KR20140112736A - Positive photosensitive resin composition - Google Patents
Positive photosensitive resin composition Download PDFInfo
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- KR20140112736A KR20140112736A KR1020130027167A KR20130027167A KR20140112736A KR 20140112736 A KR20140112736 A KR 20140112736A KR 1020130027167 A KR1020130027167 A KR 1020130027167A KR 20130027167 A KR20130027167 A KR 20130027167A KR 20140112736 A KR20140112736 A KR 20140112736A
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
The present invention relates to an alkali binder resin (A) comprising a thermally crosslinkable monomer represented by the following general formula (2) and a monomer having a vinyl ether group thermally crosslinked to the side chain of the base binder resin comprising monoglyceride represented by the following general formula (1) , An amine compound (B), a photoacid generator (C), a solvent (D), and a surfactant (E).
[Chemical Formula 1]
In Formula 1,
R 1 is a carboxyl group or a hydroxyl group, R 2 is hydrogen or a methyl group, and R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
(2)
Description
The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition which has high sensitivity and excellent storage stability, maintains a high transmittance even after a high-temperature baking process after film formation, To a resin composition.
Generally, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element, a patterned electrode protecting film, a planarizing film, an insulating film, and the like are provided. As a material for forming these films, a photosensitive resin composition having a small number of steps for obtaining a desired pattern shape and having a sufficient level of flatness among a photosensitive resin composition has been widely used conventionally.
These films are required to have excellent process resistance such as heat resistance, solvent resistance and long-time firing resistance, good adhesion to the base, and a wide process capable of forming patterns under various process conditions It is required to have a margin, a high sensitivity, a high transparency, and a low film bleeding after development. Therefore, from the viewpoint of such required properties, a resin containing a naphthoquinone diazide compound has heretofore been widely used as the above-mentioned photosensitive resin composition.
One of the characteristics required of such a photosensitive resin material is sensitivity. In the present situation in which the demand for the liquid crystal display is remarkably increased because the production time can be greatly shortened in an industrial production such as a display element, the improvement of the sensitivity is required for the photosensitive resin material of this kind Is one of the most important characteristics.
Therefore, in order to solve such a problem, Korean Patent Laid-Open Publication No. 10-2008-0089485 discloses a photoresist composition which is excellent in storage stability, has a high sensitivity and a small film loss in the unexposed portion, Discloses a positive type photosensitive resin composition which maintains a high transmittance even when exposed to a peeling liquid treatment and does not reduce the film thickness. However, the patent also has insufficient photosensitivity and the vinyl group is not well bonded to the base binder resin There is no problem.
Accordingly, an object of the present invention is to provide a chemically amplified positive photosensitive resin composition which has a high sensitivity and an excellent storage stability, maintains a high transmittance even after high-temperature baking after film formation, and has a high residual ratio of unexposed portions.
According to an aspect of the present invention for achieving the above object, the present invention provides a thermosetting thermosetting resin composition comprising a base binder resin comprising a monoclinic resin represented by the following Chemical Formula 1 and thermally crosslinking a monomer containing a vinyl ether group, (A), an amine compound (B), a photoacid generator (C), a solvent (D), and a surfactant (E) each containing a thermal crosslinking group represented by the following formula .
[Chemical Formula 1]
In Formula 1,
R 1 is a carboxyl group or a hydroxyl group, R 2 is hydrogen or a methyl group, and R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
(2)
Therefore, when the binder resin of the present invention according to the above-mentioned means for solving the above problems is used, a high transmittance can be maintained even after the high-temperature baking process after the film formation, Type positive photosensitive resin composition.
Hereinafter, specific details for carrying out the chemical amplification type positive photosensitive resin composition according to the present invention will be described.
The present invention provides a chemically amplified positive photosensitive resin composition comprising an alkali binder resin (A), an amine compound (B), a photo acid generator (C), a solvent (D), and a surfactant (E) The resin (A) is a copolymer containing a monomer containing a vinyl ester group as an acid-decomposable protecting group in a side chain of a base binder resin having an unsaturated double bond capable of undergoing a thermosetting reaction.
The alkali binder resin (A)
The positive-working photosensitive resin composition of the present invention is a positive-working photosensitive resin composition comprising a base binder resin comprising a monoclinic resin represented by the following general formula (1), wherein a monomer having a vinyl ether group is thermally crosslinked and bound to the side chain thereof, And an alkali binder resin.
