyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-N-propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, methyl ethyl ether, 2-heptanone, 3-heptanone, ethyl acetate, N-propyl acetate, isopropyl acetate, N-butyl acetate, isobutyl acetate, N-pentyl formate, isopentyl acetate, N-butyl propionate, ethyl butyrate, N-propyl butyrate, isopropyl butyrate, N-butyl butyrate, N-dimethylformamide, N-dimethylacetamide, 3-methoxybutyl alcohol, and cyclopentanone.
The negative photoresist composition for an organic insulating film of a liquid crystal display element of the present invention is formed by irradiating ultraviolet rays using a mask after spin-coating on a substrate, preferably adding a solvent to have a viscosity in the range of 2 to 20cps, and forming an organic insulating film by applying the solvent. More preferably, adjusting the viscosity to 2-10cps is more advantageous for controlling the thickness of the film to form a pinhole-free film after coating.
Further, the composition of the present invention may further comprise any one or two or more of an antioxidant, a stabilizer, and a radical scavenger.
The invention has the beneficial effects that: the invention adds the polymer with the structure shown in the general formulas I and II into the negative photoresist composition, so that the negative photoresist composition has the characteristics of high heat resistance, transparency and low electrical property, can be formed by developing with alkali developer, shortens the process, and has excellent adhesive force with metal, UV transmissivity, residual film rate and pattern stability.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention.
< A > Synthesis of Polymer of Structure shown in general formula I
Synthesis example 1
The synthesis of the polymer resin goes through three steps in total:
step one, synthesis of acrylic polymer matrix resin: 10.3g of benzyl methacrylate (Mr= 162.19), 20.3g N-phenylmaleimide (Mr= 173.17) and 16.7g of styrene (Mr=104.15) monomers were mixed, and 71.9g of glycidyl methacrylate, 4g of 1-dodecanethiol as a chain transfer agent and 480g of propylene glycol monomethyl ether acetate as a solvent were mixed with a stirrer under a nitrogen atmosphere for 30 minutes. The reactor was warmed to 60℃under a nitrogen atmosphere, and when the mixture temperature reached 60℃5g of azobisisoheptonitrile, a thermal polymerization initiator, was added and the reaction was stirred for 10 hours. A resin having an average molecular weight of 6,000 and an acid value of zero was obtained.
Step two, introducing unsaturated groups into the acrylic polymer matrix resin: the reaction vessel for the polymerization of the first polymer was heated to 80℃and 0.5g of tetraethylammonium bromide and 0.1g of a thermal polymerization inhibitor 4-methoxyphenol were added thereto, followed by stirring in an air atmosphere for 3 hours, and then 26.1g of methacrylic acid was added thereto, and the reaction vessel was heated to 100℃and reacted with stirring for 24 hours to obtain a resin (acrylic polymer resin) having a molecular weight (Mw) of 8,000 and an acid value of 5.
Step three, introducing an acid group into the acrylic polymer resin: the polymer prepared in the second step was cooled to 70℃and 30.8g of tetrahydrophthalic anhydride was added thereto, and the mixture was further stirred at 80℃for 24 hours to synthesize the desired binder resin having a molecular weight (Mw) of 10,000, mw/Mn of 1.9 and an acid value of 75mgKOH/g.
Synthesis example 2
In the case of Synthesis example 1, the amounts of the monomers added were 15.5g of benzyl methacrylate, 23.4g of N-phenylmaleimide and 9.6g of styrene. The procedure of Synthesis example 1 was followed by carrying out the procedures of first, second and third in this synthesis example to obtain a copolymer having an average molecular weight of 8,800, mw/Mn of 2.0 and an acid value of 78 mgKOH/g.
Synthesis example 3
In the same manner as in Synthesis example 1 except that the amounts of the monomers charged in this synthesis example were 7.0g of methyl methacrylate, 24.5g of N-phenylmaleimide and 16.6g of styrene, the procedure of one, two and three of this synthesis example was conducted, to obtain a copolymer having an average molecular weight of 8600, mw/Mn of 1.8 and an acid value of 74 mgKOH/g.
