CN111285955A - Alkali soluble resin, preparation method thereof and negative photoresist composition - Google Patents
Alkali soluble resin, preparation method thereof and negative photoresist composition Download PDFInfo
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- CN111285955A CN111285955A CN201911370442.4A CN201911370442A CN111285955A CN 111285955 A CN111285955 A CN 111285955A CN 201911370442 A CN201911370442 A CN 201911370442A CN 111285955 A CN111285955 A CN 111285955A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
An alkali soluble resin, a method of preparing the alkali soluble resin, and a negative photoresist composition containing the alkali soluble resin are disclosed. The alkali soluble resin can obtain the insulating transparent negative photoresist composition with excellent performances such as photosensitivity, developability, flexibility, adhesion and the like under different formulas or different experimental conditions. The insulating transparent negative photoresist composition is suitable for a flexible OLED touch display screen, is used as a protective layer of an electrode circuit, and has excellent properties of good adhesion with a high-molecular transparent film substrate, yellowing resistance, high light sensitivity, developer tolerance, high resolution, high light transmittance and the like.
Description
Technical Field
The present invention relates to an alkali-soluble resin, a method of preparing the alkali-soluble resin, and a negative photoresist composition containing the resin.
Background
The photoresist is also called photoresist/photoresist, and is mainly a photosensitive mixture composed of film-forming resin, active monomer, photoinitiator and solvent. The photoresist is classified into a positive photoresist and a negative photoresist according to a chemical reaction mechanism and a development principle. Photoresists are known as positive photoresists that decompose upon exposure to light (UV light), whereas negative photoresists that react to polymerize upon exposure to light.
The insulating transparent negative photoresist is mainly used in the field of touch screens (TP), is used as an electrode protective film of a transparent electrode circuit of a display screen, ensures the sensitivity and accuracy of a touch point of the touch screen, has yellowing resistance and high transparency, and is a key material for flat panel display. Although negative photoresist compositions having different components and different structures have been disclosed in the prior art, the problems of poor adhesion between the photoresist and the polymer transparent thin film substrate, poor developability, resolution and chemical resistance still remain.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides an alkali-soluble resin, a method for preparing the alkali-soluble resin and an insulating transparent negative photoresist composition containing the resin.
The technical scheme of the invention is as follows:
an alkali soluble resin is prepared from the resin No. 1 and the compound containing hydroxyl group R1The polymer obtained by reaction, wherein the 1 st resin is a copolymer obtained by copolymerizing four substances of a), b), c) and d):
a) one selected from glycidyl methacrylate, glycidyl acrylate, 2-vinyl oxirane, 1, 2-epoxy-9-decene, 1, 2-epoxy-5-hexene, allyl glycidyl ether and 4-vinylbenzyl glycidyl ether,
b) one selected from acrylic acid and methacrylic acid,
c) one selected from the following structural formulae (1) to (2):
d) selected from benzyl (meth) acrylate, methyl (meth) acrylate, 2-chloroethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, methoxydiglycol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol monoethylether (meth) acrylate, triethylene glycol di (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, Triethylene glycol acrylate, triethylene glycol di (meth) acrylate, dimethylaminoethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, poly (propylene glycol) methyl ether acrylate, tricyclo [5.2.1.02, 6] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, phenoxydiglycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tribromophenyl (meth) acrylate, dicyclopentene (meth) acrylate, dicyclopentenyl (meth) acrylate, and mixtures thereof, One of (dicyclopentadienyloxy) ethyl (meth) acrylate and 2, 2-bis (1-cyclopenten-1-yloxy) ethyl (meth) acrylate,
wherein the content of the first and second substances,
n in the structural formulas (1) to (2) is selected from an integer of 0 to 4;
r in the structural formulas (1) - (2) is selected from one of halogen, furyl, cyclopentyl, methyl cyclopentyl, phenyl, phenoxy and isocyano;
preferably, the hydroxyl group-containing compound R1One selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate and 4-hydroxystyrene.
Preferably, the molar ratio of the four substances a), b), c) and d) is (2-35): (21-116): (2-24): (10-50).
Preferably, the substance a and the hydroxyl group-containing compound R1The molar ratio of (1-56): (2-39).
Preferably, the acid value of the alkali-soluble resin is 25-160 mgKOH/g, more preferably 80-110 mgKOH/g. In the case where the acid value of the alkali-soluble resin satisfies the above range, the development speed of the high-insulation transparent negative-type photoresist composition can be sufficiently ensured, and the problems of compatibility and storage stability can be improved. When the acid value is less than 25mgKOH/g, the dissolution rate of the alkali-soluble resin in the unexposed area is too slow to be completely removed in the reaction process of the alkali-soluble resin and the developing solution, the residual glue is left at the edge of the glue line of the exposed pattern, and the residual glue rate is higher; when the acid value is greater than 160mgKOH/g, the dissolution rate of the alkali-soluble resin in the unexposed area in the reaction process with the developing solution is too high, over-development is easily generated, the exposed and cured glue line is excessively etched by alkali liquor, the line surface is rough, the line edge is jagged, and the pattern linearity is poor.
