KR20160087198A - Chemically amplified photosensitive resist composition and method of reducing yellowing by using the same - Google Patents

Abstract

The present invention relates to a chemically amplified photosensitive resist composition and a method for reducing yellowing using the same. More specifically, the chemically amplified photosensitive resist composition according to the present invention employs a binder resin, in which 3-hydroxy styrene and 4-hydroxy styrene are polymerized, thereby preventing the yellowing of a light- and heat-curable pattern even under a high-temperature heat treatment environment, and suppressing the deterioration in the developing property. In addition, the method for reducing the yellowing of a light- and heat-curable pattern using the chemically amplified photosensitive resist composition according to the present invention can prevent the light- and heat-curable pattern from being yellowed even under the environment in which high-temperature heat is applied.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified photosensitive resin composition and a method of reducing yellowing using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a chemical amplification type photosensitive resin composition, and more particularly, to a chemical amplification type photosensitive resin composition capable of reducing yellowing in a high-temperature baking process.

Photolithography is the most widely used method for forming various fine patterns such as a semiconductor, a thin film transistor, and a touch electrode. After a material for forming a pattern is deposited on a substrate, a resist pattern corresponding to the pattern is formed with a photoresist, Except for the portion where the resist pattern is formed, to obtain a fine pattern.

A typical method of forming a photoresist pattern using a photoresist includes a film forming process for applying a photoresist photosensitive resin composition on a vapor deposition film of a material to be patterned, a mask prepared corresponding to a pattern to be formed, A step of selectively irradiating the photoresist photosensitive resin film with light, a step of separating and removing the exposed area from the unexposed area (the parts removed in accordance with the positive system and the negative system are different from each other) And a developing step of obtaining a developing solution.

Further, it is possible to prevent the movement of the formed resin film by performing the pre-bake process before the exposure process, and to perform durability such as chemical resistance and heat resistance of the resist pattern formed by carrying out a post-bake process after the development process .

Among them, the positive photosensitive resin composition has the advantage that the resolution can be improved because it is theoretically possible to prevent the swelling phenomenon of a portion not exposed to ultraviolet rays. In addition, it is easy to remove by the peeling liquid after the film formation, and it is advantageous that the substrate recovery and the reusability are remarkably improved by removing the film when a bad panel is generated in the process.

The positive photosensitive resin composition is a composition containing a photosensitive resin (PAC (photo active compound)) added to the binder resin, such as a novolac resin system, a polyimide or a siloxane system, as well as an acrylic photosensitive resin used as a typical binder resin Such a resin composition is often insufficient in sensitivity. Particularly, there is not much difference in solubility between a portion irradiated with ultraviolet rays and a portion irradiated with ultraviolet rays, so that the resin composition often has insufficient resolution.

For example, U.S. Patent No. 4,139,391 discloses a photosensitive organic insulating film composition prepared by using a copolymer of an acrylate compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer. However, the difference in solubility between the exposed portion and the unexposed portion is not sufficiently large, so that the developing property is poor, and the binder resin to be left in the developing process is partially dissolved in the developing solution, making it difficult to obtain a fine pattern of 15 μm or less.

In order to solve such a problem, a chemically amplified photosensitive resin composition which removes a protecting group of a polymer binder through an acid catalyst reaction using an acid generated through exposed light, Was introduced.

However, in the chemically amplified photosensitive resin composition, the acid-decomposable acetal protecting group used in the polymer binder has a low boiling point due to a very small size of the product resulting from decomposition at the time of exposure, and there is a problem that a large amount of steam is generated at the time of exposure due to the high volatility There is a problem that the pattern becomes yellow when the patterns are continuously exposed to the high temperature environment formed during the heat treatment process or the manufacturing process according to the subsequent progress after the pattern formation.

U.S. Patent No. 4,139,391

An object of the present invention is to provide a chemically amplified photosensitive resin composition capable of reducing the yellowing phenomenon.

It is another object of the present invention to provide a method for reducing yellowing of light and heat curing patterns using the photosensitive resin composition according to the present invention.