[Chemical Formula 1]
In Formula 1,
R 1 is a carboxyl group or a hydroxyl group, R 2 is hydrogen or a methyl group, and R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
(2)
The alkali binder resin includes a monomer containing a vinyl ether group, which is an acid-decomposable protecting group, on the side chain of the base binder containing the monocyclic group represented by the above formula (1) having an unsaturated double bond capable of undergoing a thermosetting reaction. In addition, the alkali binder resin may be a polymer or a copolymer containing a base monomer.
The base binder resin is obtained by sequentially reacting a copolymer of a first monomer having an unsaturated bond and an epoxy group in a molecule and a second monomer having an unsaturated bond with a third monomer having an unsaturated double bond and a carboxyl group and an acid anhydride, Containing resin can be used.
The first monomer may be used without limitation as long as it is a compound having an unsaturated bond and an epoxy group in one molecule. Specific examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclodecan-8-yl (meth) acrylate and methylglycidyl (meth) acrylate, or a mixture thereof have. Preferably, glycidyl (meth) acrylate can be used.
(Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and the like. The second monomer may be any compound having an unsaturated bond polymerizable with the first monomer. Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate; unsaturated carboxylic acid esters such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (Meth) acrylate, cycloheptyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as adamantyl (meth) acrylate, norbornyl (meth) acrylate and pinenyl (meth) acrylate, oligoethylene glycol monoalkyl (meth) Mono-saturated carboxylic acid ester compounds of glycols such as benzyl (meth) acrylate, unsaturated carboxylic acids containing a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy Aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyltoluene, vinyl carboxylates such as vinyl acetate and vinyl acetate, vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile, and Maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide, or a maleimide compound selected from the group consisting of Mixtures may be used.
The third monomer may be any compound that adds an unsaturated double bond to the copolymer of the first monomer and the second monomer, and may be preferably acrylic acid or methacrylic acid. The third monomer may be used in combination with an unsaturated carboxylic acid or a monomer containing a hydroxyl group and a carboxyl group. Specifically, monomers containing an unsaturated carboxylic acid or a hydroxyl group and a carboxyl group may be used in addition to acrylic acid or methacrylic acid as the third monomer. The unsaturated carboxylic acid may be selected from the group consisting of crotonic acid, itaconic acid, maleic acid and fumaric acid, or a mixture thereof. Specific examples of the monomer containing a hydroxyl group and a carboxyl group include? - (hydroxymethyl) acrylic acid .
The acid anhydride is preferably selected from the group consisting of succinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 2-dicarboxylic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 1,1-cyclopentanediacetic anhydride, (2- 3-dimethylglutaric anhydride, 2,2-dimethylglutaric anhydride, 1,1-cyclohexane diacetic anhydride, 2-butene-1-ylsuccinic anhydride, 3-methyl- Norbornene-2,3-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, n-octylsuccinic anhydride, allylsuccinic anhydride , Bicyclo [2.2.2] octa-5-ene-2,3-dicarboxylic acid anhydride, phthalic anhydride, 4-methylphthalic anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,2- 3-methylphosphoric anhydride, Dicarboxylic acid anhydride, 2,3-dicarboxylic acid anhydride, 2,3-dicarboxylic acid anhydride, 2,3-dicarboxylic acid anhydride, At least one selected from the group consisting of dimethyl maleic anhydride, maleic anhydride, 4-tert-butyl phthalic anhydride and citraconic anhydride can be used.
The base binder resin may have from 2 to 80 mol%, preferably from 5 to 80 mol%, of the repeating units derived from the first monomer relative to the whole resin, and from 2 to 90 mol% Preferably 5 to 90 mol%. Also, the third monomer may be reacted in an amount of 2 to 100 mol%, preferably 5 to 100 mol%, based on the epoxy equivalent of the first monomer, and the acid anhydride is reacted with the first monomer and the third monomer To 2 to 100 mol%, preferably 5 to 100 mol%, based on the equivalent of the hydroxyl group produced by the reaction. The alkali binder resin having a repeating unit within the above range is excellent in developability, transparency, and thermal crosslinking property with a vinyl ether group, thereby improving sensitivity and the like.