Preferably, the weight average molecular weight of the alkali-soluble resin is 8000 to 100000, more preferably 9000 to 65000, and still more preferably 9000 to 30000. When the weight average molecular weight of the alkali-soluble resin is less than 8000, image generation failure and deterioration of chemical resistance during development may be caused; when the weight average molecular weight of the alkali-soluble resin is more than 100000, an increase in alkali resistance is caused so that development resistance is increased during development and residual gum is easily formed.
Preferably, the molecular weight distribution of the alkali-soluble resin is between 1 and 3, preferably between 1.5 and 2.5. Too narrow or too wide a molecular weight distribution affects the resolution of the negative photoresist composition.
The acid value of the alkali-soluble resin is determined by an acid-base titration method, and the molecular weight and molecular weight distribution are determined by Gel Permeation Chromatography (GPC).
The preparation method of the alkali-soluble resin comprises the following operation steps:
1) adding the four substances a, b, c and d and a proper amount of organic solvent into a reactor, heating to 80 ℃ to completely dissolve the four substances, uniformly mixing a proper amount of initiator, chain transfer agent and organic solvent, slowly dripping the mixture into a reaction container, and reacting for 2-12h at 90-150 ℃ to obtain the resin 1;
2) cooling the 1 st resin in the step 1) to 60 ℃, and slowly dropping the hydroxyl-containing compound R into the reactor1The temperature of the mixed solution of the catalyst and a proper amount of organic solvent is kept unchanged in the processes of dropwise adding and reaction, and the reaction is continued for 0.5 to 1 hour after the dropwise adding is finished. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain the alkali soluble resin.
Preferably, the substance a is one selected from glycidyl methacrylate, glycidyl acrylate, 2-vinyl oxirane, 1, 2-epoxy-9-decene, 1, 2-epoxy-5-hexene, allyl glycidyl ether and 4-vinylbenzyl glycidyl ether;
preferably, the substance b is selected from one of acrylic acid and methacrylic acid;
preferably, the substance c is selected from one of the following structural formulae (1) to (2):
preferably, the substance d is selected from benzyl (meth) acrylate, methyl (meth) acrylate, 2-chloroethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, methoxydiglycol (meth) acrylate, diglycol di (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, triethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dimethylaminoethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, poly (propylene glycol) methyl ether acrylate, tricyclo [5.2.1.02, 6] dec-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, cyclohexyl (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, phenoxydiglycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate propyl (meth) acrylate hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, poly (ethylene, One of tribromophenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (dicyclopentadienyloxy) ethyl (meth) acrylate, 2-bis (1-cyclopenten-1-yloxy) ethyl (meth) acrylate;
preferably, n in the structural formulas (1) to (2) is selected from an integer of 0 to 4;
preferably, R is selected from one of halogen, furyl, cyclopentyl, methyl cyclopentyl, phenyl, phenoxy and isocyano;
preferably, the hydroxyl group-containing compound R1One selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate and 4-hydroxystyrene.
Preferably, the molar ratio of the four substances a), b), c) and d) is (2-35): (21-116): (2-24): (10-50).
Preferably, the substance a and the hydroxyl group-containing compound R1The molar ratio of (1-56): (2-39).
The chain transfer agent in the step 1) is a substance capable of effectively transferring a chain propagation free radical, and preferably, the chain transfer agent is selected from one or more of the following substances: aliphatic mercaptans, dodecyl mercaptan, carbon tetrachloride, dithioesters, iodoform, 1-chloro-1-iodoalkane, and the like.
The initiator in the step 1) can be an azo compound initiator, a peroxide initiator and a redox initiator, and preferably, the initiator is selected from one or more of the following substances: azobisbutyronitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, dibenzoyl peroxide, and the like.
The catalyst in the step 2) is a catalyst generally used for the esterification reaction, and is not particularly limited. Preferably, the catalyst is selected from one of p-toluenesulfonic acid and zinc acetate.
The organic solvent described in step 1) and step 2) is an organic solvent generally used in this field, and is not particularly limited. Preferably, the organic solvent is selected from one of cyclohexanone, propylene glycol methyl ether acetate, xylene, ethyl acetate and propylene glycol methyl ether.
An insulating transparent negative photoresist composition comprising the alkali-soluble resin, consisting of the following components in percentage by mass:
preferably, the viscosity threshold of the negative photoresist composition is 5 to 30 mPas. Viscosity is the main parameter for determining the performance of the negative photoresist composition, and is too high to facilitate the coating of the high-insulation transparent negative photoresist; when the viscosity is too low, the solid content of the high-insulation transparent negative photoresist composition is too low, the film thickness does not meet the requirement, a film forming defect may be formed on a substrate, and the insulation protection function cannot be realized, so that the viscosity of the high-insulation transparent negative photoresist composition needs to meet the set viscosity threshold.