< B > Polymer of Structure represented by general formula II
Synthesis example 4
In a vessel equipped with a stirrer, 23g of propylene glycol monomethyl ether, 38g of phenyltrimethoxysilane and 20g of 3-methacryloxypropyl trimethoxysilane were added, the solution was heated to 60℃and then 0.1g of formic acid and 19g of ion exchange water were added, heated to 75℃and held for 2 hours. After cooling to 45 ℃, 28g of trimethyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Further, the solution temperature was set to 40 ℃ and maintained while water and methanol generated by hydrolytic condensation were removed by vacuum evaporation. Thus, a hydrolyzed condensate (B-1) (the mass fraction of the solid content was 35%, mw=1800, and Mw/mn=2.2) was obtained.
Synthesis example 5
In a vessel equipped with a stirrer, 25g of propylene glycol monomethyl ether, 22g of methyltrimethoxysilane, 17g of tetramethoxysilane and 16g of 3-methacryloxypropyl trimethoxysilane were added, after heating to a solution temperature of 60℃0.1g of formic acid and 20g of deionized water were added, heated to 75℃and maintained for 2 hours. After cooling to 45℃30g of trimethyl orthoformate was added as dehydrating agent and stirred for 1 hour. The solution temperature was set to 40 ℃ and vacuum evaporation was performed while maintaining the temperature to remove water and methanol generated by hydrolytic condensation. The hydrolysis condensate (B-2) (mass fraction of solid content was 35%, mw=2,500, mw/mn=2.3) was obtained.
Synthesis example 6
In a vessel equipped with a stirrer, 24g of propylene glycol monomethyl ether, 6g of methyltrimethoxysilane, 21g of phenyltrimethoxysilane, 17g of gamma-glycidoxypropyl trimethoxysilane and 15g of 3-methacryloxypropyl trimethoxysilane were added, and after heating until the solution temperature reached 60 ℃, 0.1g of formic acid and 17g of ion exchange water were added, heated to 75℃and held for 2 hours. After cooling to 45 ℃, 30% by mass of trimethyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Then, the solution temperature was set to 40℃and maintained at that temperature while water and methanol produced by hydrolytic condensation were removed by vacuum evaporation. The hydrolysis condensate (B-3) was obtained (mass fraction of solid content: 28g, mw=1800, mw/mn=2.0).
Component examples of negative photoresist composition
The components used to prepare the compositions of the examples and comparative examples were as follows:
< A > Polymer of the structure shown in the formula I
A-1: synthesis example 1
A-2: synthesis example 2
A-3: synthesis example 3
< B > Polymer of Structure represented by general formula II
B-1: synthesis example 4
B-2: synthesis example 5
B-3: synthesis example 6
< C > radical polymerization initiator
Ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) (Irgacure OXE-02,Ciba speciaty Chemicals Co, ltd.)
< D > ethylenically unsaturated Compounds
D-1: dipentaerythritol pentaacrylate
D-2: dipentaerythritol hexaacrylate (KAYARAD DPHA, japanese chemical Co., ltd.)
D-3: pentaerythritol triacrylate (A-TMM-3 LMN, new Zhongcun chemical industry Co., ltd.)
< E > surfactant
FZ-2122,Dow Corning Toray Silicone Co
< F > adhesion promoter
Gamma-isocyanatopropyl triethoxysilane, shin-Etsu Co
< G > organic solvent
(G1) Organic solvent (vapor pressure of 0.1mmHg or more and less than 1mmHg at 20 ℃ C.)
