CN116693856A - Adhesive resin and application thereof - Google Patents

Adhesive resin and application thereof Download PDF

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Publication number
CN116693856A
CN116693856A CN202310783117.0A CN202310783117A CN116693856A CN 116693856 A CN116693856 A CN 116693856A CN 202310783117 A CN202310783117 A CN 202310783117A CN 116693856 A CN116693856 A CN 116693856A
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formula
photoresist composition
binder resin
negative photoresist
groups
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崔淑英
毕研刚
滕福爱
洪海哲
刘天用
豆帆
颜俊雄
朱洪维
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Yantai Shield Materials Technology Co ltd
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Yantai Shield Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention relates to an adhesive resin and application thereof, belonging to the technical field of photoresist, wherein the structure of the adhesive resin comprises the following general formula I and/or general formula II:

Description

Adhesive resin and application thereof
Technical Field
The invention relates to an adhesive resin and application thereof, and belongs to the technical field of photoresist.
Background
A general liquid crystal display device (Liquid Crystal Display, hereinafter referred to as LCD) is a display device for use in, for example, televisions and graphic displays. A thin film transistor liquid crystal display (thin film transistor liquid crystal display, hereinafter abbreviated as LCDTFT-LCD) is one type of liquid crystal display, and uses thin film transistor technology to improve image quality, mainly including three components of a Color Filter (CF) substrate, liquid crystal, and a thin film transistor (Thin FilmTransistor, hereinafter abbreviated as TFT) substrate, has high-speed response characteristics and can be applied to many pixels, and thus, has made a great contribution to achieving high image quality, large size, color, and the like of a display screen comparable to a Cathode Ray Tube (CRT).
An LCD device generally includes an LCD panel and a light source providing light to the LCD panel. The LCD panel includes a plurality of pixels and a plurality of Thin Film Transistors (TFTs). An organic insulating film having a low dielectric constant is coated on the upper surface of the substrate on which the above structure is formed, and as the negative photoresist composition for forming the organic insulating film, a binder resin, a polyfunctional monomer having an ethylenically unsaturated bond, and a composition in which a photoresist is added to a solvent are preferably used. However, when an organic insulating film is formed using a negative photoresist composition containing a conventional binder resin, not only a sufficiently low dielectric constant is not exhibited, but also adhesion to a metal is poor, a residual film rate after development is low, resulting in poor flatness of a pattern. Therefore, an adhesive suitable for an organic insulating film is required.
Disclosure of Invention
The present invention addresses the above-described problems of the prior art by providing an adhesive resin and application thereof.
It is an object of the present invention to provide a binder resin having a structure comprising the following general formula I and/or general formula II:
wherein at least one R is a photoreactive acrylic acid, methacrylic acid or an organic group containing an unsaturated bond, and the other R are each independently selected from H atoms, glycidyl epoxy esters, and alkyl groups having 1 to 5 carbon atoms;
Z 1 each independently selected from the group consisting of linear alkyl or alkenyl groups having 1 to 24 carbon atoms, cyclic alkyl or alkenyl groups, aromatic hydrocarbons, glyceryl groups, methacrylate groups, amine groups, and carboxyl groups;
n is an integer from 1 to 40;
wherein a, b, c are the molar ratio of each monomer, 0.ltoreq.a <1, 0.ltoreq.b <1, 0.ltoreq.c <1, a+b+c=1;
x is independently selected from hydrogen atom or alkyl with 1 to 5 carbon atoms;
Y 1 and Y 2 Each independently selected from alkyl groups having 1 to 12 carbon atoms, phenyl groups, epoxy groups, glyceryl groups, oxy groups, benzyl groups, cyclic saturated hydrocarbons, and hydroxyalkyl groups.
Based on the technical scheme, the invention can also make the following improvements:
further, the average molecular weight of the general formula I is 200 to 20000, and the dispersity is 1 to 5.0.
Further, the average molecular weight of the general formula II is 2000 to 50000, the dispersity is 1.6 to 3.0, and the acidity is 30to 150KOHmg/g.
Further, the weight ratio of the resin represented by the general formula I to the resin represented by the general formula II is 0.1:99.9-99.9:0.1.