The reactive diluent monomer contains at least one unsaturated carbon-carbon double bond, which reacts with a radical generated by the photoinitiator to initiate polymerization. Preferably, the reactive diluent monomer is a mixture of a bifunctional monomer containing a vinyl group and a polyfunctional monomer containing a vinyl group, and the mass ratio of the bifunctional monomer containing a vinyl group to the polyfunctional monomer containing a vinyl group is as follows: 1:1 to 1: 10.
Preferably, the vinyl group-containing bifunctional monomer is selected from one of the following: ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dicyclopentadiene acrylate, tripropylene glycol di (meth) acrylate.
Preferably, the polyfunctional vinyl-containing monomer is selected from one or more of the following: trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol trimaleate, propoxylated trimethylolpropane tri (meth) acrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate.
The photoinitiator is a mixed photoinitiator composed of a free radical photoinitiator and a cationic photoinitiator, and the free radical photoinitiator and the cationic photoinitiator can be mixed in any proportion.
Preferably, the free radical photoinitiator is selected from one of benzoin and derivatives thereof, benzil ketals and derivatives thereof, dialkoxyacetophenones, α -hydroxyalkylphenone, α -aminoalkylphenones, acylphosphine oxides, esterified oxime ketone compounds, aryl peroxy esters, halogenated methyl aryl ketones, organic sulfur-containing compounds, benzoyl formate esters, benzophenone and derivatives thereof, thioxanthone and derivatives thereof, bisimidazoles or camphorquinone.
More preferably, the free radical photoinitiator is selected from one of Irgacure 651, Irgacure184, BP, ITX, Darocure 1173, Irgacure 907, TPO and Irgacure 369.
The cationic photoinitiator is another important photoinitiator, is beneficial to ring-opening polymerization reaction, can improve the adhesion of a photoresist and a high-molecular transparent film, and is suitable for the monomers of the cationic photoinitiator, such as epoxy compounds, vinyl ethers, lactones, acetals, cyclic ethers and the like. Preferably, the cationic photoinitiator is selected from one of the following: diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers. More preferably, the cationic photoinitiator is selected from one of Irgacure 261 and Irgacure 250.
The auxiliary agent is an adhesion promoter, a leveling agent, a defoaming agent, an antioxidant and a stabilizer, and the mass ratio of the auxiliary agent to the auxiliary agent is (1-5): 0.05-3): 0.1-5): 0.1-1): 0.1-3. Wherein the adhesion promoter is one or a mixture of more than two of hydroxyalkyl acrylate, acrylic acid, acrylate containing a shuttle functional group or phosphate ester adhesion promoter containing an unsaturated functional group, and can be one or two of a hume 1121 adhesion promoter, Sartomer CD9051, A-172 silane coupling agent of Union carbon company and methacrylate phosphate ester; preferably a humble 1121 or a-172. The leveling agent is one or more of acrylic compounds, organic silicon compounds and fluorocarbon compounds, and organic silicon compounds such as TEGO1484, BYK333, BYK349 and the like are preferred. The antifoaming agent is solvent antifoaming agent 2700 or 3100 from Germany, antifoaming agent Airex900 or Airex920 from Digao, and the like; solvent-based antifoaming agents 3100 are preferred. The antioxidant is one or more of hindered phenolic compounds, phosphite compounds, thio compounds and composite compounds, preferably hindered phenolic compounds, such as BHT, 2246, 1010, 1076 and the like. The stabilizer is one or more of ferrocene compounds, anhydride compounds and phenol compounds, and the ferrocene compounds are ferrocene, methyl ferrocene and ethyl ferrocene; the acid anhydride compound is phthalic anhydride, maleic anhydride or succinic anhydride; the phenol compound is hydroquinone, p-methoxyphenol, 2, 6-di-tert-butyl-p-cresol. Preference is given to ferrocene, methyl ferrocene, ethyl ferrocene, phthalic anhydride, hydroquinone and/or p-methoxyphenol.
Preferably, the solvent is composed of 1 to 4 solvents with different boiling points, and is selected from the following substances: any mixture of ethanol, acetone, ethylene glycol propyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl lactate, n-hexane, toluene, xylene, n-butyl acetate, sec-butyl acetate, butyl monoethylene glycol, methyl monoethylene glycol, ethyl monoethylene glycol, butyl monopropylene glycol, ethyl monoethylene glycol acetate, butyl monoethylene glycol acetate, ethylene glycol ethyl ether acetate, butyl ethylene glycol, methyl diethylene glycol methyl ether, ethyl diethylene glycol ethyl ether, butyl diethylene glycol butyl ether, dimethyl diethylene glycol, tetrahydrofuran, diethyl diethylene glycol ethyl ether, butyl diethylene glycol, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclohexanone, etc., but not limited thereto.
In the present invention, "()" in methyl (meth) acrylate means and/or, the explanation applies to "(methyl)" in other compounds.
