CN108073042B - Positive photosensitive resin composition - Google Patents

Positive photosensitive resin composition Download PDF

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Publication number
CN108073042B
CN108073042B CN201711098303.1A CN201711098303A CN108073042B CN 108073042 B CN108073042 B CN 108073042B CN 201711098303 A CN201711098303 A CN 201711098303A CN 108073042 B CN108073042 B CN 108073042B
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photosensitive resin
resin composition
weight
positive photosensitive
amine
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CN108073042A (en
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金东明
尹赫敏
吕泰勋
金宣炯
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Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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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
    • 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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

The present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to a positive photosensitive resin composition having excellent sensitivity, resolution, pattern profile, post-exposure delay margin (PED margin), etc., particularly, excellent repulsive force and heat resistance to etching solution permeation due to a large chromophore structure having lipophilicity, and excellent wet etching adhesion and heat resistance, dispersity by using a photoacid generator whose acid diffusion rate is easily controlled due to an acid structure containing a long alkyl chain. Therefore, the positive photosensitive resin composition of the present invention can be used for elements accompanied with wet etching processes such as displays, semiconductors, microelectromechanical systems (MEMS), electronic paper (E-paper), etc., and is particularly suitable for large-area high-resolution displays such as thin film transistor liquid crystal displays (TFT-LCD), organic Light Emitting Diodes (OLED) or organic thin film transistors (O-TFT).

Description

Positive photosensitive resin composition
Technical Field
The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition excellent in sensitivity, resolution, pattern profile, post-exposure delay margin (PED margin), and the like, particularly excellent in wet etching adhesion, heat resistance, and dispersibility.
Background
The recent hot topic of the display market is mass production of thin film transistor liquid crystal display ultra high definition televisions (TFT-LCD UHD (Ultra High Density) TV) and organic light emitting diode televisions (OLED TV). As OLED televisions are beginning to be mass-produced, thin film transistor liquid crystal displays (TFT-LCDs) have developed a high resolution strategy for the superior image quality against Organic Light Emitting Diodes (OLEDs). The competition pattern of mobile phones or tablet computers in the IT market is transferred to the television market.
The realization of high resolution is conditioned by the linewidth being smaller than existing wiring structures. However, photoresists used in the display field have reached the limit of the mechanism, and thus development of materials of novel design for achieving high resolution is required.
For mass production of large substrates mainly used for production of televisions, the process margin for the spread and Delay (Delay) needs to be much better than the technical hurdle for producing small substrates for mobile devices. In order to achieve high resolution, materials and equipment used in semiconductors can be used, but current semiconductor equipment and materials do not meet the large-scale production due to disadvantages in terms of dispersion and Delay (Delay). Therefore, there is a need for a material that is excellent in dispersion and process margin to Delay (Delay) in order to be able to achieve Ultra High Definition (UHD) levels of high resolution, as well as to produce large area displays.
In general, a dry etching process is different from a wet etching process, has an excellent vertical and horizontal etching selectivity, has advantages in terms of process margin, but has a limited size of a substrate applicable to the dry etching process, is not suitable for producing a large-area display, and thus it is required to develop a material that can employ the wet etching process. In addition, the wet etching process is often accompanied by a baking process (bak process) to further secure chemical resistance of the material, and if the heat resistance is poor, reflow (Reflow) may cause CD reduction or clogging to decrease the resolution, and thus it is required to develop a material excellent in heat resistance.
Disclosure of Invention
Technical problem
In order to solve the problems of the prior art as described above, an object of the present invention is to provide a positive photosensitive resin composition excellent in sensitivity, resolution, pattern profile, post-exposure delay margin (PED margin) and the like, particularly excellent in wet etching adhesion, heat resistance and dispersibility.
Another object of the present invention is to provide a pattern forming method of an element using the positive photosensitive resin composition, and an element manufactured by the pattern forming method.