Another object of the present invention is to provide an organic-inorganic hybrid negative photoresist composition comprising the above binder resin.
Further, the weight of the binder resin is 5% -30% of the total weight of the composition.
Further, 5 to 35% of a polyfunctional monomer having an ethylenic unsaturated bond is included.
The polyfunctional monomer having an ethylenic unsaturated bond may be a polymerizable compound having an ethylenic unsaturated bond which is generally used in photosensitive compositions, for example, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, trimethylpropane di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentadiene alkyd ester, pentatetrol tetrahydroacrylate, acryl acrylate having 2 to 14 acryl groups, compound obtained by esterifying polyvalent alcohols such as ethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate and α, β -unsaturated carboxylic acid esters, compound obtained by adding (meth) acrylic acid to glyceryl-containing compound such as trimethylpropane tri (ethylene glycol) ether acrylic acid addition, compound obtained by adding (meth) acrylic acid to glyceryl-containing compound such as bisphenol a di (propylene glycol) ether acrylic acid addition, compound having hydroxyl group-unsaturated bond such as toluene diisocyanate addition of β -hydroxyethyl (meth) acrylate, compound having hydroxyl group-unsaturated bond with polyvalent carboxylic acid and ester compound of polyvalent carboxylic acid, compound with polyisocyanate addition, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylpropane tetraacrylate, trimeric ester (2-oxyethyl acrylate), ethylene glycol epoxy phthalate, ethylene propylene glycol, propylene glycol epoxy cyanate, melamine, amyl proxy acid ester tetra-cyanamide, noethylene glycol diacrylate, ethylene glycol phthalate, propylene glycol phthalate, trimethylol propylene glycol ester triacrylate, and the like. They may be used alone or in combination of 2 or more thereof.
Further, 0.5% -10% of photoinitiator is also included.
As the photoinitiator, an existing photoinitiator, such as xylyl or xylyl photoinitiator, may be used. If the photoinitiator itself has a color, it has an effect of reducing transparency, and thus, high transparency can be achieved by the photoinitiator having appropriate sensitivity in a wavelength band used during exposure and having no color itself. Generally, a photoinitiator for a bridge reaction using an acrylic multifunctional monomer is used in combination with an ultraviolet wavelength, and the most widely used ultraviolet wavelength mercury lamp has a wavelength in the range of 310 to 420nm, so that a photoinitiator that generates radicals in this wavelength region can be used. Examples of such photoinitiators include benzophenone-based and triazine-based photoinitiators such as Irgacure 369, irgacure 907, CGI 124, and CGI 242EPD/BMS mixtures. For example, benzophenone, 1-hydroxy-1-phenylcyclohexane, benzyldimethyl ketone, 1-benzyl-1-dimethylamino-1- (4-pentadiene-phenylketone) propane, 2-pentadiene-2- (4-methyl methacrylate) phenylpropane, thioxanthone (thioxanthone), 1-chloro-4-propoxyphenylketone, isopropoxyphenylacetone, diethoxyphenylacetone, ethoxyphenylacetone, 4-phenyl-4-methyldiphenylsulfanilamide, phenylbutyl ether, 2-hydroxy-2-phenylpropane, 2-hydroxy-2- (4-isopropyl) benzoic acid ethyl ester, 4-butylbenzene trichloromethane, 4-phenoxybenzene dichloromethane, ethyl benzoate, 1, 7-di (9-acrylic acid) hexane, 9-n-butyl-3, 6-bis (2-morpholinoisobutylmercaptane), diphenyl (2, 4, 6-trimethylbenzoyl) -phosphonate, 10-butyl-2-aminoketone, 4' -diethylamino) -2- [2- (4-isopropyl) benzoic acid ethyl ester, 4-butylbenzene- [2- (4-methoxy) -2, 6-methyl ] -1, 6- [ 1-trichloromethyl ] -3, 6-bis- [1, 6-dichloro-phenylmethane, 5-trichloromethyl ] -1- [1, 6-dichloro-benzo [1, 6-trimethyl-benzo ] naphthalene, 3] dioxol-5-yl-4, 6-trichloromethyl [1,3,5] trichloromethane, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2-benzene-4, 6-bis (trichloromethyl) -s-triazine, 2-naphthalene-4, 6-bis (trichloromethyl) -s-triazine, and the like, are used singly or as a mixture of two or more.
Further, the epoxy-or amine-based compound is contained in an amount of 0.001% -0.1%.
When a silicon-based additive having an epoxy group or an amine group is added, the adhesion between the ITO electrode and the negative photoresist composition is further improved, and the heat resistance after curing is also improved. By way of illustration, the silicon-based compounds are trimethoxysilane, methyldimethoxysilane, dimethoxysilane, 3, 4-epoxybutyltrimethoxysilane, 2- (3, 4-oxirane) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane, (3-aminopropyl) trimethylsilane, (N, N-diethyl-3-aminopropyl) trimethylsilane, N-beta (aminoethyl) gamma-aminopropyl trimethoxysilane and the like, which may be used alone or in combination.