In order to accomplish the above object, the present invention provides a chemically amplified photosensitive resin composition comprising a binder resin containing a repeating unit represented by the following formula (1), a photoacid generator, and a solvent.

[Chemical Formula 1]

Wherein R ₁ , R _2, R ₃ and R ₄ are independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, R ₁ and R ₂ or R ₃ and R ₄ may form a ring having 3 to 10 carbon atoms bonded to each other, o + r is 10 ~ 70mol%, p + q is 30 ~ 90mol%, o + q≥p + r Im).

As described above, the chemically amplified photosensitive resin composition according to the present invention uses a binder resin polymerized by simultaneously polymerizing 3-hydroxystyrene and 4-hydroxystyrene, so that even in a high temperature heat treatment environment, The development can be prevented, and at the same time, deterioration of the developability can be suppressed.

In addition, the method of reducing yellowing of light and heat curing patterns using the chemically amplified photosensitive resin composition according to the present invention is characterized in that the light and heat curing patterns to be produced are not yellow Do not.

FIG. 1 is a graph showing the change of yellowing due to oxidation of hydroxystyrene. FIG.

The present invention relates to a chemically amplified photosensitive resin composition capable of preventing yellowing by including a binder resin containing a repeating unit represented by the formula (1), a photoacid generator, and a solvent, and a method for reducing yellowing using the same.

Hereinafter, the present invention will be described in more detail.

The chemical amplification type photosensitive resin composition of the present invention comprises a binder resin, a photoacid generator, and a solvent.

The binder resin according to the present invention includes a repeating unit represented by the following formula (1). However, in the present invention, each repeating unit represented by the formula should not be construed as limited as shown in the formula, and the sub-repeating unit in parentheses can be freely positioned at any position of the chain within a predetermined mole% range. That is, although the parentheses in the chemical formulas are represented by one block for expressing the mol%, each sub-repeating unit may be located in a block or separately in each of the resins.

[Chemical Formula 1]

Wherein R ₁ , R _2, R ₃ and R ₄ are independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, R ₁ and R ₂ or R ₃ and R ₄ may form a ring having 3 to 10 carbon atoms bonded to each other, o + r is 10 ~ 70mol%, p + q is 30 ~ 90mol%, o + q≥p + r Im).

The binder resin according to the present invention is characterized in that each of the 3-hydroxystyrene monomer and the 3-hydroxy group contains a sub-repeating unit derived from a styrene monomer protected with an acetal acid-decomposable acetal protecting group in a predetermined content range or more, Yellowing can be prevented.

When only the 4-hydroxystyrene monomer is used alone or in excess, there is a problem that the light and heat curing patterns become yellow at high temperatures. The specific mechanism is shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

The repeating unit formed from the 4-hydroxy monomer (including the case where the acid-decomposable acetal protecting group is removed after the light and heat curing) is oxidized at high temperature and converted into a quinone structure. When these quinone structures are adjacent to each other, Thereby forming a resonance structure. The UV-vis spectral results obtained by analyzing the absorption wavelength for each of these structures are shown in Fig.

Referring to FIG. 1, it can be seen that when the tautomerization is performed, the absorption wavelength belongs to the visible ray region band, and the maximum absorption wavelength for each structure is shown in Table 1 below.

rescue Maximum absorption wavelength (nm)

Binder1.

243 Binder 2.

286 Totomer

433

The present invention grasps the yellowing mechanism of 4-hydroxystyrene at high temperature and changes the position of the hydroxy group of hydroxystyrene, thereby preventing the oxidation of the repeating unit and reducing the yellowing of the light and heat curing pattern.

In the binder resin of the present invention, the repeating unit formed from a 3-hydroxystyrene monomer (including the case where the acid-decomposable acetal protecting group is removed after the light and heat curing) is relatively more than the 4- , The oxidation of the formed light and heat curing pattern can be prevented and the yellowing can be reduced.

Furthermore, by including the repeating unit formed from the 4-hydroxystyrene monomer (including the case where the acid-decomposable acetal protecting group is removed after the light and heat curing) in a predetermined amount, properties such as developability of the resin composition and crosslinking property at low temperature Can be excellently maintained.