Technical proposal
To achieve the above object, the present invention provides a positive photosensitive resin composition comprising:
a) A copolymer represented by the following chemical formula 1;
b) Photoacid generator having a melting point of 90 ℃ to 300 ℃, a carbon number of an Alkyl group (Alkyl group) of an Acid of 6 to 20, and a solubility to propylene glycol monomethyl ether acetate (Propylene glycol monomethyl ether acetate) of 1% to 15%;
d) An organic base; a kind of electronic device with high-pressure air-conditioning system
e) The solvent is used for the preparation of the aqueous solution,
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
the R is 1 Is an acetal group (acetic), a ketal group (ketal),
x+y+z=1, x is 0.1 to 0.9, specifically x is 0.1 to 0.7; y is 0.0 to 0.6, specifically y is 0.1 to 0.4; z is 0.1 to 0.9, specifically z is 0.1 to 0.7.
In addition, the present invention provides a pattern forming method of an element using the positive photosensitive resin composition.
In addition, the present invention provides an element patterned by the patterning method.
Effects of the invention
The positive photosensitive resin composition of the present invention has excellent sensitivity, resolution, pattern profile, post-exposure delay margin (PED margin), etc., particularly because of having a large (bulk) Chromophore (chromophone) structure having lipophilicity, excellent repulsive force against etching liquid permeation and heat resistance, and excellent wet etching adhesion, heat resistance and dispersivity by using a photoacid generator that easily controls the acid diffusion rate due to an acid structure containing a long alkyl chain. Therefore, the positive photosensitive resin composition of the present invention can be used for elements accompanied with wet etching processes such as displays, semiconductors, microelectromechanical systems (MEMS), electronic paper (E-paper), etc., and is particularly suitable for large-area high-resolution displays such as thin film transistor liquid crystal displays (TFT-LCD), organic Light Emitting Diodes (OLED) or organic thin film transistors (O-TFT).
Detailed Description
The present invention will be described in detail below.
The positive photosensitive resin composition of the present invention comprises:
a) A copolymer represented by the following chemical formula 1;
b) Photoacid generator having a melting point of 90 ℃ to 300 ℃, a carbon number of an Alkyl group (Alkyl group) of an Acid of 6 to 20, and a solubility to propylene glycol monomethyl ether acetate (Propylene glycol monomethyl ether acetate) of 1% to 15%;
d) An organic base; a kind of electronic device with high-pressure air-conditioning system
e) The solvent is used for the preparation of the aqueous solution,
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
the R is 1 Is an acetal group, a ketal group,
x+y+z=1, x is 0.1 to 0.9, specifically x is 0.1 to 0.7; y is 0.0 to 0.6, specifically y is 0.1 to 0.4; z is 0.1 to 0.9, specifically z is 0.1 to 0.7.
Specifically, the positive photosensitive resin composition of the present invention comprises:
a) 100 parts by weight of a copolymer represented by chemical formula 1;
b) 3 to 15 parts by weight of a photoacid generator having a melting point of 90 to 300 ℃, an Alkyl group (Alkyl group) of an Acid having 6 to 20 carbon atoms, and a solubility to propylene glycol monomethyl ether acetate (Propylene glycol monomethyl ether acetate) of 1 to 15%;
d) 0.01 to 5 parts by weight of an organic base; a kind of electronic device with high-pressure air-conditioning system
e) A solvent which brings the solids content to 10 to 50% by weight.
The copolymer represented by chemical formula 1 of the present invention has increased solubility due to the photoacid generator of the present invention, and can be prepared by a conventional copolymer preparation method such as radical polymerization or anionic polymerization.
In one specific example, the copolymer represented by chemical formula 1 is prepared by a radical polymerization method, which is as follows: hydroxystyrene, styrene and acetal styrene (or ketalstyrene) are subjected to radical polymerization in the presence of a solvent and a polymerization initiator, then precipitated and filtered, unreacted monomers are removed by a vacuum drying process, and then dissolved in methanol to prepare a resin solution and hydrolyzed in the presence of ammonia and acetic acid, then precipitated and filtered, and finally a copolymer can be prepared by a vacuum drying process.
The weight average molecular weight (Mw) of the copolymer represented by chemical formula 1 in terms of polystyrene in the present invention is preferably 3000 to 50000, more preferably 5000 to 30000. The weight average molecular weight of the copolymer within the above range has an advantage in that the requirements for the film residue ratio and the photosensitive speed (Photo speed) can be satisfied at the same time.