Further, a solvent is also included.
The solvent to be added to the negative photoresist composition of the present invention may be a general solvent, and in consideration of the compatibility of the binder resin, the polyfunctional monomer having an ethylene unsaturated bond, the photoinitiator and other compounds, the solvent used in the present invention may be selected from diethylene glycol dimethyl ether (DMC), diethylene glycol dimethyl ether (MEC), methyl methoxy propyl ester, ethylene glycol dimethyl ether (EEP), propylene glycol dimethyl ether (PGMEA), propylene glycol dimethyl ether, methyl acrylate, propyl acrylate, methyl cellulose, ethyl cellulose, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, methyl isobutyl ketone, cyclohexanone, dimethoxyformamide (DMF), N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ -butadiene, diglycine (Diglyme), methyl cellulose, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, etc., and two or more thereof may be used singly or in combination. The solvent is preferably added to the negative photoresist composition to have a viscosity in the range of 2 to 30cps, more preferably, to have a viscosity adjusted to 10 to 25cps, and the film is relatively easy to adjust without pinholes of the film after coating.
Other additives such as a photo-increasing/decreasing agent, a thermal polymerization inhibitor, a defoaming agent, and a leveling agent may be added to the negative photoresist composition of the present invention, depending on the use requirements, without departing from the scope of the present invention.
It is another object of the present invention to provide an application of the negative photoresist composition for preparing an organic insulating film of a high aperture ratio liquid crystal display element. The negative photoresist composition is applied with a solvent, spin-coated on a substrate, irradiated with ultraviolet rays using a mask, and formed into an organic insulating film by a method of developing with an alkali developer.
The resin of the general formula I of the present invention is a resin formed by condensation reaction of a silicon compound and introduction of an organic group having photoreactivity, and when used as a binder resin in an organic-inorganic hybrid negative photoresist composition, an organic insulating film having a low dielectric constant can be formed, and excellent characteristics of an organic-inorganic mixture can be achieved by forming a network by photoreaction and introducing an inorganic substance into the organic insulating film. Therefore, the process yield is improved, and the manufacturing cost is reduced. The resins of the general formula I preferably have an average molecular weight of 200 to 20,000 and a dispersity of 1 to 5.0, more preferably 500 to 10,000 and a dispersity of 1.1 to 2.5.
In addition, in the organic-inorganic hybrid negative photoresist composition for the preparation of an organic insulating film for a high aperture ratio liquid crystal display element of the present invention, it is preferable to add a monomer copolymer having double bond with a monomer containing carboxylic acid, that is, a resin represented by the above formula II, in addition to the binder resin represented by the formula I as a binder resin. For example, the resin of formula I and the resin of formula II may be added in a weight ratio of 0.1:99.9 to 99.9:0.1. Preferably, the resins of formula II have an average molecular weight of 2000 to 50,000, a dispersity of 1.0 to 5.0, an acidity of 30to 200KOHmg/g, preferably an average molecular weight of 3000 to 20,000, a dispersity of 1.6 to 3.0 and an acidity of 50 to 150KOHmg/g. If the negative photoresist composition containing both the resin of formula I and the resin of formula II is coated to form a pattern, there is no defect such as residue after development, and there is an advantage in that the planarization rate is more excellent. In particular, Y of formula II 1 As the alkyl group having 1 to 12 carbon atoms, phenyl group, epoxy group, glyceryl group, oxo group, benzyl group, cyclic saturated hydrocarbon, hydroxyalkyl group, etc., not only chemical resistance can be improved but also a pattern model can be adjusted, contributing to improvement of adhesion. In addition, Y 2 Unlike a conventional binder resin made of an acrylic copolymer resin including an aromatic group, it includes a structure having a larger alicyclic structure, not only can the residual film rate be improved, but also the glass transition temperature is high, thereby improving heat resistance and chemical resistance, and improving transparency. In addition, the curing degree and the film residue ratio of the negative photoresist composition are improved by the carbonate (Carbamate) -containing acrylate.