The binder resin of the present invention may be composed only of the repeating unit represented by the formula (1), and if necessary, may further contain a repeating unit derived from a comonomer copolymerizable with the styrene monomer.

Examples of the comonomer include an acrylate monomer and specific examples thereof include ethylene glycol di (meth) acrylate, 1,6-hexane diol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (Meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- methoxyethyl (meth) acrylate, 2- ethoxyethyl (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, di (Meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate,? -Phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (Meth) acrylate, (Meth) acrylate, octafluoropentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

In addition to the above acrylate-based monomer, there may be used at least one monomer selected from the group consisting of p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and other aromatic vinyl compounds; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like may be contained singly or in combination of two or more.

The weight average molecular weight of the binder resin according to the present invention is preferably 5,000 to 30,000 in view of maintaining excellent resolution, pattern straightness, and the like at the time of pattern formation.

The content of the binder resin is not particularly limited within a range capable of performing the function, and may be, for example, 5 to 50 wt%, and preferably 10 to 40 wt% of the total weight of the composition. When the content of the binder resin is 5 wt% or more and 50 wt% or less of the total weight of the composition, it is possible to maximize the effect of improving the sensitivity and resolution with an appropriate viscosity.

The photoacid generator according to the present invention is a compound which generates an acid by irradiation with an actinic ray or radiation.

Examples of the photoacid generator include, but are not limited to, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, Ortho-nitrobenzylsulfonate-based compounds and triprazine-based compounds. These may be used alone or in combination of two or more.

The content of the photoacid generator is not particularly limited within a range that can perform its function. For example, it may be contained in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on 100 parts by weight of the binder resin . When the content of the photoacid generator is within the above range with respect to 100 parts by weight of the binder resin, the chemical change due to the catalytic action of the acid can sufficiently take place and uniform application can be performed when applying the composition.

The type of the solvent according to the present invention is not particularly limited and any solvent can be used as long as it can dissolve the above-mentioned components, has a proper drying speed, and can form a uniform and smooth coating film after evaporation of the solvent.

Specific examples thereof include ethers, acetates, esters, ketones, amides, and lactones. These may be used alone or in combination of two or more.

Specific examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; And dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether.

Specific examples of the acetates include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; And dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate.

Specific examples of the esters include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, n-propyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, isopropyl myristate, Propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3- Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, and diethylene glycol methyl ethyl ester.

Specific examples of the ketone include methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone.

Specific examples of amides include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Specific examples of the lactones include? -Butyrolactone.

It is preferable to use propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof in view of coating properties and uniformity of the film thickness of the insulating film.

The content of the solvent is not particularly limited within a range capable of performing the function, and may be, for example, 40 to 90% by weight, preferably 50 to 80% by weight, of the total weight of the composition. When the content of the solvent is 40 wt% or more and 90 wt% or less based on the total weight of the composition, the solids content and viscosity can be maintained at an appropriate level, and coating properties are increased.

The photosensitive resin composition of the present invention may further contain other commonly used additives such as a basic compound, a surfactant, an adhesion improver, a heat crosslinking agent, a light stabilizer, a light and heat curing accelerator, a halation inhibitor (leveling agent) But may be further included within the scope not departing from the purpose.

The kind of the basic compound is not particularly limited, and can be arbitrarily selected from those used as the chemically amplified resist. Specific examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. These may be used alone or in combination of two or more.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, Amine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Specific examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

Specific examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N- But are not limited to, dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, , Pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] - undecenes.

Specific examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide.

Specific examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

The content of the basic compound is not particularly limited within a range that can perform its function, but may be 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the binder resin. If the content of the basic compound is 0.001 part by weight or more and 1 part by weight or less based on 100 parts by weight of the binder resin, there is an advantage that an interlayer insulating film having good heat resistance and solvent resistance can be formed.

The surfactant is a component that improves the adhesion between the substrate and the photosensitive resin composition.

