KR102351287B1 - Photosensitive Resin Composition, Cured Film Prepared Therefrom, and Electronic Device Comprising the Cured Film - Google Patents

Abstract

The present invention is an alkali-soluble acrylate resin; photopolymerizable compounds; photoinitiator; and a photosensitizer; and a photosensitive resin composition comprising an aromatic or heteroaromatic compound substituted with an alkoxysilane or alkylalkoxysilane terminal as the photosensitizer, a cured film formed therefrom, and an electronic device comprising a cured film will be.

Description

Photosensitive resin composition, a cured film formed therefrom, and an electronic device comprising a cured film TECHNICAL FIELD

The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and an electronic device including the cured film.

In the TFT circuit manufacturing process of a liquid crystal display device, a photosensitive resin composition is uniformly applied to a conductive metal film such as aluminum, copper, molybdenum, etc., a semiconductor film such as amorphous silicon, or an insulating film such as a silicon oxide film or silicon nitride film formed on a substrate. and baking to form a photoresist film, selectively exposing it to light irradiation, developing and removing the unexposed portion to form a photoresist pattern, and then using the patterned photoresist film as a mask to form a photoresist film as a mask for the conductive metal After the microcircuit pattern is transferred to the lower layer by wet or dry etching of the film, semiconductor film, or insulating film, the unnecessary photoresist layer is removed with a stripper (removing solution).

That is, the photosensitive resin composition can be irradiated with light, polymerized, and cured, so it is used in photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCD, photoresists for resin black matrix, or transparent photosensitive materials. .

In addition, the photosensitive resin composition is being manufactured for the purpose of composing liquid crystal display devices such as TVs and monitors in addition to the conventional use of notebooks and mobiles as the uses of LCDs are advanced and diversified. Demand for rapid response and mechanically excellent properties is increasing.

In particular, when a pattern is formed by a photolithography method or an insulating protective film is formed through exposure to the front surface, a characteristic of rapidly responding to light, ie, light sensitivity, is a very important factor.

In the above process, if the photosensitivity of the photosensitive resin composition is not good, the time required for the exposure process is long and the number of treatments per unit time is decreased, so there is a problem in that productivity is lowered. Therefore, when the UV absorption wavelength of the photopolymerization initiator does not match the emission wavelength of the exposure machine, a sensitizer is generally added to the photosensitive resin composition to improve photosensitivity. The injected sensitizer transmits the light of the exposure machine to the photoinitiator to activate the photoinitiator to cause photoinitiation.

In particular, in the case of a negative photosensitive composition among the photosensitive compositions, the effective amount of light reaching the lower part of the film is low, so the photoinitiation efficiency is significantly lower than that of the upper part. taper) indicates the pattern shape.

In order to prevent the occurrence of such a reverse tapered pattern, a photosensitizer was added to match the light efficiency of the upper and lower parts, but despite the input of the photosensitizer, there was little difference in the concentration of the photosensitizer in the upper and lower parts. Therefore, the actual effect due to the input of the photosensitizer was very insignificant.

For example, in Korean Patent Application Laid-Open No. 10-2012-0118600, 9(10H)-acridone in which an alkyl having 2 to 11 carbon atoms is substituted at position 10, and chloro at position 2 in Korean Patent Application Laid-Open No. 10-2012-0021488 9(10H)-acridone substituted and substituted with an alkyl having 2 to 11 carbon atoms at positions 10 Although the alkyl-substituted anthracene of 6 is disclosed as a photosensitizer for the photosensitive resin composition, the concentration of the photosensitizer at the upper and lower parts of the film is almost the same, so the photoinitiation efficiency of the lower part of the film is significantly lower than that of the upper part, and there is a lack of photocuring in the lower part of the film In the end, there was a problem in that the pattern phenomenon was obtained as a reverse taper.

Therefore, in order to match the upper and lower light efficiency in the photosensitive resin composition, there is a need for a technique for increasing the lower photoinitiation efficiency as much as the upper photoinitiating efficiency by further improving the photosensitivity of the lower part of the film.

Korean Patent Publication 10-2012-0118600 Korean Patent Laid-Open Patent No. 10-2012-0021488 Korean Patent Laid-Open Patent No. 10-2015-0105120 Korean Patent Laid-Open Patent No. 10-2015-0105121

It is an object of the present invention to provide an improved photosensitive resin composition having improved sensitivity and resolution through an increase in the degree of lower photocrosslinking.

Another object of the present invention is to provide a cured film obtained by curing the photosensitive resin composition and an electronic device including the same.