The invention has the beneficial effects that: the organic insulating film formed by using the negative photoresist composition to which the binder resin of the present invention is added not only exhibits a low dielectric constant and strong adhesion to metals, but also has excellent heat resistance, UV transmittance, film residue ratio, flatness and pattern stability.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
The structure of the resin compound of the general formula I is shown in Table 1.
The average molecular weight of the resin compounds shown in Table 1 is about 500 to 20000, and the dispersity is 1 to 5.0.
TABLE 1 Structure of resin Compounds of general formula I
The following illustrates the synthesis of a portion of the resin compounds of formula I described above, and the resin compounds of formula I in Table 1 can be obtained by adjusting the different monomers in any of the following synthetic modes. The monomer in the first formula refers to a siloxane structural monomer and an acrylic monomer, wherein the siloxane monomer can be one or more of benzene trimethoxy silane, methyl triethoxy silane, epoxypropyl trimethoxy silane, propenyl trimethoxy silane and the like, and the acrylic monomer can be acrylic carboxylic acid monomer such as methacrylic acid or acrylic acid and the like.
Example 1
To a reactor equipped with a stirrer and a reflux cooling device, 0.3mol of phenyltrimethoxysilane, 0.15mol of methyltrimethoxysilane, and 0.15mol of methyltriethoxysilane were added, and 150mL of Propylene Glycol Methyl Ether Acetate (PGMEA) was further added, 1g of an oxalic acid catalyst was added, and after the solution temperature reached 60 ℃, 10g of ion-exchanged water was added, and the mixture was heated to 75℃and maintained for 3 hours, to obtain a hydrolytic condensate in the following formula.
2g of oxalic acid and 0.3mol of methacrylic acid were added to the resulting hydrolysis condensate, followed by reaction at 75℃for 3 hours. 20g of toluene was added to remove water, and then toluene, water and methanol were removed at 40℃and below 30 Torr. The photoreactive group-introduced product had an average molecular weight (Mn) of 3700 and a molecular weight distribution (Mw/Mn) of 2.0.
Example 2
150mL of diacetone alcohol, 0.3mol of phenyltrimethoxysilane, and 0.1 mol of methyltrimethoxysilane were charged into a reactor equipped with a stirrer and a reflux cooling device, and stirred at room temperature. An aqueous solution of 0.1g oxalic acid and 27g deionized water were then added and then heated to 75 ℃. After the temperature reached 75 ℃, the reaction was maintained for 3 hours to obtain a hydrolysis condensate.
3.5g of p-hydroxybenzenesulfonic acid and 0.2 mol of methacrylic acid were added to the resulting hydrolysis condensate, followed by reaction at 75℃for 3 hours. 20g of toluene was added to remove the resulting water, and then toluene, water and methanol were removed at 40℃and below 30 torr. The average molecular weight (Mn) of the product into which the reactive group containing a double bond or the like was introduced was 3700, and the molecular weight distribution (Mw/Mn) was 2.0.
The introduction reaction of the organic group using the above siloxane is carried out by synthesizing the siloxane by a conventionally known method, then adding a corresponding organic acid (methacrylic acid or acrylic acid) as a catalyst, and then carrying out dehydration reaction in a solvent using hydroxybenzenesulfonic acid.
The present invention can also be correspondingly obtained by adding different monomers to obtain resin compounds containing different substituent types in table 1.
The structure of the resin compound of the general formula II is shown in Table 2.
The average molecular weight of the resin compounds shown in Table 2 is about 4000 to 12000, the dispersity is about 2.3 to 2.7, and the acidity is about 60 to 95.
TABLE 2 Structure of resin Compounds of general formula II
The following illustrates the synthesis of a portion of the resin compounds of formula II described above, and the resin compounds of formula II in Table 2 can be obtained by adjusting the different monomers in any of the following synthetic modes.
Example 3
Synthesis of Compounds of formula IIa
A mixed solution of 700g of propylene glycol methyl ether acetate, 65g of methacrylic acid, 264 g by weight of benzyl methacrylate and 26g of 2-hydroxyethyl acrylate was injected into a flask equipped with a cooler and a stirrer. After the above-mentioned liquid composition was thoroughly mixed in a mixing vessel at 600rpm, 7.5g of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added. The polymerization mixture was slowly warmed to 50℃and kept at that temperature for 6 hours to obtain a copolymer solution. 0.005g of a phosphate was added to the reaction system to terminate the polymerization reaction, to obtain a polymer. The flask temperature was cooled to 20℃to obtain an acrylic copolymer, at which time the average molecular weight (Mw) of the acrylic polymer in the obtained polymer solution was 5000 and Mw/Mn was 2.0.