The photoacid generator of item b) above used in the present invention has a melting point of 90 to 300 ℃, a carbon number of Alkyl group (Alkyl group) of Acid (Acid) of 6 to 20, a solubility to propylene glycol monomethyl ether acetate (Propylene glycol monomethyl ether acetate, PGMEA) of 1 to 15%, more specifically, preferably, a melting point of 90 to 200 ℃, a carbon number of Alkyl group of Acid (Acid) of 6 to 15, and a solubility to Propylene Glycol Monomethyl Ether Acetate (PGMEA) of 3 to 10%.
If the melting point of the photoacid generator of the present invention is lower than 90 ℃, heat resistance is lowered and reflow is aggravated, resulting in a lowered resolution; if the number of carbon atoms of the alkyl group is less than 6, the acid diffusion rate is too high, and the CD deviation at each position becomes large, resulting in a decrease in the dispersity; if the solubility to PGMEA exceeds 15%, the solubility to the etching solution (Etchant) increases, the penetration rate increases, and the etching bias (Etch bias) increases (wet etching adhesion decreases).
As the photoacid generator, specifically, one selected from the group consisting of (Z) -N- (cyclohexylsulfonyloxy) -4-methoxyiminobenzyl cyanide ((Z) -N- (cyclohexylsulfonyloxy) -4-methoxybenzimidocyl cyanide), (Z) -N- (toluenesulfonyloxy) iminobenzyl cyanide ((Z) -N- (tosyloxy) benzimidoyl cyanide), (Z) -4-methoxy-N- (toluenesulfonyloxy) iminobenzyl cyanide ((Z) -4-methoxy-N- (tosyloxy) benzimidoyl cyanide), (Z) -N- (cyclohexylsulfonyloxy) iminobenzyl cyanide ((Z) -N- (cyclohexylsulfonyloxy) benzimidoyl cyanide), (Z) -N- (cyclohexylsulfonyloxy) -3, 4-dimethoxyiminobenzyl cyanide ((Z) -N- (cyclohexylsulfonyloxy) -3,4-dimethoxybenzimidoyl cyanide), (Z) -N- (3-cyclohexylsulfonyloxy) -4-methoxybenzyl cyanide ((Z) -3- (cyclohexylsulfonyloxy) 3-propylsulfonyloxy) 23-propylsulfonyloxy (Z) -2- ((Z) -2- (3-cyclohexylpropylsulfonyloxyimino) thiophene-3 (2H) -subunit) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (3-cyclohexylpropylsulfonyliminoo) thiophen-3 (2H) -yline) -2-o-tolylacetonile), (Z) -N- (cyclohexylmethylsulfonyloxy) -4-methoxyiminobenzyl cyanide ((Z) -N- (cyclohexylmethylsulfonylmethyliminoxy) -4-methoxybenzimidoyl cyanide), (Z) -2- ((Z) -2- (octylsulfonyloxyimino) thiophene-3 (2H) -subunit) -2-o-tolylacetonitrile ((Z) -2- (octylsulfonyliminoo) thiophen-3 (2H) -ylimino) -2-o-tolylacetonitrile ((Z) -2- (octylsulfonyliminoo) thiophen-3 (2H) -yline) -2-o-tolylacetonitrile), (Z) -2-o-tolylacetonile-2- (cyclohexylmethylsulfonyloxy) -4-methoxyiminone-4-methoxyiminocyanide ((Z) -2-methylsulfonylmethylcyanide ((Z) -2H) -2-sulfonyliminoo) -2- (2H) -tolylthio-3- (2H) -iminomethyl) thiophene-3- (2H) -iminomethyl) 2-oxoiminomethyl) sulfide One or more compounds selected from the group consisting of (Z) -2- ((Z) -2- (cyclohexylmethylsulfonyloxyimino) thiophen-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (cyclyloxymethyl-thioyimino) thiophen-3 (2H) -ylide) -2-o-tol ylaceto nitrile), (Z) -2- ((E) -5- (octylsulfonyloxyimino) thiophen-2 (5H) -ylidene) -2-phenylacetonitrile ((Z) -2- ((E) -5- (octylendolyloxyimino) thiophen-2 (5H) -ylide) -2-phenylaceto nitrile).