The base binder resin may have a weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) of 3,000 to 100,000, preferably Lt; RTI ID = 0.0 > 30,000. ≪ / RTI > More preferably, when the weight average molecular weight of the base binder resin is 7,000 to 20,000, the residual film ratio of the unexposed portion increases, the taper angle can be improved, and the resolution can be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the base binder resin may be 1.5 to 4.0, preferably 1.5 to 3.0. More preferably, the molecular weight distribution is 1.5 to 2.0, and the resolution is excellent.
The base binder resin may have an acid value of 50 to 180 (mgKOH / g). Preferably from 70 to 160, and more preferably from 100 to 130, the resolution and the residual film ratio are improved.
The base binder resin may be prepared by: a) polymerizing a first monomer having an unsaturated bond and an epoxy group and a second monomer having an unsaturated bond polymerizable with the first monomer to form a copolymer ; b) reacting the copolymer produced in step a) with a third monomer to which an unsaturated double bond is added, thereby adding an unsaturated double bond to the copolymer; c) reacting the copolymer produced in step b) with an acid anhydride. Hereinafter, the reaction scheme will be described in detail for each step.
The step a) is a step of polymerizing a first monomer and a second monomer to form a copolymer, for example, as shown in Reaction Scheme 1 below.
[Reaction Scheme 1]
Specifically, in Scheme 1, a solvent is introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is replaced with nitrogen in air. Thereafter, the temperature of the solvent is raised to 40 to 140 DEG C, and then the first monomer, the second monomer and the polymerization initiator are added, and the solution is stirred and dissolved at room temperature or under heating. Followed by stirring at 40 ° C to 140 ° C for 1 hour to 10 hours to obtain a copolymer.
The solvent may be added in an amount of 0.5 to 20 parts by weight based on the content of the first monomer and the second monomer. Specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone Methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propyleneglycol monomethylethylacetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, But are not limited to, ether, toluene, xylene, ethylbenzene, chloroform, and dimethyl sulfoxide, or a mixture thereof.
The polymerization initiator may be at least one selected from the group consisting of diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, Organic peroxides such as butyl peroxy-2-ethyl hexanoate; And 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl-2,2'-azobis (2-methylpropionate ), And the like, or a mixture thereof, but the present invention is not limited thereto.
The chain transfer agent may further include a chain transfer agent to control the molecular weight or the molecular weight distribution in the step a). Examples of the chain transfer agent include, but are not limited to,? -Methylstyrene dimer or mercapto compound. The chain transfer agent may be included in an amount of 0.005 to 5 parts by weight based on the first monomer and the second monomer.
The polymerization conditions may be appropriately adjusted by a person skilled in the art in consideration of the amount of heat generated by the production equipment or polymerization.
In step b), a copolymer of a first monomer and a second monomer is reacted with a third monomer to add an unsaturated double bond to the copolymer, for example, as shown in the following reaction scheme 2.
[Reaction Scheme 2]
In step b), a copolymer of a first monomer and a second monomer is reacted with a third monomer to form an unsaturated double bond in the copolymer, as shown in Scheme 2. Specifically, the reactants and the solvent of step a) are introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask is replaced with nitrogen in air. Thereafter, the reaction product and the solvent of step a) are heated to 40 to 140 DEG C, and then the third monomer and the polymerization initiator are added and stirred and dissolved at room temperature or under heating. From the dropping solution, And further stirred at 40 to 140 ° C for 1 hour to 10 hours to react with the epoxy group of the first monomer and the carboxylic acid moiety of the third monomer so that the unsaturated double bond portion of the third monomer finally remains Get the coalesce.
Step c) is a step of reacting the copolymer with the third monomer and further reacting with the acid anhydride, for example, as shown in Reaction Scheme 3 below.
[Reaction Scheme 3]
Specifically, in the reaction scheme 3, the copolymer obtained by the polymerization in the reaction scheme 1 is reacted with the third monomer in the reaction scheme 2, and then the acid anhydride is added thereto at a temperature of 50 ° C to 150 ° C, And heated to 130 DEG C to react to obtain a base binder resin. Through the step of reacting with the acid anhydride as described above, the base binder resin of the present invention can form a long branch which reacts with an acid to exhibit a stereoscopic effect, and through this, the effect of easily bonding with the vinyl group of the vinyl ether compound have.
In the alkali binder resin of the present invention, the vinyl ether compound is thermally crosslinked to the side chain of the base binder resin to include a thermal crosslinking group represented by the following formula (2).