The invention has the following beneficial effects: the alkali soluble resin of the invention can obtain the insulating transparent negative photoresist composition with excellent performances such as photosensitivity, developability, adhesiveness and the like under different formulas or different experimental conditions. The insulating transparent negative photoresist composition prepared by the invention is suitable for a flexible OLED touch display screen, is used as a protective layer of an electrode circuit, and has excellent properties of good adhesion with a high-molecular transparent film substrate, yellowing resistance, high light sensitivity, developer tolerance, high resolution, high light transmittance and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Synthesis of alkali-soluble resin:
example 1
14.2g of glycidyl methacrylate, 90.0g of methacrylic acid, 16.2g of phenyl methacrylate, 50g of methyl methacrylate and 500g of cyclohexanone are added into a 1000mL four-mouth bottle provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.5g of dibenzoyl peroxide, 0.35g of dithioester and 50g of cyclohexanone are mixed and shaken uniformly, then added into a reaction bottle from the dropping funnel, the temperature does not exceed 90 ℃, the dripping is finished for 35min, and then the reaction is carried out for 6h at 125 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.03g of p-toluenesulfonic acid, 30g of hydroxyethyl methacrylate and 10g of cyclohexanone was added dropwise over 2 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 40 min. The product is cooled to room temperature, filtered, the solvent is removed, washed with petroleum ether and dried, thus obtaining the alkali-soluble resin A.
The weight-average molecular weight of the alkali-soluble resin A was 9000, the molecular weight distribution was 2.1, and the acid value was 80 mgKOH/g.
Example 2
16.9g of glycidyl methacrylate, 72.0g of acrylic acid, 13.8g of 2-phenoxyethyl methacrylate, 65g of 2-hydroxyethyl methacrylate and 500g of propylene glycol methyl ether acetate are added into a 1000mL four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.35g of azobisisobutylamidine hydrochloride, 0.05g of dodecyl mercaptan and 50g of propylene glycol methyl ether acetate are mixed, shaken uniformly, added into a reaction flask from the dropping funnel, the temperature is not more than 90 ℃, the reaction is finished for 30min, and then the reaction is carried out for 3h at 115 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of zinc acetate, 45g of hydroxyethyl acrylate and 10g of propylene glycol methyl ether acetate was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin B.
The weight-average molecular weight of the alkali-soluble resin B was 15000, the molecular weight distribution was 1.9, and the acid value was 85 mgKOH/g.
Example 3
12g of glycidyl methacrylate, 100g of methacrylic acid, 15g of dicyclopentanyl methacrylate, 65g of ethylhexyl methacrylate and 500g of xylene are added into a 1000mL four-neck flask provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ for complete dissolution, 0.35g of azobisbutyronitrile, 0.02g of aliphatic thiol and 50g of xylene are mixed, shaken uniformly, added into a reaction flask from the dropping funnel, the temperature does not exceed 90 ℃, and the reaction is finished after 40min, and then the reaction is carried out for 2h at 120 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of p-toluenesulfonic acid, 60g of 4-hydroxystyrene and 10g of xylene was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin C.
The weight-average molecular weight of the alkali-soluble resin C was 30000, the molecular weight distribution was 2.3, and the acid value was 110 mgKOH/g.
Example 4
16.9g of glycidyl methacrylate, 72.0g of acrylic acid, 13.8g of tetrahydrofuran methacrylate, 110g of dicyclopentenyl methacrylate and 500g of propylene glycol methyl ether acetate were put into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.5g of dimethyl azodiisobutyrate, 0.1g of carbon tetrachloride and 50g of propylene glycol methyl ether acetate were mixed and shaken uniformly, then added from the dropping funnel into a reaction flask at a temperature of not more than 90 ℃ for 32min to finish dropping, and then reacted at 130 ℃ for 5 hours.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of zinc acetate, 50g of hydroxypropyl acrylate and 10g of propylene glycol methyl ether acetate was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin D.
The weight-average molecular weight of the alkali-soluble resin D was 25000, the molecular weight distribution was 2.0, and the acid value was 80 mgKOH/g.
Example 5
24g of glycidyl methacrylate, 90g of methacrylic acid, 20g of 2-chloromethyl ethyl acrylate, 60g of triethylene glycol monoethyl ether methacrylate and 500g of ethyl acetate are added into a 1000mL four-mouth bottle provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.45g of azobisbutyronitrile, 0.05g of iodoform and 50g of ethyl acetate are mixed, shaken uniformly, added into a reaction bottle from the dropping funnel, the temperature is not higher than 90 ℃, the dripping is finished for 36min, and then the reaction is carried out for 2h at 140 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of p-toluenesulfonic acid, 30g of 2-4-hydroxybutyl methacrylate and 10g of ethyl acetate was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin E.
The weight-average molecular weight of the alkali-soluble resin E was 15000, the molecular weight distribution was 2.3, and the acid value was 95 mgKOH/g.