Example 4
Synthesis of Compound of formula IIb
A mixed solution of 800g of propylene glycol methyl ether acetate, 72g of methacrylic acid, 107g of methyl methacrylate, 317g of benzyl methacrylate was charged into a flask equipped with a cooler and a stirrer. After the above-mentioned liquid composition was thoroughly mixed in a mixing vessel at 600rpm, 7.5g of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added. The polymerization mixture was slowly warmed to 50℃and kept at that temperature for 6 hours to obtain a copolymer solution. 0.00500g of a phosphate was added to the reaction system to terminate the polymerization reaction, thereby obtaining a polymer. The flask temperature was cooled to 20℃to obtain an acrylic copolymer, at which time the average molecular weight (Mw) of the acrylic polymer in the obtained polymer solution was 5000 and Mw/Mn was 2.0.
Example 5
Synthesis of formula IIa-1
Monomer benzyl methyl methacrylate 195.0g, glycidyl methacrylate 97.5g, methacrylic acid 97.5g were placed in a polymerization vessel charged with 14g AIBN and 610g propylene glycol monomethacrylate, and stirred at 80℃for 5 hours to obtain 1000g of a resin polymer solution. The resin obtained had an average molecular weight of 8000, a degree of distribution of 2.2 and an acidity of 85mgKOH/g.
Example 6
Synthesis of formula IIc
187.2g of monomeric cyclopentadiene methacrylate, 97.5g of glyceryl methacrylate and 97.5g of methacrylic acid were placed in a polymerization vessel charged with 14g of AI BN and 610g of methyl acrylate, and stirred at 80℃for 5 hours to obtain 1000g of a resin polymer solution. The average molecular weight of the obtained resin was 21000, the degree of distribution was 2.3, and the acidity was 95mgKOH/g.
Preparation of negative photoresist composition
In a reaction mixing tank equipped with a sun-proof film and a stirrer, a negative photoresist composition was prepared according to the composition and content shown in Table 3 below, and the composition was stirred at room temperature, and a solvent was applied to the composition to prepare a negative photoresist composition for forming an organic insulating film of a high aperture ratio liquid crystal display element having a viscosity of about 4 to 7 cps.
TABLE 3 preparation of negative photoresist compositions of application examples 1-16
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In Table 3 above, DPHA is ethylene glycol terephthalate
A-187 (3-glycidoxypropyl) trimethoxysilane (Silquest Corp.)
I-907 Irgacure 907 (Ciba Specialty Chemicals company product)
Irgacure 369 (Ciba Specialty Chemicals company product)
Leveling agent, namely leveling agent of silica gel series is used. (BYK company product)
Application example 1
4g of the siloxane acrylic polymer of formula I-a prepared in Table 1 above, 3g of the acrylic copolymer of formula IIa prepared in Table 2 above (wherein a/b/c is MAA/GMA/BzMA=25/25/50), 0.70g of the photoinitiator Irgacure-907, irgacure-3690.05g, 6g of the crosslinking monomer dipentaerythritol hexaacrylate, and 0.05g of the siloxane-ethyleneoxy surface compound (siloxane-propyleneoxy) for increasing the adhesion of the substrate to the coating film were mixed, and propylene glycol methyl ether acetate was dissolved in the mixture to a solid concentration of 17%, followed by filtration with a 0.2 μm microporous filter to prepare a negative type photoresist composition.
Application example 2
4g of the siloxane acrylic polymer of formula I-a prepared in Table 1 above, the acrylic copolymer of formula IIc prepared in Table 2 above (wherein a/b/c is methyl methacrylate/glycidyl methacrylate/dicyclopentyl acrylate=25/35/40), a photoinitiator, 0.3g of Irgacure-907, 0.05g of Irgacure-369, a crosslinkable monomer dipentylsilane, and 6g of a binder were mixed, propylene glycol methyl ether acetate was dissolved in the above mixture to have a solid concentration of 17%, and then filtered with a 0.2 μm microporous filter, to prepare a negative type photoresist composition.
Comparative example
Negative type resist compositions for forming an organic insulating film of a high aperture ratio liquid crystal display device were produced as comparative examples 1 to 5 in the same components and contents as in application examples 1 to 5 except that the binder resin represented by the following formula 3 was used instead of the binder resin (average molecular weight 15000) of application example 1 described above.
In the above formula 3, o is 0.52, p is 0.3, q is 0.08, and r is 0.1.
Wherein, the preparation process of the compound of the formula 3:
a mixed solution of 400g of propylene glycol methyl ether acetate, 52g of methacrylic acid and 16g of styrene, 104g of methacrylic acid and 26g of 2-hydroxyethyl acrylic acid was injected into a flask equipped with a cooler and a stirrer. After the above-mentioned liquid composition was thoroughly mixed in a mixing vessel at 600rpm, 5.0g of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added. The polymerization mixture was slowly warmed to 50℃and kept at that temperature for 6 hours to obtain a copolymer solution. 0.005g of a phosphate was added as a polymerization inhibitor to the obtained polymer. The flask temperature was cooled to 20℃to obtain an acrylic copolymer, at which time the average molecular weight (Mw) of the acrylic polymer in the obtained polymer solution was 4000 and Mw/Mn was 2.0.
Specific embodiments of comparative examples 1 to 5 were as follows, compositions according to the formulation amounts of Table 4, were mixed with a photoinitiator, 0.3g Irgacure-907, 0.05g Irgacure-369, a crosslinkable monomer dipentylsilane, and 6g binder, propylene glycol methyl ether acetate was dissolved in the above mixture to have a solid concentration of 17%, and then filtered through a 0.2 μm microporous filter, to prepare negative type resist compositions.
TABLE 4 compositions and amounts used for preparation of negative photoresist compositions of comparative examples 1-5
In the above application examples and comparative examples, evaluation of the negative type resist composition was performed according to the criteria on a substrate such as a silicon wafer or a glass plate, and the results thereof are shown in tables 5 and 6 below.
(1) Measurement of dielectric constant
A negative photoresist was coated on a substrate on which an aluminum electrode was formed using a spin coater to form a film, and a dielectric constant measuring unit was manufactured, and the dielectric constant was measured by an impedance matcher.
(2) Adhesion of metals to inorganic substances (Adhesion)
The photoresist composition was pre-baked at 90 c for 1 minute after being coated on a substrate at 250rpm using a spin coater for 30 seconds, exposed at 90mJ, post-baked at 220 c for 60 minutes (postrake), formed into a photoresist film, and put into an automatic Autoclave, and fermented at 100 c for 1 hour. The test piece fermented in the automatic scraper is scraped by a bevel cutter, the substrate is exposed, and then is stuck by an adhesive tape and is detached. If more than 80 of the 100 cells are not separated from the substrate, the judgment is good, otherwise the judgment is bad "
(3) UV transmittance
The photoresist composition was pre-baked at 90 c for 1 minute after being coated on a substrate at 250rpm using a spin coater for 30 seconds, developed in a TMAH developer for 50 seconds, rinsed with pure water for 60 seconds, dried with compressed air, and post-baked at 220 c for 60 minutes to form a photoresist film of about 3.0 to 3.5 μm, and transmittance in a 400nm region was measured by UV.
(4) Residual film rate
The photoresist composition was spin-coated on a substrate, and the thickness ratio (%) of the film formed after the pre-bake and the post-bake to remove the solvent was measured.
(5) Patterning
The silicon wafer on which the photoresist pattern was formed was cut from the vertical direction of the hole pattern, and the result was observed with an electron microscope from the cross-sectional direction of the pattern. The pattern side walls stand at an angle of 80 degrees or more with respect to the substrate, and the film is not reduced "good", and the reduction of the film is regarded as "film reduction".
(6) Chemical resistance
After the photoresist composition was coated on a substrate using a spin coater, a photoresist film formed through a pre-bake, an exposure process, a post-bake, and the like was immersed in a stripper, an etching solution at 40 ℃ for 10 minutes, and then whether the transmittance and thickness of the photoresist film were changed was observed. When the transmittance and the thickness were not changed, it was judged as "good", and when the transmittance and the thickness were changed, it was judged as "bad".
Table 5 Performance data sheets of application examples 1 to 16
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Table 6 Performance data sheets for comparative examples 1-5
As can be seen from the data, the negative photoresist composition prepared from the resin compound has the advantages of low dielectric constant, good adhesion performance, high residual film rate, and good UV transmittance, pattern formation and chemical resistance. Therefore, the method can be effectively used for preparing the organic insulating film of the high-aperture-ratio liquid crystal display device.
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 (9)