(2)
As the vinyl ether compound thermally crosslinked to be bonded to the side chain of the base binder resin of the present invention, the use of the vinyl ether group compound represented by the following formula 3 or 4 is preferable in view of developing without residual film or residue in the exposure section Do.
(3)
(n is an integer of 1 to 10, k is an integer of 1 to 10, and R < 2 >
[Chemical Formula 4]
(m represents an integer of 1 to 10)
N in formula (3) and m in formula (4) each represent the number of vinyl ether groups in one molecule. Also, it is preferable that n in the formula (3) and m in the formula (4) have an integer of 1 to 4 in that they are developed without a residual film or residue in the exposure part.
Specific examples of the compound represented by Formula 3 or Formula 4 include isobutyl vinyl ether, cyclohexyl vinyl ether, vinyl hexanoate, 2-ethylhexyl vinyl ether, bis (4- (vinyloxymethyl) cyclohexylmethyl) (4-vinyloxy) butyl terephthalate, bis (4- (vinyloxy) butyl) terephthalate, di (ethylene glycol) divinyl ether, Bis (4- (vinyloxy) butyl isophthalate and cyclohexanedimethanol divinyl ether).
A method for obtaining the final binder resin of the base binder resin and the compound having the vinyl ether group is not particularly limited, but can be obtained, for example, by the following Reaction Scheme 4.
[Reaction Scheme 4]
Specifically, in the above Scheme 4, the compound having the base binder resin and the vinyl ether group is maintained in a solvent at a temperature of 35 to 80 캜, and the cross-linking reaction of the carboxyl group and the vinyl ether group of the base binder resin is carried out. The solvent to be used is not particularly limited as long as it dissolves the base binder resin and the compound having a vinyl ether group. Specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl Butanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, But are not limited to, methyl ether, toluene, xylene, ethylbenzene, chloroform, and dimethyl sulfoxide, or mixtures thereof.
When the alkali-binding resin (A) is used, the content thereof may be 5 wt% to 40 wt%, preferably 10 wt% to 35 wt% based on the total amount of the positive photosensitive resin composition of the present invention By weight, and more preferably 15% by weight to 30% by weight. If the amount of the alkali-binder resin (A) to be used is less than 5% by weight, the resulting copolymer is hardly dissolved in the aqueous alkali solution. If the amount of the alkali-binder resin (A) The solubility thereof tends to become excessively large, which may cause a decrease in the residual film yield.
The amine compound (B)
The positive photosensitive resin composition of the present invention includes an amine compound (B) in order to enhance storage stability. The amine compound of the above component (B) is not particularly limited, and examples thereof include triethanolamine, tributanolamine, trimethylamine, triethylamine, tinnormalpropylamine, triisopropylamine, trinormalbutylamine, tri tertiary amines such as tert-butylamine and diazabicyclooctane; Aromatic amines such as pyridine and 4-dimethylaminopyridine; Primary amines such as benzylamine and n-butylamine; Or secondary amines such as diethylamine and dinormalbutylamine.
The amine compound (B) may be used singly or in combination of two or more.
When the amine compound (B) is used, the content thereof may be 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, per 100 parts by weight of the alkali binder resin (A), more preferably 0.005 to 1 part by weight, 0.01 to 0.5 parts by weight. If the amount of the amine compound (B) is less than 0.005 parts by weight, the storage stability of the positive photosensitive resin composition can not be sufficiently enhanced. If the amount of the amine compound (B) is more than 5 parts by weight, May be lowered.
mine Generator (C)
The positive photosensitive resin composition of the present invention comprises a photoacid generator (C). The photoacid generator generates an acid by causing radiation such as light or an electron beam to act on the resist composition containing the photoacid generator or the photoacid generator, and the acid generated from the photoacid generator acts on the resin component, And dissociates the acid labile groups present in the solvent to increase the solubility in the developer. The photoacid generator (PAG) is directly or indirectly irradiated with an acid (sulfonic acid, carboxylic acid, etc.) by irradiation with light (ultraviolet rays such as g, h, i line, ArF, KrF, F2 laser light or electron beam) Etc.), and the kind and structure thereof are not particularly limited as far as they have such a substance.