The kind of the surfactant is not particularly limited, and various surfactants such as a fluorine-containing surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant and a silicone surfactant can be used. These may be used alone or in combination of two or more.

Specific examples of the fluorine-containing surfactant include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade name, SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (trade name, manufactured by Asahi Glass Co., Ltd.) and SOLSPERSE 20000 (trade name, manufactured by Lubrizol Japan Limited).

Specific examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylolethane, and ethoxylates or propoxylates thereof (e.g., glycerol propoxylate or glycerine ethoxylate); Polyoxyethylene lauryl ether such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, product of BASF), polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, and the like.

Specific examples of the cationic surfactant include a phthalocyanine-modified compound such as EFKA-745 (trade name, product of Morishita & Co., Ltd.), an organosiloxane such as KP341 (trade name, product of Shin-Etsu Chemical Co., Ltd.) Polymer; (Meth) acrylic acid type (co) polymer such as POLYFLOW No. 75, No. 90, No. 95 (trade name, product of Kyoeisha Chemical Co., Ltd.), W001 (trade name, product of Yusho Co., Ltd.) .

Specific examples of the anionic surfactant include W004, W005 and W017 (trade names, manufactured by Yusho Co., Ltd.).

Specific examples of the silicone surfactant include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade names, products of Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 (Trade name, product of Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, 323 and 330 (trade name, BYK Chemie).

The content of the surfactant is not particularly limited within a range capable of performing the function, but may be 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the binder resin. If the content of the surfactant is 0.01 to 5 parts by weight based on 100 parts by weight of the binder resin, the effect of improving adhesion between the substrate and the resin composition can be maximized.

The adhesion improver is effective for improving the adhesion between an inorganic substance serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film and adjusting the taper angle with the substrate Do.

The kind of the adhesiveness improver is not particularly limited, and specific examples include a silane coupling agent and a thiol-based compound, preferably a silane coupling agent.

The type of the silane coupling agent is not particularly limited, and specific examples include? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldi Alkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclo Hexyl) ethyltrialkoxysilane, vinyltrialkoxysilane and the like, and preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, more preferably γ-glycidoxy Propyl trialkoxysilane. These may be used alone or in combination of two or more.

The content of the adhesion improver is not particularly limited within a range that can perform its function, but may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. When the content of the adhesion improver is more than 0.1 parts by weight and less than 20 parts by weight based on 100 parts by weight of the binder resin, the adhesiveness to the insulating film can be improved and the effect of adjusting the taper angle with the substrate can be maximized.

The heat crosslinking agent is a component which improves the heat resistance by allowing the cross-linking reaction to occur smoothly through UV irradiation and heat treatment when forming the insulating film as a composition.

The type of thermal crosslinking agent is not particularly limited, and specific examples include polyacrylate resin, epoxy resin, phenol resin, melamine resin, organic acid, amine compound, anhydrous compound and the like. These may be used alone or in combination of two or more.

The content of the thermal cross-linking agent is not particularly limited within a range that can perform the function, but may be 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the heat crosslinking agent is within the above range with respect to 100 parts by weight of the binder resin, the heat resistance improving effect is maximized.

The light stabilizer is a component that improves the light resistance of the photosensitive resin composition.

The type of light stabilizer is not particularly limited, and specific examples thereof include benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, hindered amine-based compounds and the like. These may be used alone or in combination of two or more.

The content of the light stabilizer is not particularly limited within a range that can function, but may be 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the light stabilizer is within the above range with respect to 100 parts by weight of the binder resin, the effect of improving the light resistance is maximized.

The present invention provides a method for reducing yellowing using the photosensitive resin composition according to the present invention.

An embodiment of the method for reducing yellowing of the present invention will be described in more detail as follows.

First, a chemical amplification type photosensitive resin composition containing a binder resin containing a repeating unit represented by the general formula (1), a photo acid generator and a solvent as described above is applied to a substrate to form a film.

The method of applying the photosensitive resin composition is not particularly limited, and can be carried out by, for example, spin coating, flex coating, roll coating, slit-and-spin coating or slit coating.