Example 6
24g of glycidyl methacrylate, 56.0g of acrylic acid, 22.4g of 1-methylcyclopentyl methacrylate, 80g of tetrahydrofuran methacrylate and 500g of propylene glycol methyl ether were put into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.35g of azobisisobutylamidine hydrochloride, 0.1g of 1-chloro-1-iodoalkane and 50g of propylene glycol methyl ether were mixed, shaken well, put into a reaction flask from the dropping funnel, the temperature was not more than 90 ℃, the reaction was completed for 38min, and then the mixture was reacted at 90 ℃ for 12 h.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of zinc acetate, 49.6g of hydroxypropyl methacrylate and 10g of propylene glycol methyl ether was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin F.
The weight-average molecular weight of the alkali-soluble resin F was 26000, the molecular weight distribution was 2.1, and the acid value was 85 mgKOH/g.
Example 7
Adding 80g of glycidyl methacrylate, 50g of methacrylic acid, 80g of isocyano ethyl methacrylate, 120g of (dicyclopentadienyloxy) ethyl methacrylate and 500g of xylene into a 1000mL four-mouth bottle provided with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, heating to 80 ℃ to completely dissolve the glycidyl methacrylate, mixing and shaking 0.55g of azobisbutyronitrile, 0.1g of dodecyl mercaptan and 50g of xylene, adding the mixture into a reaction bottle from the dropping funnel, keeping the temperature not higher than 90 ℃, completing dropping for 35min, and reacting for 6h at 120 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of p-toluenesulfonic acid, 30g of 2-methacrylic acid-4-hydroxybutyl ester and 10g of xylene was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin G.
The weight-average molecular weight of the alkali-soluble resin G was 65000, the molecular weight distribution was 2.3, and the acid value was 102 mgKOH/G.
Example 8
50g of glycidyl methacrylate, 72.0g of acrylic acid, 50g of 2-phenoxyethyl methacrylate, 82g of 3-chloro-2-hydroxypropyl methacrylate and 500g of ethyl acetate are added into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser tube, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.5g of azobisisobutylamidine hydrochloride, 0.1g of dodecyl mercaptan and 50g of ethyl acetate are mixed, shaken uniformly, added into a reaction flask from the dropping funnel, the temperature is not more than 90 ℃, the dripping is finished for 40min, and then the reaction is carried out for 3h at 115 ℃.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of zinc acetate, 55.5g of 4-hydroxybutyl acrylate and 10g of ethyl acetate was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product was cooled to room temperature, filtered, the solvent was removed, washed with petroleum ether, and dried to obtain an alkali-soluble resin H.
The weight-average molecular weight of the alkali-soluble resin H was 40000, the molecular weight distribution was 2.2, and the acid value was 110 mgKOH/g.
Comparative example 1
72.0g of acrylic acid, 13.8g of 2-phenoxyethyl (meth) acrylate, 65g of 2-hydroxyethyl (meth) acrylate and 500g of propylene glycol methyl ether acetate were put into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ to be completely dissolved, 0.35g of azobisisobutylamidine hydrochloride, 0.05g of dodecylmercaptan and 50g of propylene glycol methyl ether acetate were mixed, shaken well, put into a reaction flask from the dropping funnel, at a temperature of not more than 90 ℃ for 30min, and reacted at 115 ℃ for 3 hours.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of p-toluenesulfonic acid, 45g of hydroxyethyl acrylate and 10g of propylene glycol methyl ether acetate was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product is cooled to room temperature, filtered, the solvent is removed, washed with petroleum ether and dried, thus obtaining the alkali-soluble resin I.
The weight-average molecular weight of the alkali-soluble resin I was 8000, the molecular weight distribution was 2.3, and the acid value was 80 mgKOH/g.
Comparative example 2
100g of methacrylic acid, 15g of dicyclopentanyl (meth) acrylate, 65g of ethylhexyl (meth) acrylate and 500g of xylene are placed in a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, heated to 80 ℃ for complete dissolution, 0.35g of azobisbutyronitrile and 50g of xylene are mixed and shaken well, then added from the dropping funnel into a reaction flask at a temperature of not more than 90 ℃ for 40min, and reacted at 120 ℃ for 6 h.
Then, the reaction temperature was cooled to 60 ℃ and a mixed solution containing 0.05g of p-toluenesulfonic acid, 60g of hydroxypropyl acrylate and 10g of xylene was added dropwise over 1.5 hours, the temperature was kept constant during the addition and the reaction, and after the addition, the reaction was continued for 1 hour. The product is cooled to room temperature, filtered, the solvent is removed, washed with petroleum ether and dried, thus obtaining the alkali-soluble resin J.
The weight-average molecular weight of the alkali-soluble resin J was 23000, the molecular weight distribution was 3.6, and the acid value was 100 mgKOH/g.