As the photoacid generator (C), conventionally known or conventionally used photoacid generators are all not particularly limited and can be applied in the present invention. For example, diazomethane compounds, onium salt compounds, sulfone An imide compound, a disulfone compound, a sulfonic acid derivative compound, a nitrobenzyl compound, a benzoyl silicate compound, an iron isocyanate compound, a halogen-containing triazine compound, an acetophenone derivative compound and a cyano group-containing oxime sulfonate compound can be used . In the present invention, the photoacid generators (C) may be used alone or in combination of two or more. Of course, these compounds are a few examples of a very large number of applicable photoacid generators, and of course are not limited thereto.
The photoacid generator (C) may be contained in an amount of 0.2 to 80 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the alkali binder resin (A). When the amount of the photoacid generator (C) is less than 0.2 parts by weight, the decomposition at the vinyl ether compound portion forming the thermally crosslinked alkali-soluble resin (A) does not progress sufficiently during the exposure, It is difficult to obtain the relief of the positive photosensitive resin composition, and when it exceeds 30 parts by weight, the storage stability of the positive photosensitive resin composition becomes poor.
Solvent (D)
The positive photosensitive resin composition of the present invention includes a solvent (D) for dissolving the alkali binder resin (A), the amine compound (B) and the photoacid generator (C). Further, the solvent (D) used in the present invention can dissolve the later-described surfactants (E) to (F) to be added as needed. As the solvent (D) usable in the present invention, there are no particular limitations on the type and structure of the solvent as long as it has such solubility, but the following solvents can be preferably used.
Examples of the solvent (D) usable in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl crossovinate acetate, ethyl crossovinate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, , Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3- Ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, , N, N-dimethylformamide, N, N-dimethylacetoamide and N-methylpyrrolidone. From the viewpoint of good film stability and high stability, propylene glycol monomethyl ether, propylene glycol mono Methyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate and the like are particularly preferably used. These solvents may be used singly or in combination of two or more.
When the above-mentioned solvent (D) is used, its content may be in the range of 50% by weight to 90% by weight based on the total amount of the positive photosensitive resin composition of the present invention. When the amount of the solvent (D) is less than 50% by weight, the coating property is ununiform due to the high viscosity, so that a uniform film thickness can not be obtained on the large glass substrate. If the amount exceeds 90% by weight, It can not be obtained sufficiently.
Surfactant (E)
The positive photosensitive resin composition of the present invention may further contain a surfactant (E) so as not to reduce the effect of the present invention in order to improve the applicability.
Examples of the surfactant (E) include, but are not limited to, a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. Specific examples of the surfactant (E) include megafixes F-470, F471, F475, F482 and F489 of Dainippon Ink Kagaku Kogyo Co., Ltd. as a specific example of a fluorochemical surfactant. Specific examples of silicone surfactants include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400, GE TSU-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4452 and the like. The above-mentioned surfactants (E) may be used singly or in combination of two or more.
The surfactant (E) may be contained in an amount of 0.2 wt% or less, preferably 0.1 wt% or less, based on the total amount of the positive photosensitive resin composition. When the amount of the surfactant (E) used is more than 0.2% by weight, the effect of improving the coating property with an increase in the amount of the surfactant (E) is not economical.
Additive (F)
The above-mentioned additive (F) may be optionally added, for example, other polymer compounds, a curing agent, an adhesion promoter, an antioxidant, an ultraviolet absorber and an antiflocculant.
Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .
The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.
The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. When the adhesion promoter is used, the content thereof may be generally 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total solid content of the positive photosensitive resin composition of the present invention.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
The positive photosensitive resin composition of the present invention can be produced, for example, by the following method.
(A), the amine compound (B) and the photoacid generator (C), the surfactant (E) and the additive (F) to be used if necessary and the additional solvent (D) So as to obtain the target positive photosensitive resin composition.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
Preparation of Base Binder Resin
≪ Synthesis Example 1 &
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was replaced with nitrogen in air. After heating at 80 ° C, glycidyl A solution in which 3.6 g of azoisobutyronitrile was added to a mixture containing 82.5 g (0.6 mol) of methacrylate, 35.4 g (0.4 mol) of vinyltoluene and 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel And the mixture was stirred for further 5 hours at 80 ° C. Subsequently, the atmosphere in the flask was replaced with air with nitrogen, and 43.2 g [0.6 mol (100 mol% with respect to the epoxy group of the glycidyl methacrylate used in the present reaction) of acrylic acid], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone (0.3 mol) of succinic anhydride was added thereto, and the reaction was further continued at 110 ° C for 2 hours to obtain a solid acid value of 95.8 mgKOH / g ≪ / RTI > The weight average molecular weight in terms of polystyrene measured by GPC was 12,000 and the molecular weight distribution (Mw / Mn) was 2.3.