The substrate to which the photosensitive resin composition is applied is not particularly limited as long as it is a substrate on which a light and heat curing pattern can be formed, and may be, for example, glass or a polymer substrate. In another aspect, the substrate may be a flexible substrate, in which case the polymer substrate described above may be used.

Examples of the polymer substrate include polyethersulphone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylenetaphthalate (PEN), polyethyeleneterephthalate (PET) Polyphenylene sulfide (PPS), polyallylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP ) May be used alone or in combination of two or more. However, the present invention is not limited thereto.

Further, the substrate may be formed with another layer on which a pattern is to be formed through photolithography. Such a layer may be a conductive layer, and the conductive layer may be formed of a metal, a metal oxide, a carbon-based material, or the like.

After the film forming step of applying the photosensitive resin composition to the substrate, a heat treatment step (pre-baking) may be further performed. Through this heat treatment process, volatile components such as residual solvent are removed. The heat treatment temperature is about 70 to 200 占 폚, preferably 80 to 130 占 폚. The film thickness after the heat treatment process may be about 1 to 8 mu m.

Next, the formed film is exposed and cured.

After the film-forming process is completed, an exposure process is performed in which light is irradiated to induce curing of the irradiated region. Exposure may be performed with a front exposure, and selective exposure may be performed through a mask to form a pattern of a predetermined type if necessary.

It is preferable to use an apparatus such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated onto the entire exposed portion in the exposure process and accurate alignment of the mask and the substrate is achieved.

The light to be used is not particularly limited as long as it can cure the photosensitive resin composition. Examples of the light include excimer laser, deep ultraviolet light, ultraviolet light, visible light, electron beam, X-ray or g-ray (wavelength: 436 nm) Ray (wavelength: 365 nm), h-ray (wavelength: 405 nm), or a mixture thereof. The exposure can be performed by contact, proximity, projection exposure or the like.

After the curing is completed, a developing process may be carried out, in which the coating film is brought into contact with a developing solution to dissolve and develop the exposed portion to form a desired pattern shape, if necessary.

Any of a liquid addition method, a dipping method, and a spraying method may be used as the developing method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Next, after curing, heat treatment is performed at 80 to 280 ° C.

The heat treatment according to the present invention may be an intentional process (for example, post-baking) for forming a light and heat curing pattern for inducing thermal crosslinking when a heat crosslinking agent is added to the photosensitive resin composition, And a heat treatment process that is applied to manufacture or combine other components in the manufacturing process of the product using the pattern after the heat curing pattern is manufactured.

The heat treatment temperature according to the present invention is a temperature which includes both the temperature for thermal crosslinking and the heat treatment conditions to be applied in the subsequent process and is the temperature at which the hydroxystyrene in which the alkyl group is not substituted at the alpha position is oxidized, 280 ° C. The repeating unit formed of hydroxystyrene in which the alkyl group is not substituted at the alpha position in the above temperature range is oxidized, but the light and the thermosetting pattern formed according to the present invention are not oxidized and the yellowing rate is remarkably lowered.

The light and heat curing patterns that can be formed from the photosensitive resin composition of the present invention are not limited to specific ones. For example, in addition to ordinary photoresist patterns applied to photolithography, various patterns in an image display device, A planarizing film pattern, a protective film pattern, an insulating film pattern, a black matrix pattern, a column spacer pattern and the like, but is not limited thereto.

The light and heat curing pattern according to the present invention can be applied not only to a conventional liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

≪ Example 1 >

Preparation of binder resin

Hydroxy styrene (84 g, 0.7 mol) and 4-hydroxystyrene (36 g, 0.3 mol) were dissolved in 500 g of propylene glycol methyl ether acetate (PGMEA) and heated to 70 캜. Respectively. A solution of 3 g of an azonitrile-based initiator 2,2'-azobis (2,4-dimethyl-valeronitrile) (Vazo 52G) and 8 g of chain-chain transfer agent 1-dodecanethiol in 20 g of PGMEA was added dropwise to a funnel , And slowly added for 6 hours.