Preparation of an insulating transparent negative photoresist composition:
example A
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 25% of the alkali-soluble resin A obtained in example 1, 1841.0% of a radical photoinitiator Irgacure, 2500.5% of a cationic photoinitiator Irgacure, 2% of trimethylolpropane tri (meth) acrylate, 2.5% of ethylene glycol di (meth) acrylate, 4% of an auxiliary agent (a leveling agent BYK 333: an adhesion promoter Delumu 1211: a defoamer Airex 900: an antioxidant BHT: a stabilizer hydroquinone ═ 1: 1: 0.5: 0.5: 1), 33% of cyclohexanone and 32% of ethylene glycol monomethyl ether, and uniformly stirring and mixing the components to obtain the high-performance epoxy resin.
Example B
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 20% of the alkali-soluble resin B obtained in example 2, 3.5% of a radical photoinitiator BP, 3.5% of a cationic photoinitiator Irgacure 2611.5%, 7.5% of dipentaerythritol pentaacrylate, 2.5% of dicyclopentadiene acrylate, 5% of an auxiliary agent (a leveling agent TEGO 1484: SartomerCD 9051: a defoaming agent 3100: an antioxidant 1076: 5: a stabilizer hydroquinone ═ 1: 0.5: 1), 30% of diethylene glycol monomethyl ether and 30% of ethylene glycol monobutyl ether, and uniformly stirring and mixing the components to obtain the aqueous alkali-soluble resin B, wherein the results are shown in Table I.
Example C
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 20% of the alkali-soluble resin C obtained in example 3, 1.5% of a radical photoinitiator TPO, 2501% of a cationic photoinitiator Irgacure, 7.5% of dipentaerythritol pentaacrylate, 5% of pentaerythritol tri (meth) acrylate, 2.5% of dicyclopentadiene acrylate, 4.5% of an auxiliary agent (a leveling agent TEGO 1484: Sartomer CD 9051: an antifoaming agent Airex 900: an antioxidant 2246: a stabilizer hydroquinone ═ 1: 1.5: 0.5: 0.5: 1), 30% of ethylene glycol monomethyl ether acetate and 28% of butyl acetate, and the mixture is stirred and mixed uniformly, and the result is shown in Table I.
Example D
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: the alkali-soluble resin D18%, the cationic photoinitiator Irgacure 2501%, the free radical photoinitiator ITX 0.5%, the tripropylene glycol di (meth) acrylate 2%, the propoxylated trimethylolpropane tri (meth) acrylate 8%, the auxiliary agent (the leveling agent TEGO 1484: Sartomer CD 9051: the antifoaming agent Airex 900: the antioxidant 1010: the stabilizer hydroquinone 1: 1: 0.5: 0.1: 1) 3.5%, the diethylene glycol dimethyl ether 35%, and the ethylene glycol methyl ether 32% obtained in example 4 were uniformly stirred and mixed, and the results are shown in Table I.
Example E
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: the alkali-soluble resin E15%, the cationic photoinitiator Irgacure 2612%, the radical photoinitiator Irgacure 1843%, the triethylene glycol di (meth) acrylate 1%, the ditrimethylolpropane tetraacrylate 9%, the auxiliary agent (the leveling agent TEGO 1484: a-172: the antifoaming agent 3100: the antioxidant 1010: 5% of the stabilizer p-methoxyphenol 1: 2: 1: 0.5: 0.5), the butyl cellosolve acetate 35%, the ethylene glycol monoethyl ether acetate 30%, which were obtained by stirring and mixing uniformly, were as shown in table one.
Example F
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: the alkali-soluble resin F25%, the cationic photoinitiator Irgacure 2611.5%, the radical photoinitiator TPO 0.5%, the pentaerythritol trimaleate 1%, the dicyclopentadiene acrylate 10%, the auxiliary agent (the leveling agent BYK 349: the adhesion promoter a-172: the defoamer Airex 900: the antioxidant 1076: the stabilizer p-methoxyphenol 1: 1: 0.5: 0.5: 1) 4%, the butyl cellosolve 29%, and the cyclohexanone 29% obtained in example 6 were uniformly stirred and mixed, and the results are shown in table one.
Example G
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 25% of the alkali-soluble resin G obtained in example 7, 2611.5% of a cationic photoinitiator Irgacure, 0.5% of a radical photoinitiator TPO, 2% of butanediol di (meth) acrylate, 8% of dipentaerythritol hexaacrylate, 4% of an auxiliary agent (a leveling agent BYK 349: an adhesion promoter A-172: a defoamer Airex 900: an antioxidant 1076: a stabilizer p-methoxyphenol ═ 1: 1: 0.5: 0.5: 1), 29% of butyl cellosolve, and 30% of cyclohexanone, and the mixture was stirred and mixed uniformly, and the result was obtained as shown in Table I.
Example H
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 25% of the alkali-soluble resin H obtained in example 8, 2611.5% of cationic photoinitiator Irgacure 2611.5%, 0.5% of free radical photoinitiator TPO, 4% of hexanediol di (meth) acrylate, 6% of propoxylated trimethylolpropane tri (meth) acrylate, 4% of auxiliary agent (leveling agent BYK 349: adhesion promoter A-172: defoamer Airex 900: antioxidant 1076: stabilizer p-methoxyphenol ═ 1: 1: 0.5: 0.5: 1), 29% of butyl cellosolve, and 30% of cyclohexanone, and uniformly stirring and mixing the components to obtain the aqueous alkali-soluble resin, wherein the results are shown in Table I.