≪ Synthesis Example 2 &
190 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was replaced with nitrogen in air, and after heating at 80 ° C, glycidyl A solution obtained by adding 3.6 g of azoisobutyronitrile to a mixture containing 99.51 g of methacrylate, 31.91 g of vinyltoluene and 160 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel, Lt; / RTI > for 5 hours. Subsequently, 50.44 g of acrylic acid, 6.61 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C for 4 hours. Subsequently, 35.43 g of succinic anhydride (0.3 mol) were added, and the reaction was further continued at 110 ° C for 2 hours to obtain a resin A having a solid acid value of 99.5 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 5,900.
≪ Synthesis Example 3 &
180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was replaced with nitrogen in air, and after the temperature was raised to 80 DEG C, glycidyl methane A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 99.51 g of acrylate, 31.91 g of vinyltoluene, 6.61 g of dicyclopentanylmethacrylate and 140 g of propylene glycol monomethyl ether acetate was added dropwise to a solution of 2 Over a period of time, and stirring was further continued at 80 캜 for 5 hours. Subsequently, 50.44 g of acrylic acid, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 DEG C for 4 hours, followed by the addition of 23.62 g of succinic anhydride Thereafter, the reaction was further continued at 110 DEG C for 2 hours to obtain a resin A having a solid acid value of 65.7 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 11,200 and the molecular weight distribution (Mw / Mn) was 2.3.
≪ Synthesis Example 4 &
190 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was replaced with nitrogen in air. After the temperature was raised to 80 DEG C, glycidyl methane A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 99.51 g of acrylate, 53.54 g of ethylhexyl methacrylate, 6.61 g of dicyclopentanyl methacrylate and 190 g of propylene glycol monomethyl ether acetate was added dropwise Was added dropwise to the flask over 2 hours from the lot, and stirring was further continued at 80 캜 for 5 hours. Subsequently, 50.44 g of acrylic acid, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 DEG C for 4 hours. Subsequently, 41.33 g of succinic anhydride was added Thereafter, the reaction was further continued at 110 DEG C for 2 hours to obtain a resin P6 having a solid acid value of 98.6 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 18,600 and the molecular weight distribution (Mw / Mn) was 2.3.
The above results are shown in Table 1 below.
GMA: Glycidyl Methacrylate
AA: acrylic Acid
VT: Vinyl toluene
TCDMA: tricyclodecyl methacrylate
EHMA: 2-Ethylhexyl Methacrylate
SA: Succinic anhydride
PGMEA: Propylene Glycol Monomethyl Ether Acetate
(2) Preparation of binder resin
≪ Synthesis Example 5 &
75.0 g of Synthesis Example 1, 15.0 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent were mixed and reacted at 60 DEG C for 18 hours with stirring Prot-Binder PB1 with Mw of 25,000 was obtained.
≪ Synthesis Example 6 &
75.0 g of Synthesis Example 2, 7.8 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent were mixed and reacted at 60 ° C for 18 hours with stirring Prot-Binder PB2 with a Mw of 13,000 was obtained.
≪ Synthesis Example 7 &
By mixing 75.0 g of Synthesis Example 3, 15.0 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent and stirring at a temperature of 60 ° C for 18 hours Prot-Binder PB3 with Mw of 24,500 was obtained.
≪ Synthesis Example 8 &
75.0 g of Synthesis Example 3, 7.83 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent were mixed and reacted at 60 ° C for 18 hours with stirring Prot-Binder PB4 with a Mw of 23,500 was obtained.
≪ Synthesis Example 9 &
75.0 g of Synthesis Example 3, 5.1 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent were mixed and reacted at 60 ° C for 18 hours with stirring Prot-Binder PB5 with Mw of 23,000 was obtained.
≪ Synthesis Example 10 &
75.0 g of Synthesis Example 4, 7.8 g of a bifunctional vinyl ether compound, 1,4-cyclohexanedimethanol divinyl ether and 30 g of propylene glycol methyl ether acetate as a solvent were mixed and reacted at 60 ° C for 18 hours with stirring Prot-Binder PB7 with a Mw of 37,000 was obtained.