1. A binder resin characterized in that the structure thereof comprises the following general formula i and/or general formula ii:
wherein at least one R is a photoreactive acrylic acid, methacrylic acid or an organic group containing an unsaturated bond, and the other R are each independently selected from H atoms, glycidyl epoxy esters, and alkyl groups having 1 to 5 carbon atoms;
Z 1 each independently selected from the group consisting of linear alkyl or alkenyl groups having 1 to 24 carbon atoms, cyclic alkyl or alkenyl groups, aromatic hydrocarbons, glyceryl groups, methacrylate groups, amine groups, and carboxyl groups;
n is an integer from 1 to 40;
wherein a, b, c are the molar ratio of each monomer, 0.ltoreq.a <1, 0.ltoreq.b <1, 0.ltoreq.c <1, a+b+c=1;
x is independently selected from hydrogen atom or alkyl with 1 to 5 carbon atoms;
Y 1 and Y 2 Each independently selectAlkyl, phenyl, epoxy, glyceryl, oxy, benzyl, cyclic saturated hydrocarbon, and hydroxyalkyl having 1 to 12 carbon atoms.
2. The binder resin according to claim 1, wherein the average molecular weight of formula i is 500 to 20000 and the dispersity is 1 to 5.0.
3. The binder resin according to claim 1, wherein the average molecular weight of formula ii is 2000 to 20000, the dispersity is 1.6 to 3.0, and the acidity is 30to 150KOHmg/g.
4. The binder resin of claim 1 wherein the weight ratio of the resin of formula i to the resin of formula ii is 0.1:99.9 to 99.9:0.1.
5. A negative photoresist composition comprising the binder resin of any one of claims 1 to 4.
6. The negative photoresist composition according to claim 5, wherein the binder resin is present in an amount of 5% to 30% by weight based on the total weight of the composition.
7. The negative photoresist composition according to claim 6, further comprising 5% to 35% of a polyfunctional monomer having an ethylenically unsaturated bond, and 0.5% to 10% of a photoinitiator.
8. The negative photoresist composition according to claim 7, further comprising 0.001% -0.1% of an epoxy or amine based silicon based compound.
9. Use of the negative photoresist composition according to claim 5 to 8, for preparing an organic insulating film for a high aperture ratio liquid crystal display element.
CN202310783117.0A 2023-06-29 2023-06-29 Adhesive resin and application thereof Pending CN116693856A (en)

Priority Applications (1)

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CN202310783117.0A CN116693856A (en) 2023-06-29 2023-06-29 Adhesive resin and application thereof

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Application Number Priority Date Filing Date Title
CN202310783117.0A CN116693856A (en) 2023-06-29 2023-06-29 Adhesive resin and application thereof

Publications (1)

Publication Number Publication Date
CN116693856A true CN116693856A (en) 2023-09-05

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Family Applications (1)

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Country Status (1)

Country Link
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