The photoacid generator is preferably contained in an amount of 3 to 15 parts by weight, more preferably 3 to 10 parts by weight, relative to 100 parts by weight of the copolymer of item a). When the content of the photoacid generator is within the above range, the requirements for wet etching adhesion, heat resistance, and dispersibility can be satisfied at the same time.
In addition, the positive photosensitive resin composition of the present invention contains c) an organic amine. For example, the organic amine may be selected from primary amines such as ethylamine, n-propylamine, acrylamide, ethanolamine, benzylamine, and the like; secondary amines such as diethylamine, n-propylamine, etc.; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, tributylamine, triethylamine, triisobutylamine, triisooctylamine, trioctylamine, dimethyldodecylamine (dimethylldodecylamine) and the like; quaternary amines such as tetrabutylammonium hydroxide, tetramethylammonium hydroxide, trimethylsulfur hydroxide, triphenylsulfur hydroxide, etc.; alcohol amines such as diethanolamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, and the like.
The content of the organic amine is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, relative to 100 parts by weight of the copolymer of item a). When the content of the organic amine is in the range, the requirements on the photosensitive speed and the residual film rate can be met at the same time.
In addition, the solvent of the above item e) used in the present invention has the effect of achieving flatness and avoiding the generation of coating specks to form a uniform pattern profile.
The solvent is not particularly limited as long as it is compatible with the components of the above items a), b), and c) and the additives selected for use in the present invention, and specifically, the solvent may be used: alcohols such as methanol, ethanol, benzyl alcohol, hexanol, etc.; glycol alkyl ether acetates such as glycol methyl ether acetate, glycol ethyl ether acetate, and the like; glycol alkyl ether propionate, such as glycol methyl ether propionate, glycol ethyl ether propionate, etc.; ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and the like; diethylene glycol alkyl ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like; propylene glycol alkyl ether propionate, such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and the like; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether and the like; dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and the like; butanediol monomethyl ethers such as butanediol monomethyl ether, butanediol monoethyl ether, etc.; or dibutylene alkyl ethers such as dibutylene dimethyl ether, dibutylene diethyl ether, etc.
The solvent is preferably capable of making the solid content of the total photosensitive resin composition 10 to 50% by weight, more preferably capable of making the solid content of the total photosensitive resin composition 10 to 40% by weight. If the solid content of the total composition is less than 10 wt%, the coating thickness becomes thin, and the coating flatness may be lowered; if the solid content exceeds 50% by weight, the coating thickness becomes thick, and a load may be imposed on the coating apparatus during the coating process.
For the positive photosensitive resin composition of the present invention composed of the above-described components, other additives useful for the positive photosensitive resin composition may be optionally contained as needed. Examples of the additive include, but are not limited to, melamine crosslinking agents, silane coupling agents, surfactants, stabilizers, and dyes. Specifically, the additives may be appropriately selected to be added to the composition within a range not to change physical properties, wherein the additives may be added in an amount of 0.01 to 10 parts by weight, respectively, relative to 100 parts by weight of the copolymer of item a).
The photosensitive resin composition of the present invention composed of the above components is preferably used after filtration through a microporous filter of 0.1 to 0.2. Mu.m.
In addition, the present invention provides a patterning method of an element using the positive photosensitive resin composition and an element patterned by the patterning method, and in particular, the element may be a display, a semiconductor, a microelectromechanical system (MEMS), an electronic paper (E-paper), a display element such as a thin film transistor liquid crystal display (TFT-LCD), an Organic Light Emitting Diode (OLED), or an organic thin film transistor (O-TFT).
In the method for forming a pattern of an element of the present invention, other steps than using the positive photosensitive resin composition may be performed according to a known pattern forming method.
In a more specific example, the pattern forming method of the OLED substrate is as follows by forming a pattern of the OLED substrate using the positive photosensitive resin composition:
first, the positive photosensitive resin composition of the present invention is applied to the surface of a substrate, and the solvent is removed by prebaking to form a coating film. The coating method may be a known method, for example, a slit coating method, a spray method, a roll coating method, a spin coating method, or the like. The pre-baking is preferably carried out at a temperature of 80-120 ℃.