≪ Synthesis Example 11 &
40 g (333 mmol) of poly (p-hydroxystyrene) and 47 mg (0.25 mmol) of p-toluenesulfonic acid hydrate were placed in an eggplant-shaped flask and dissolved in 720 g of propylene glycol monomethyl ether acetate. This solution was subjected to azeotropic dehydration by distillation under reduced pressure at a temperature of 60 ° C and a pressure of 10 Torr or less. The weight of the solution after distillation was 337 g. This solution was transferred to a 500 ml four-necked flask purged with nitrogen, to which 7.3 g (101 mmol) of ethyl vinyl ether and 1.9 g (46 mmol) of propylene were added dropwise, and they were reacted at 25 DEG C for 5 hours . To the reaction solution, 62.3 g of propylene glycol monomethyl ether acetate and 320 g of methyl isobutyl ketone were added, further 240 ml of ion-exchanged water was added, and the mixture was stirred. Then, the mixture was allowed to stand to take out the organic layer portion. 240 ml of ion-exchanged water was again added to the organic layer, and the mixture was stirred and washed, and the mixture was allowed to stand to separate the liquid. After the washing with the ion exchange water and the liquid separation were performed again, the organic layer was taken out and distilled under reduced pressure to remove water and methyl isobutyl ketone by azeotropic distillation with propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether Acetate solution. A solution of the partially etherified poly (p-hydroxystyrene) with the resulting 1-ethoxyethyl and isopropyl groups was obtained. To obtain a resin A having a solid acid value of 10 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 10,000 and the molecular weight distribution (Mw / Mn) was 1.5.
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above polymer was carried out by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)
Column temperature: 40 DEG C
Mobile phase solvent: tetrahydrofuran
Flow rate: 1.0 ml / min
Injection amount: 50 μl
Detector: RI
Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)
Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)
The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).
Preparation of chemical amplification type photosensitive resin composition
< Example 1>
19.78 parts of the alkali-soluble resin prepared in <Synthesis Example 5>, 0.59 parts of NIT, manufactured by Heraeus Co., Ltd., 0.26 part of 9,10-dibutoxyanthracene, 3 parts of 3-glycidoxypropyl tri 0.66 part of ethoxysilane, 69.48 parts of propylene glycol methyl ether acetate, 3.96 parts of gamma-butyllactone, and 5.27 parts of ethylene glycol dimethyl ether were mixed to prepare a positive type photosensitive resin composition.
< Example 2>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin used in Example 1 was changed to the resin of Synthesis Example 6.
< Example 3>
A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin used in Example 1 was changed to the resin of Synthesis Example 7.
< Example 4>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin used in Example 1 was changed to the resin of Synthesis Example 8.
< Example 5>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin used in Example 1 was changed to the resin of Synthesis Example 9.
< Comparative Example 1>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin used in Example 1 was changed to the resin of Synthesis Example 10.
< Comparative Example 2>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the resin used in Example 1 was changed to the resin of Synthesis Example 11.
Experimental Example
Using the chemically amplified photosensitive resin compositions of the above Examples and Comparative Examples, the following evaluations were carried out.
[Evaluation of membrane loss]
The positive photosensitive composition was coated on a glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 캜 for 125 seconds to form a coating film. This film was immersed in a 2.38 mass% TMAH aqueous solution for 60 seconds, followed by water washing with ultra-pure water for 20 seconds, and then by post-baking at 230 deg. C for 30 minutes to form a cured film. The difference between the above-mentioned pre-baked coating film and post-baked cured film was determined, and the degree of film reduction of the unexposed portion by the process was evaluated. The evaluation results are shown in Table 2 below. In the above evaluation, the film thickness was measured using a Stylus profiler 6M manufactured by DEKTAK.
[Evaluation of light transmittance (transparency) after high-temperature firing]
The positive photosensitive composition was applied on a glass substrate using a spin coater, and then a coating film was formed by pre-baking on a hot plate at a temperature of 100 캜 for 125 seconds. This coating film was immersed in a 2.38 mass% TMAH aqueous solution for 60 seconds, followed by water washing with ultra pure water for 20 seconds. Subsequently, post-baking was performed by heating at 230 DEG C for 30 minutes to form a cured film having a thickness of 3.2 mu m. The cured film was measured for transmittance at a wavelength of 520 nm using an ultraviolet visible spectrophotometer (Olympus OSP-SP2000) and is shown in Table 2 below. In this evaluation, the film thickness was measured using a Stylus profiler 6M manufactured by DEKTAK.