Comparative example I
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: 20% of the alkali-soluble resin I obtained in the comparative example 1, 1.5% of a free radical photoinitiator TPO, 2501% of a cationic photoinitiator Irgacure, 7.5% of dipentaerythritol pentaacrylate, 5% of pentaerythritol tri (meth) acrylate, 2.5% of dicyclopentadiene acrylate, 4.5% of an auxiliary agent (a leveling agent TEGO 1484: Sartomer CD 9051: an antifoaming agent Airex 900: an antioxidant 2246: a stabilizer hydroquinone ═ 1: 1.5: 0.5: 0.5: 1), 30% of ethylene glycol monomethyl ether acetate and 28% of butyl acetate, and the alkali-soluble resin I, the free radical photoinitiator TPO, the cationic photoinitiator Irgacure, the dipentaerythritol pentaacrylate, the antioxidant and the.
Comparative example J
In the embodiment, the insulating transparent negative photoresist is prepared from the following components in percentage by mass: the alkali-soluble resin J15%, the cationic photoinitiator Irgacure 2612%, the free radical photoinitiator Irgacure 1843%, the tripropylene glycol di (meth) acrylate 1%, the ditrimethylolpropane tetraacrylate 9%, the auxiliary agent (the leveling agent TEGO 1484: A-172: the antifoaming agent 3100: the antioxidant 1010: 5% of the stabilizer p-methoxyphenol 1: 2: 1: 0.5: 0.5), the butyl cellosolve acetate 35%, and the ethylene glycol ethyl ether acetate 30% obtained in comparative example 2 were uniformly stirred and mixed, and the results are shown in Table I.
Test examples
The photoresist compositions prepared in examples a-comparative example J were viscosity tested as follows: the viscosity (model: Bohler-Fei DV2T) was measured using a rotary viscometer, specifically, 1ml of the sample was placed in a test cell of the viscometer and the viscosity was read for 30sec at a constant temperature of 25 ℃ and 50 rpm.
Application Performance testing was performed on the photoresist compositions prepared in examples A-comparative example J:
the test samples were prepared as follows:
according to an experimental scheme, the prepared negative photoresist composition is coated on a clean polymer optical thin film PET substrate plated with a transparent electrode in a spin coating mode, the thickness of the negative photoresist is within the range of 2-3 mu m, the negative photoresist is pre-baked for 90 seconds at the temperature of 100 ℃, then a Masker plate is covered for UV exposure, and the exposure amount is 150mj/cm2Developing the exposed sample with inorganic alkali solution (the inorganic alkali solution is 0.0045% KOH aqueous solution by mass percent), putting the developed sample into an oven, baking for 30min at 130 ℃ to obtain a sample with a pattern opposite to that of a Masker plate, and measuring the etching resistance, yellowing resistance, resolution, adhesive force, transmittance, flexibility and adhesive force, wherein the test method comprises the following steps:
testing of etching resistance: etching with KOH (4.5 wt%, 45 deg.C/5 min) and 10% aqua regia at 40 deg.C for 5min, and examining whether there is demoulding on the surface by Scanning Electron Microscope (SEM).
And (3) transmittance detection: and detecting by using an ultraviolet-visible spectrophotometer (model: Shimadzu UV265), specifically, testing the waveband at 360-750 nm, and reading the transmittance value at 400nm to obtain the transmittance.
Anti-yellowing test: and (3) baking the prepared sample at 230 ℃ for 30min, and then testing the transmittance, specifically, testing the waveband of 360-750 nm, and reading the transmittance value at 400nm to obtain the obtained transmittance. The yellowing resistance is expressed as the percentage of the transmittance measured after the sample is baked and the transmittance measured before the sample is baked, and the greater the percentage value is, the better the yellowing resistance is.
And (3) testing the resolution ratio: the resolution was measured using a Scanning Electron Microscope (SEM), and the line width of the smallest dimension of the formed pattern was measured, with the smaller the resolution value, the higher the resolution.
And (3) testing the adhesive force: and detecting by using a hundred-grid knife detection method. Detecting by using a hundred-grid knife, and testing conditions: the width of the edge of the hundred-grid cutter is about 1 cm-1.2 cm, every 1 mm-1.2 mm is an interval, 10 grids are provided in total, 10 linear cutter marks with the same interval appear when the linear cutter marks are marked down, the linear cutter marks are marked down at the vertical position to form a 100-grid square with 10 x 10, and the cuts are up to the base material; and brushing the brush in the diagonal direction for five times respectively, then adhering the brush in the grid by using a 3M Transparent Tape 600 Tape, quickly pulling up the 3M Tape, and grading the number of the adhesive stuck by the Tape according to the percentage of the grid. The adhesion grades comprise 1B, 2B, 3B, 4B and 5B, wherein 1B represents that the edge of the cut is stripped off in a large scale and/or some squares are partially or completely stripped off, and the area of the edge of the cut is more than 35% of that of the grid area but not more than 65%; 2B indicates partial or full peeling along the edges of the cut and/or partial cells are peeled in one piece. The area peeled off was more than 15% but less than 35%, 3B indicated that there was peeling at the edges and/or intersections of the cuts, the area was more than 5% but less than 15%, 4B indicated that there was small pieces peeled off at the intersections of the cuts, and the actual breakage in the cross-hatched area was not more than 5%), 5B indicated that the edges of the cuts were completely smooth, and the edges of the grid did not have any peeling.