G1-1: diethylene glycol methyl ethyl ether (20 ℃,0.75 mmHg)
G1-2: ethylene glycol monobutyl ether (20 ℃,0.76 mmHg)
(G2) Organic solvent (vapor pressure at 20 ℃ C. Is 1mmHg or more and 20mmHg or less)
G2-1: propylene glycol methyl ether (20 ℃,6.7 mmHg)
G2-2: propylene glycol monomethyl ether acetate (20 ℃,3.75 mmHg)
G2-3: cyclohexanone (20 ℃,3.4 mmHg)
Example 1
70g of the polymer (A-1) synthesized in Synthesis example 1, 30g of the polymer (B-1) synthesized in Synthesis example 4, 2g of ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) as a radical polymerization initiator, 3g of dipentaerythritol pentaacrylate as an ethylenically unsaturated compound (D-1), 2.0g of dipentaerythritol hexaacrylate (D-2), 2g of pentaerythritol triacrylate (D-3), and 1.5g of FZ-2122.1 g as a surfactant were added to a container. Then, propylene glycol monomethyl ether solvent was added so that the solid content concentration mass fraction became 20%, to prepare a negative photoresist composition.
Examples 2-11 and comparative examples 1-2
Examples 2-11 and comparative examples 1-2 negative type resist compositions were prepared in the same manner as in example 1, except that the types and amounts of the respective components were changed as shown in tables 1, 2.
The negative photoresist compositions prepared as described in the above examples and comparative examples were used for the following performance evaluation.
In comparative examples 1 to 2, a positive resist composition for an organic insulating film of a high aperture ratio liquid crystal display element was produced in the same manner except that the binder resin (average molecular weight 10000) represented by the following formula 3 was used instead of the polymers having the structures represented by the general formulae i and ii in example 1 described above, and the components and contents of the composition were changed according to the compositions shown in the following table 2.
In the above formula 3, p is 0.3, q is 0.2, and r is 0.5.
1. Photosensitive evaluation of negative photoresist composition
On the silicon substrate, for examples 1 to 11 and comparative examples 1 to 2, after each composition was coated using a spin coater, it was prebaked at 100℃for 2 minutes using a hot plate to form a coating film having a thickness of 1.5. Mu.m. For the obtained coating film, a Canon PLA.+ -. 501F exposure machine (ultra-high pressure mercury lamp) was used, and a silicon wafer was placed under a mask having a 3.0 μm line width pattern and exposed. The material of the exposed portion was removed by changing the exposure time in a tetramethyl ammonium hydroxide (TMAH) solution with a mass fraction of 2.31%, at 25 ℃, for washing for 10 seconds. Then, the substrate was washed under ultrapure water for 1 minute, dried, and patterned on the silicon substrate. At this time, the space line width (low portion) was 0.30 μm to measure the minimum exposure amount required, and the photosensitivity was as shown in tables 1 and 2. When the minimum exposure is less than 200 (J/m) 2 ) When the photosensitive property was considered to be good.
2. Refractive index evaluation of interlayer insulating film
A cured film was formed on a silicon substrate, the refractive index of the cured film was obtained, and the cured film was measured at 633nm using Auto EL IV NIR iii. When the refractive index is higher than 1.50, the material is considered to be useful as an interlayer insulating film.
3. Evaluation of Heat resistance of interlayer insulating film
A cured film was formed on a silicon substrate, and the film thickness (T2) of the obtained cured film was measured. Then, the silicon substrate forming the cured film was further baked at 240℃in a clean oven, and then the film thickness of the cured film was measured (T2), and by further baking, the film thickness change rate { (T2-T2)/T2 } ×100% was calculated. The results are shown in tables 1 and 2. When this value is 3% or less, heat resistance is good.
4. Evaluation of transmittance of interlayer insulating film
In the same manner as the "photosensitivity evaluation", a thin film was formed on a glass substrate. On the obtained film, canon PLA.+ -. 501F exposure devices (ultra-high pressure mercury lamps) were used respectively to give a cumulative exposure of 3000J/m 2 After exposure, the cured film was obtained by heating at 220℃for 1 hour in a clean oven. The light transmittance of the glass substrate having such a cured film was measured in a wavelength range of 400 to 100nm using a spectrophotometer "TU-1110" (manufactured by Beijing General Analytical Instrument Co.). The results are shown in tables 1 and 2. When the minimum light transmittance exceeds 15%, the light transmittance is good.