Then, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, x-rays, etc., and post-Exposure baking (PEB) and blanket Exposure (Flood Exposure) as needed, according to a pattern prepared in advance, and then unnecessary portions are removed using a developer, thereby forming a predetermined pattern.
Further, after development, the pattern is formed by washing with ultrapure water for 30 seconds to 90 seconds to remove unnecessary portions, and then drying, and the pattern is subjected to heat treatment at a temperature of 130 to 250 ℃ for 3 times using a heating device such as an oven, thereby finally obtaining the pattern.
The positive photosensitive resin composition of the present invention has excellent sensitivity, resolution, pattern profile, post-exposure delay margin (PED margin), etc., particularly because of having a large chromophore structure having lipophilicity, excellent repulsive force and heat resistance to etching liquid permeation, and excellent wet etching adhesion and heat resistance, dispersivity by using a photoacid generator that easily controls the acid diffusion rate due to an acid structure containing a long alkyl chain. Therefore, the invention is suitable for large-area high-resolution displays such as thin film transistor liquid crystal displays (TFT-LCD), organic Light Emitting Diodes (OLED) or organic thin film transistors (O-TFT).
The following examples are given to aid those skilled in the art in understanding the present invention, but are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
Examples (example)
Example 1 (preparation of photosensitive resin composition)
The copolymer (R) represented by the formula 1 1 Is an acetal group, x=0.3, y=0.3, z=0.4, weight average molecular weight in terms of polystyrene: 12000 As a result of the increased solubility of the photoacid generator, relative to 100 parts by weight of the copolymer,a positive type photosensitive resin composition was prepared using 5 parts by weight of (Z) -2- ((Z) -2- (octylsulfonyloxyimino) thiophene-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (octylinder foxyimino) thiophen-3 (2H) -yline) -2-o-tolylacetonitrile) as a photoacid generator, using 0.5 parts by weight of triethylamine as an organic base, and dissolving using propylene glycol monomethyl ether acetate to make the solid content of the mixture 20% by weight, and then filtering using a microporous filter of 0.1. Mu.m.
Example 2
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (Z) -2-o-tolyl-2- (tosyloxyimino) thiophene-3 (2H) -ylidene) acetonitrile ((Z) -2-o-tolyl-2- (tosyloxyiminoo) thiophen-3 (2H) -ylethylene) as a photoacid generator was used in the preparation of the positive photosensitive resin composition, thereby obtaining a positive photosensitive resin composition.
Example 3
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (Z) -2- ((Z) -2- (cyclohexylmethylsulfonyloxyimino) thiophen-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (cyclohexyl methyl sulfonyl) hinged) thio phen-3 (2H) -ylidine) -2-o-tolylaceto nitrile) was used as a photoacid generator in the preparation of a positive type photosensitive resin composition, thereby preparing a positive type photosensitive resin composition.
Example 4
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (Z) -2- ((E) -5- (octylsulfonyloxyimino) thiophene-2 (5H) -ylidene) -2-phenylacetonitrile ((Z) -2- ((E) -5- (octylinoyloxymethyl) thiophen-2 (5H) -ylethylene) -2-phenylacetonile) was used as a photoacid generator in the preparation of the positive type photosensitive resin composition, thereby preparing a positive type photosensitive resin composition.
Example 5
Based on the above example 1, a positive type photosensitive resin composition was prepared except that a polystyrene resin was usedThe weight average molecular weight of the alkene converted is 12000 and R 1 A positive photosensitive resin composition was produced in the same manner as in example 1 except that the copolymer was a ketal group.
Example 6
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 3 parts by weight of N-hydroxynaphthalimide hexane sulfonate (N-Hydroxynaphthalimide hexanesulfonate) was used as a photoacid generator in the preparation of the positive photosensitive resin composition, thereby preparing a positive photosensitive resin composition.
Example 7
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (Z) -2- ((Z) -2- (dodecylsulfonyloxyimino) thiophen-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (dodecylsulfenyxyimino) thiophen-3 (2H) -yline) -2-o-tolylaceto nitrile) was used as a photoacid generator in the preparation of a positive type photosensitive resin composition, thereby preparing a positive type photosensitive resin composition.