[Evaluation of Hole size]
After the positive photosensitive composition was applied on a glass substrate using a spin coater, prebaking was performed on a hot plate at a temperature of 100 DEG C for 125 seconds, and an exposure machine (MIDAS company MDS-60M) A patterned mask was sandwiched between the glass substrates and light irradiation was performed. This film was immersed in a 2.38 mass% TMAH aqueous solution for 60 seconds, followed by water washing with ultra pure water for 20 seconds and then by post-baking at 230 deg. C for 30 minutes to form a 3.2 m thick cured film. The size of the hole formed by the 15 mu m hole portion of the mask in the thus formed coating film was measured and described in Table 2 below.
As shown in Table 3, Examples 1 to 5 exhibited excellent results for decreasing the light transmittance at a high temperature and decreasing the film thickness. In addition, it can be said that the same level of Hole size is shown in the mask of the same Hole size, which shows the same level of sensitivity.
Claims (10)
[Chemical Formula 1]
In Formula 1,
R 1 is a carboxyl group or a hydroxyl group, R 2 is hydrogen or a methyl group, and R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
(2)
The monomer containing the vinyl ether group
A positive photosensitive resin composition comprising a vinyl ether group represented by the following formula (3) or (4):
(3)
(n is an integer of 1 to 10, k is an integer of 1 to 10, and R < 2 >
[Chemical Formula 4]
(m represents an integer of 1 to 10)
The alkali binder resin (A) is contained in an amount of 5% by weight to 40% by weight based on the total amount of the positive photosensitive resin composition,
The amine compound (B) is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the alkali binder resin (A)
The photoacid generator (C) is contained in an amount of 0.2 to 80 parts by weight based on 100 parts by weight of the alkali binder resin (A)
Wherein the solvent (D) is contained in an amount of 50% by weight to 90% by weight based on the total amount of the positive photosensitive resin composition.
The amine compound (B) may be at least one compound selected from the group consisting of triethanolamine, tributanolamine, trimethylamine, triethylamine, tinnornylpropylamine, triisopropylamine, trinormalbutylamine, tri-tert-butylamine, diazabicyclooctane, Wherein the positive photosensitive resin composition is at least one selected from the group consisting of 4-dimethylaminopyridine, benzylamine, n-butylamine, diethylamine and dinormalbutylamine.
The photoacid generator (C) may be at least one compound selected from the group consisting of a diazomethane compound, an onium salt compound, a sulfonimide compound, a disulfone compound, a sulfonic acid derivative compound, a nitrobenzyl compound, a benzoyl silicate compound, Wherein the positive photosensitive resin composition is at least one selected from the group consisting of an acetophenone derivative compound and a cyano group-containing oxime sulfonate compound.
The solvent (D) is at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cresol, ethyl cresol, ethyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,? -Butyrolactone, ethyl 2-hydroxypropionate, 2 Methyl ethyl ketone, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy- Propyl methacrylate, ethyl propionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, Butyl acetoacetate amides, and N- methylpyrrolidone positive photosensitive resin composition, characterized in that at least one member selected from the group consisting of pyrrolidone.
Wherein the positive photosensitive resin composition further comprises at least one of a surfactant (E) and an additive (F).
Wherein the surfactant (E) is at least one selected from the group consisting of a fluorine-based surfactant, a silicon-based surfactant and a nonionic surface-active agent.
Wherein the surfactant (E) is contained in an amount of 0 to 0.2% by weight based on the total amount of the positive photosensitive resin composition.
Wherein the additive (F) is at least one selected from the group consisting of a polymer compound, a curing agent, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.
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| KR1020130027167A KR20140112736A (en) | 2013-03-14 | 2013-03-14 | Positive photosensitive resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016175627A1 (en) * | 2015-04-30 | 2016-11-03 | 주식회사 동진쎄미켐 | Positive type photosensitive resin composition for display device and display device comprising same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016175627A1 (en) * | 2015-04-30 | 2016-11-03 | 주식회사 동진쎄미켐 | Positive type photosensitive resin composition for display device and display device comprising same |
| KR20160130046A (en) * | 2015-04-30 | 2016-11-10 | 삼성디스플레이 주식회사 | Positive photosensitive resin composition for display device and display device comprising the same |
| CN107533293A (en) * | 2015-04-30 | 2018-01-02 | 株式会社东进世美肯 | Positive photosensitive resin composition for display device and display device comprising same |
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