Testing flexibility and adhesive force: and (3) testing by using a bending tester, specifically, repeatedly bending the coated sample, wherein the inner radius and the outer radius of the bending are 1mm, the times are 10 ten thousand, and then observing whether the film layer at the bending part cracks or falls off under a scanning electron microscope.
The test data are shown in table one.
Watch 1
As can be seen from the table I, the alkali soluble resin of the present invention can obtain the insulating transparent negative photoresist composition with excellent performances such as photosensitivity, developability, flexibility and adhesion under different specific formulations or different experimental conditions. The insulating transparent negative photoresist composition prepared by the invention can be used as a protective layer of an electrode circuit in a flexible OLED touch display screen, and has excellent properties of good adhesion with a polymer transparent film substrate, yellowing resistance, high sensitivity, developer tolerance, high resolution, high light transmittance and the like.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and do not limit the protection scope of the present invention. It will be understood by those skilled in the art that various deductions and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. An alkali-soluble resin, characterized in that the alkali-soluble resin is composed of a 1 st resin and a hydroxyl group-containing compound R1The polymer obtained by reaction, wherein the 1 st resin is a copolymer obtained by copolymerizing four substances of a), b), c) and d):
a) one selected from glycidyl methacrylate, glycidyl acrylate, 2-vinyl oxirane, 1, 2-epoxy-9-decene, 1, 2-epoxy-5-hexene, allyl glycidyl ether and 4-vinylbenzyl glycidyl ether,
b) one selected from acrylic acid and methacrylic acid,
c) one selected from the following structural formulae (1) to (2):
d) selected from benzyl (meth) acrylate, methyl (meth) acrylate, 2-chloroethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, methoxydiglycol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol monoethylether (meth) acrylate, triethylene glycol di (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, Triethylene glycol acrylate, triethylene glycol di (meth) acrylate, dimethylaminoethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, poly (propylene glycol) methyl ether acrylate, tricyclo [5.2.1.02, 6] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, phenoxydiglycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tribromophenyl (meth) acrylate, dicyclopentene (meth) acrylate, dicyclopentenyl (meth) acrylate, and mixtures thereof, One of (dicyclopentadienyloxy) ethyl (meth) acrylate and 2, 2-bis (1-cyclopenten-1-yloxy) ethyl (meth) acrylate,
wherein the content of the first and second substances,
n in the structural formulas (1) to (2) is selected from an integer of 0 to 4;
r in the structural formulas (1) - (2) is selected from one of halogen, furyl, cyclopentyl, methyl cyclopentyl, phenyl, phenoxy and isocyano;
the hydroxyl group-containing compound R1One selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl 2-methacrylate and 4-hydroxystyrene.
2. The alkali-soluble resin as claimed in claim 1, wherein the molar ratio of the four substances a), b), c) and d) is (2-35): (21-116): (2-24): (10-50).
3. The alkali-soluble resin according to claim 1, wherein the substance a and the hydroxyl group-containing compound R1The molar ratio of (1-56): (2-39).
4. The alkali-soluble resin according to claim 1, wherein the acid value of the alkali-soluble resin is 25 to 160 mgKOH/g.
5. The alkali-soluble resin according to claim 1, wherein the weight average molecular weight of the alkali-soluble resin is 8000 to 100000.
6. A negative photoresist composition comprising the alkali-soluble resin according to any one of claims 1 to 5, characterized by comprising the following components in mass percent:
7. the negative photoresist composition of claim 6, wherein the viscosity threshold of the negative photoresist composition is 5 to 30 mPas.
8. The negative photoresist composition of claim 6, wherein the reactive diluent monomer is a mixture of a vinyl-containing difunctional monomer and a vinyl-containing polyfunctional monomer, and the mass ratio of the vinyl-containing difunctional monomer to the vinyl-containing polyfunctional monomer is: 1:1 to 1: 10.
9. The negative photoresist composition of claim 8, wherein the vinyl group-containing bifunctional monomer is one selected from the group consisting of ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dicyclopentadiene acrylate, tripropylene glycol di (meth) acrylate; the multifunctional monomer containing vinyl is selected from one or more of trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol trimaleate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
10. The negative photoresist composition of claim 6, wherein the photoinitiator is a mixture consisting of a radical photoinitiator and a cationic photoinitiator.
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