In addition, 3 g of the initiator (Vazo 52G) was added to the reaction mixture and after 3 hours of reaction the polymerization inhibitor 2,5-bis (1,1-dimethylbutyl) hydroquinone (2,5-bis ), And the polymerization was terminated. Vinyl ethyl ether (14.4 g, 0.2 mol) was added, and the mixture was further reacted at the same temperature for 2 hours to protect 20 mol% of the hydroxyl group with an acetal group. (I.e., o: 24 mol%, p: 14 mol%, q: 56 mol%, and r: 6 mol%) as a result of the reaction with the vinyl ether in proportion to the molar ratio. The weight average molecular weight of the binder resin thus prepared was 14,500.

Preparation of Photosensitive Resin Composition

100 parts by weight of the binder resin thus prepared, 1 part by weight of a compound represented by the following formula (2) as a photoacid generator, and 120 parts by weight of propylene glycol methyl ethyl acetate as a solvent were mixed to prepare a photosensitive resin composition.

(2)

Formation of light and heat curing patterns

A photosensitive resin composition prepared by a spinner was coated on a 0.7 mm thick glass substrate (Corning 1737, Corning) and heated on a hot plate at 100 캜 for 125 seconds to volatilize the solvent to obtain a photosensitive resin composition layer .

Thereafter, in order to obtain a contact hole pattern having a diameter of 10 mu m, the exposure portion was exposed with an i-line stepper (NSR-205i11D, Nikon Corporation) using a mask having a square pattern opening with sides of 10 mu m.

The substrate after exposure was subjected to a puddle development with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 40 seconds using a developer, and then heated in an oven at 230 DEG C for 30 minutes to obtain a cured pattern.

≪ Example 2 >

Preparation of binder resin

The procedure of Example 1 was repeated using 3-hydroxystyrene (96 g, 0.8 mol) and 4-hydroxystyrene (24 g, 0.2 mol) to prepare a resin having a weight average molecular weight of 14,300.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

≪ Example 3 >

The procedure of Example 1 was repeated except that the content of vinyl ethyl ether was changed to 28.8 g (0.4 mol) to prepare a resin having a weight average molecular weight of 15,200.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

<Example 4>

By proceeding in the same manner as in Example 1 using the content of vinyl ethyl ether (7.2 g, 0.1 mol), a resin having a weight average molecular weight of 14,800 was prepared.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

&Lt; Comparative Example 1 &

Preparation of binder resin

4-Hydroxystyrene (120 g, 1 mol) was dissolved in 500 g of propylene glycol methyl ether acetate (PGMEA), heated to 70 캜 and completely mixed in a nitrogen purge state. A solution obtained by dissolving 3 g of an azonitrile-based initiator 2,2'-azobis (2,4-dimethyl-valeronitrile) (Vazo 52G) and 8 g of 1-dodecanethiol as a chain transfer agent in 20 g of PGMEA was added to a solution of 6 Hour.

3 g of an initiator (Vazo 52G) was added to the reaction mixture. After 3 hours of reaction, the polymerization was terminated by the addition of a polymerization inhibitor 2,5-bis (1,1-dimethylbuthyl) hydroquinone. Vinyl ethyl ether (14.4 g, 0.2 mol) was added thereto, and the mixture was further reacted at the same temperature for 2 hours to protect 20 mol% of the hydroxyl group with an acetal group.

The weight average molecular weight of the binder resin thus produced was 14,700.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

&Lt; Comparative Example 2 &

Preparation of binder resin

The procedure of Example 1 was repeated using 3-hydroxystyrene (24 g, 0.2 mol) and 4-hydroxystyrene (96 g, 0.8 mol) to prepare a resin having a weight average molecular weight of 13900.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

&Lt; Comparative Example 3 &

Preparation of binder resin

The procedure of Example 1 was repeated using 4-hydroxystyrene (6 g, 0.05 mol) and 3-hydroxystyrene (114 g, 0.95 mol) to prepare a resin having a weight average molecular weight of 13900.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the binder resin prepared above was used to obtain a light and heat curing pattern.