Comparative example 1
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of α - (n-octanesulfonyloxy imino) -4-methoxybenzyl cyanide (α - (n-octanesulfenyxyimino) -4-methoxybenzyl cyanide) was used as a photoacid generator in the preparation of the positive photosensitive resin composition, thereby preparing a positive photosensitive resin composition.
Comparative example 2
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (3-propanesulfonyloxy imino-5H-thiophen-2-ylidene) -o-tolylacetonitrile (3-propanesulfonyloxy-5H-thiophen-2-ylethylene) -o-tolylacetonile) was used as a photoacid generator in the preparation of the positive photosensitive resin composition, thereby preparing a positive photosensitive resin composition.
Comparative example 3
The same procedure as in example 1 was conducted except that the copolymer represented by the following chemical formula 2 (a=0.5, b=0.5, and the weight average molecular weight in terms of polystyrene was 12000) was used as a copolymer in the preparation of the positive photosensitive resin composition, except that the positive photosensitive resin composition was prepared.
[ chemical formula 2]
Comparative example 4
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of α - (n-octanesulfonyloxy imino) -benzyl cyanide (α - (n-octanesulfenyloxy imido) -benzol cyanide) was used as a photoacid generator in the preparation of the positive photosensitive resin composition, thereby preparing a positive photosensitive resin composition.
Comparative example 5
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 5 parts by weight of (Z) -2- ((Z) -2- (butylcyclohexyldodecylsulfonyloxyimino) thiophen-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (butylcyclyloxycyclyldocaryholder) thiophen-3 (2H) -ylide ne) -2-o-tolylaceto nitrile) was used as a photoacid generator in the preparation of the positive type photosensitive resin composition, thereby preparing a positive type photosensitive resin composition.
Comparative example 6
Based on the above example 1, the same procedure as in the above example 1 was conducted except that 0.3 parts by weight of (Z) -2- ((Z) -2- (naphthylsulfonyloxyimino) thiophen-3 (2H) -ylidene) -2-o-tolylacetonitrile ((Z) -2- ((Z) -2- (naphthylsulfonyliminoo) thiophen-3 (2H) -ylene) -2-o-tolylacetonile) was used as a photoacid generator in the preparation of the positive type photosensitive resin composition, thereby preparing a positive type photosensitive resin composition.
The physical properties of the positive photosensitive resin compositions of examples 1 to 7 and comparative examples 1 to 6 were measured in the following manner and are shown in table 1 below.
A) Sensitivity: the positive type photosensitive resin composition solutions prepared in examples 1 to 7 and comparative examples 1 to 6 were coated on a glass (glass) substrate evaporated with IZO of 370 cm using a slit coater, vacuum dried (VCD) to 0.5torr, and then prebaked on a heating plate at 100 ℃ for 90 seconds, thereby forming a film of 2.0 μm. Using a pattern mask (pattern mask) with a Line (Line) CD of 2 μm, and irradiating with an exposure machine at an intensity of 10mW/cm in a Broadband (Broadband) 2 Is a ultraviolet ray of (a). Then, after development with 2.38 wt% aqueous tetramethylammonium hydroxide at 23℃for 70 seconds, the resultant was washed with ultrapure water for 60 seconds. The sensitivity was measured by using a Scanning Electron Microscope (SEM) based on the exposure amount of the Line CD of 3.0. Mu.m.
B) Reflux: the patterned film (Pattern) formed in the measurement of the sensitivity of item A) above was further baked on a hot plate at 130℃for 150 seconds to see whether or not the Line section was reflowed. The size increased by the change in CD due to the reflow is represented by O when it is smaller than 0.2. Mu.m, and the size increased by 0.2. Mu.m or more is represented by X.
C) Dispersity (Uniformity): the lines (lines) of the Pattern film formed in the measurement of the sensitivity of item A) above were divided into 15 equal parts according to the positions of the substrate, and the CD at each position was detected by a top view. The degree of dispersion is expressed by the value of [ average CD-most deviated CD ], and the smaller the value, the better the degree of dispersion. The dispersion degree is represented by O when smaller than 0.2. Mu.m, by delta when within the range of 0.2 to 0.5. Mu.m, and by X when larger than 0.5. Mu.m.