5. Evaluation of Dry etching resistance of interlayer insulating film
A cured film was formed on a silicon substrate, and an etching gas CF was used by using a dry etching apparatus CDE-10N (manufactured by Shibaura Mechatronics co., ltd.) 4 50 mL/min, O 2 The dry etching was performed at 10 mL/min with an output of 400mW and an etching time of 10 seconds, and the film heads before and after the treatment were measured. The results are shown in tables 1 and 2. When the film thickness is reduced by less than 1.0 μm, the dry etching property is good.
Table 1 examples and physical property test tables thereof
Table 2 comparative examples and physical properties test table thereof
From the results shown in tables 1 and 2, the cured film formed from the negative photoresist composition of the present invention, using the polymers of the structures shown in the general formulae I and II, has the characteristics of good heat resistance, high transmittance and good dry etching property, as compared with the negative photoresist composition formed from only one of the polymers of the structures shown in the general formulae 3 and II in Table 2.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A negative photoresist composition for an organic insulating film of a liquid crystal display element, characterized by comprising 100 parts by mass of a polymer having a radical reactive group, 0.05 to 30 parts by mass of a radical polymerization initiator, 5 to 60 parts by mass of an ethylenically unsaturated compound, 0.001 to 5 parts by mass of a surfactant, 0.001 to 5 parts by mass of an adhesion promoter and 45 to 2000 parts by mass of a solvent;
the polymer with the free radical reactive group comprises polymers with structures shown in the following general formulas I and II;
the general formula I has the following structure:
wherein,
a, b, c, d are the mol ratio of each monomer, 0.ltoreq.a <1, 0.ltoreq.b <1, 0.ltoreq.c <1, 0.ltoreq.d <1, a+b+c+d=1;
x is a hydrogen atom or a methyl group;
Y 1 is an alkyl group having 1 to 15 carbon atoms, a hydroxyalkyl group or an epoxy resin;
Y 2 an olefinic group having a double bond and having 1 to 15 carbon atoms;
Y 3 is any one of the structures shown in structural formulas (I) to (VII):
in the structural formulae (I) to (VII), R 2 Is an olefin having 1 to 10 carbon atoms; r is R 3 Is a hydrocarbon compound having 1 to 10 carbon atoms; r is R 4 Is hydrogen or methyl;
the general formula II has the following structure:
wherein n is more than or equal to 1 and less than or equal to 3;
R 1 any one selected from alkyl group with 1-10 carbon atoms, olefin group with 2-10 carbon atoms or aryl-bearing alkyl group with 6-15 carbon atoms;
R 2 selected from alkyl groups having 1 to 6 carbon atoms.
2. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the polymer represented by the general formula I has an average molecular weight of 2000 to 50000, a dispersity of 1.0 to 5.0, and an acid value of 60 to 140KOHmg/g.
3. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the average molecular weight of the polymer represented by the general formula ii is 500 to 10000.
4. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the polymer represented by the general formula ii is purified by any one of reverse osmosis membrane treatment, ion exchange treatment, distillation; the water is used in an amount of 0.1 to 3mol.
5. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the radical polymerization initiator is any one or two or more of an oxime compound, an acetophenone compound, and a biimidazole compound.
6. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 5, wherein the radical polymerization initiator is a bisimidazole compound used in combination with an amino sensitizer or a combination of an amino sensitizer and a thiol compound; the amino sensitizer is an aliphatic or aromatic compound having a dialkylamino group.
7. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the ethylenically unsaturated compound is any one or a combination of two or more of monofunctional acrylate, difunctional acrylate, and trifunctional acrylate.
8. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the surfactant is one or a combination of two or more of a fluorine-based surfactant, a silicone-based surfactant and a nonionic surfactant.
9. The negative resist composition for an organic insulating film of a liquid crystal display element according to claim 1, wherein the adhesion promoter is any one or a mixture of two or more of trimethoxysilylbenzoic acid, gamma-oxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, N-phenylaminopropyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
10. The negative photoresist composition for an organic insulating film of a liquid crystal display element according to claim 1, further comprising any one or two or more of an antioxidant, a stabilizer, and a radical scavenger.
CN202311097310.5A 2023-08-29 2023-08-29 Negative photoresist composition for organic insulating film of liquid crystal display element Pending CN117148676A (en)

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