Test Example

The following evaluations were carried out on the resin compositions prepared according to Examples and Comparative Examples, and the results are shown in Table 2 below.

(1) Sensitivity

The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were coated with a spinner on a glass substrate (Corning 1737, Corning) having a thickness of 0.7 mm and heated on a hot plate at 100 占 폚 for 125 seconds to volatilize the solvent To form a photosensitive resin composition layer having a thickness of 4.0 m.

Thereafter, in order to obtain a contact hole pattern having a diameter of 10 mu m, the exposure portion was exposed with an i-line stepper (NSR-205i11D, Nikon Corporation) using a mask having a square pattern opening with sides of 10 mu m.

The substrate after exposure was subjected to a puddle development in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 40 seconds using a developing solution and heated in an oven at 230 DEG C for 30 minutes (post-baking) to obtain a cured film.

Subsequently, the substrate was cut vertically, and the exposure amount to make a 10-μm contact hole in each composition was selected as the sensitivity. The results are shown in Table 2 below.

(2) Transmittance (primary yellowing evaluation)

The transmittance of the substrate prepared in Test Example (1) was measured at 400 nm using a spectrophotometer, and the occurrence of yellowing was evaluated. When the transmittance was less than 90%, yellowing occurred. The results are shown in Table 2 below.

(3) Evaluation of heat stability (secondary yellowing evaluation)

The substrate prepared in Test Example (1) was allowed to stand in an oven at 230 ° C for 2 hours, and the transmittance at 400 nm was measured to evaluate the heat resistance stability (secondary yellowing evaluation) by the difference in transmittance before and after being left standing. .

division Foreclosure The ratio of 3-OH: 4-OH styrene Sensitivity
(mJ / cm ² ) Transmittance
(Primary yellowing)
(%) Heat stability
(Reduced transmittance,
Secondary yellowing) Example 1 0.2 7: 3 33 91 -3.5 Example 2 0.2 8: 2 35 92 -2.9 Example 3 0.4 7: 3 38 91 -3.3 Example 4 0.1 7: 3 31 91 -3.2 Comparative Example 1 0.2 0:10 34 85 -22.1 Comparative Example 2 0.2 2: 8 33 88 -15.7 Comparative Example 3 0.2 0.05: 0.95 33 85 -20.3

Referring to Table 2, in Examples 1 to 4, in which 3-hydroxystyrene and 4-hydroxystrene were contained in the above range as the binder resin, the light and heat curing patterns had a transmittance of 90% It was confirmed that yellowing did not occur, and sensitivity and heat stability were also excellent.

On the other hand, in the case of Comparative Examples 1 to 3 which did not contain all of 3-hydroxystyrene and 4-hydroxystrene as the binder resin or exceeded the above range, the transmittance was 86% on average, .

Claims (7)

1. A chemically amplified photosensitive resin composition comprising a binder resin comprising a repeating unit represented by the following formula (1), a photoacid generator, and a solvent:
[Chemical Formula 1]

Wherein R ₁ , R _2, R ₃ and R ₄ are independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms, R ₁ and R ₂ or R ₃ and R ₄ may form a ring having 3 to 10 carbon atoms bonded to each other, o + r is 10 ~ 70mol%, p + q is 30 ~ 90mol%, o + q≥p + r Im). The method according to claim 1,
o + r is 30 to 50 mol%, and p + q is 50 to 80 mol%. The method according to claim 1,
Wherein the binder resin is contained in an amount of 5 to 50% by weight in the whole composition. The method according to claim 1,
Wherein the chemical amplification type photosensitive resin composition comprises a photoacid generator and a solvent. 5. The method of claim 4,
Wherein the photoacid generator comprises 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin,
Wherein the solvent comprises 40 to 90% by weight of the total composition. A photocurable pattern formed by the chemical amplification type photosensitive resin composition according to any one of claims 1 to 5. The method according to claim 6,
Wherein the photo-curable pattern is at least one selected from the group consisting of a photoresist pattern, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a black matrix pattern and a column spacer pattern.

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