D) Wet etching adhesion: the patterned film (Pattern) formed during the reflow test in item B) was etched in an indium tin oxide (IZO) etchant at 40℃for 25 seconds, and then washed with ultrapure water for 60 seconds. The IZO film on the Line section was examined for etching deflection, expressed as O when the etching deflection was less than 0.2. Mu.m, expressed as delta when the etching deflection was in the range of 0.2 to 0.5. Mu.m, and expressed as X when the etching deflection was greater than 0.5. Mu.m.
[ Table 1]
[ Table 2]
Sensitivity (mJ) Reflow (Reflow) Dispersity of Etching adhesion
Example 1 23 △ ○ ○
Example 2 25 ○ ○ △
Example 3 24 ○ ○ ○
Example 4 20 △ ○ ○
Example 5 24 △ ○ ○
Example 6 35 ○ △ ○
Example 7 37 △ ○ ○
Comparative example 1 30 × ○ ×
Comparative example 2 20 △ × △
Comparative example 3 Unpatterned × × ×
Comparative example 4 29 × △ ×
Comparative example 5 45 × △ ○
Comparative example 6 150 × △ ×
As is apparent from tables 1 and 2 above, the positive type photosensitive resin compositions prepared in examples 1 to 7 above according to the present invention are significantly superior in sensitivity, reflow (Reflow), dispersibility and etching adhesion to those of comparative examples 1 to 6, and thus the positive type photosensitive resin compositions of the present invention can obtain better results in a pattern preparation process for display elements.
The foregoing describes the embodiments of the present invention, and those skilled in the art can make various modifications and adaptations to the present invention without departing from the scope of the technical idea of the present invention.

Claims (6)

1. A positive photosensitive resin composition comprising:
a) 100 parts by weight of a copolymer represented by the following chemical formula 1;
b) 3 to 15 parts by weight of a photoacid generator having a melting point of 90 to 300 ℃, the alkyl group of the acid having 6 to 20 carbon atoms, and a solubility to propylene glycol monomethyl ether acetate of 1 to 15%;
d) 0.01 to 5 parts by weight of an organic base; a kind of electronic device with high-pressure air-conditioning system
e) A solvent which brings the solids content to 10 to 50% by weight,
chemical formula 1
In the chemical formula 1 described above, a compound having the formula,
the R is 1 Is an acetal group, a ketal group,
x+y+z=1, x is 0.1 to 0.7, y is 0.1 to 0.4, and z is 0.1 to 0.7.
2. The positive type photosensitive resin composition of claim 1, wherein,
the copolymer of chemical formula 1 of the above a) has a weight average molecular weight (Mw) of 3000 to 50000 in terms of polystyrene.
3. The positive type photosensitive resin composition of claim 1, wherein,
the photoacid generator of b) is (Z) -2- ((Z) -2- (octylsulfonyloxy imino) thiophene-3 (2H) -subunit) -2-o-tolylacetonitrile, (Z) -2-o-tolyl-2- (toluenesulfonyloxy imino) thiophene-3 (2H) -subunit) acetonitrile, (Z) -2- ((Z) -2- (cyclohexylmethylsulfonyloxy imino) thiophene-3 (2H) -subunit) -2-o-tolylacetonitrile, or (Z) -2- ((E) -5- (octylsulfonyloxy imino) thiophene-2 (5H) -subunit) -2-phenylacetonitrile.
4. The positive type photosensitive resin composition of claim 1, wherein,
the organic base of d) is more than one selected from primary amine, secondary amine, tertiary amine, quaternary amine and alcohol amine.
5. The positive type photosensitive resin composition of claim 4, wherein,
the primary amine is ethylamine, n-propylamine, acrylamide, ethanolamine or benzylamine; the secondary amine is diethylamine; the tertiary amine is trimethylamine, methyldiethylamine, dimethylethylamine, tributylamine, triethylamine, triisobutylamine, triisooctylamine, trioctylamine or dimethyldodecylamine; the quaternary amine is tetrabutylammonium hydroxide or tetramethylammonium hydroxide; the alcohol amine is diethanolamine, dimethylethanolamine, methyldiethanolamine or triethanolamine.
6. The positive-type photosensitive resin composition according to claim 1, further comprising:
melamine crosslinking agents, silane coupling agents, surfactants, stabilizers or dyes.
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