The present invention is an alkali-soluble acrylate resin; photopolymerizable compounds; photoinitiator; and a photosensitizer, wherein the photosensitizer provides a photosensitive resin composition comprising an aromatic or heteroaromatic compound in which an alkoxysilane or an alkylalkoxysilane is substituted at the terminal.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer may have a structure showing a light absorption peak in the 380-450 nm region.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer is tri (C1-C10) alkoxysilane, di (C1-C10) at the end of the anthracene-based, benzophenone-based or acridone-based photosensitizer. Alkoxy(C1-C10)alkylsilane or di(C1-C10)alkyl(C1-C10)alkoxysilane may be substituted.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer may be represented by the following formula (1).

[Formula 1]

In Formula 1,

L ₁ is C1-C10 alkylene or C3-C20 cycloalkylene;

R ₁ is C1-C10 alkyl or C1-C10 alkoxy;

R ₂ and R ₃ are each independently C1-C10 alkoxy;

R ₄ is hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl or halogen.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer may be one or more selected from the following structures.

In the photosensitive resin composition according to an embodiment of the present invention, the alkali-soluble acrylate resin may be a copolymer of an ethylene-based monomer and a monomer selected from an ethylene-based monomer having an acidic group.

In the photosensitive resin composition according to an embodiment of the present invention, the photopolymerizable compound may be a polyfunctional monomer having an ethylenically unsaturated bond.

In the photosensitive resin composition according to an embodiment of the present invention, the photoinitiator is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, an imidazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime It may be at least one selected from the group-based compounds.

In the photosensitive resin composition according to an embodiment of the present invention, at least one selected from a silane coupling agent, a surfactant, and a solvent may be further included.

In the photosensitive resin composition according to an embodiment of the present invention, based on 100 parts by weight of the alkali-soluble acrylate resin, 10 to 300 parts by weight of the photopolymerizable compound, 0.1 to 10 parts by weight of the photoinitiator, and 0.01 parts by weight of the photosensitizer to 10 parts by weight.

In addition, the present invention provides a cured film obtained by curing the photosensitive resin composition and an electronic device including the same.

The photosensitive resin composition of the present invention contains an aromatic or heteroaromatic compound substituted with an alkoxysilane or an alkylalkoxysilane at the terminal as a photosensitizer, thereby increasing the photosensitizer concentration in the lower part of the film to increase the lower photocrosslinking degree. Significantly improves sensitivity and resolution.

In the case of the conventional photosensitizer, there is almost no difference in concentration in the upper and lower parts, so the photoinitiation efficiency of the lower part of the film is significantly lower than that of the upper part, and the photocrosslinking is not performed well in the lower part of the film. While the effect is insignificant, the photosensitizer included in the photosensitive resin of the present invention has an alkoxysilane or alkylalkoxysilane functional group introduced at the terminal, unlike conventional photosensitizers, and the alkoxysilane or The alkylalkoxysilane functional group is adsorbed on the surface of the substrate by a condensation reaction with a surface hydroxyl group of the substrate (SiNx, etc.) to increase the concentration of the photosensitizer at the bottom of the membrane, thereby increasing the degree of photocrosslinking at the bottom.

That is, the photosensitive resin composition of the present invention can significantly improve sensitivity and resolution by increasing the degree of photocrosslinking at the bottom of the film due to the photosensitizer introduced with alkoxysilane or alkylalkoxysilane.

In addition, the photosensitive resin composition of the present invention can manufacture an excellent and highly reliable cured film and an electronic device including the same by having the excellent properties as described above.

Advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be embodied in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Hereinafter, the photosensitive resin composition according to the present invention, an organic insulating film using the same, and a display device including the organic insulating film will be described in detail.

As used herein, the term “alkoxy” refers to a functional group derived from a straight-chain or pulverized hydrocarbon, and may have 1 to 10 carbon atoms, and is preferably selected from methoxy, ethoxy, propoxy and butoxy. However, the present invention is not limited thereto.

In addition, in this specification, unless otherwise specified, "exposure" refers to a mercury lamp; Excimer laser, X-ray, EUV light, etc., as well as exposure by far ultraviolet rays typified by particle beams, such as electron beams and ion beams, are included.

Conventionally, a photosensitizer was added to the photosensitive resin composition to improve photosensitivity, but in the case of a general photosensitizer, there is little difference in the concentration of the photosensitizer in the upper and lower portions. In the lower part, there was a problem in that the lack of photocuring occurred and eventually the pattern phenomenon was obtained as a reverse taper.

Accordingly, the present inventors have found that a photosensitive resin composition having improved properties can be prepared by solving the conventional problems by using an aromatic or heteroaromatic compound having an alkoxysilane functional group introduced therein as a photosensitizer, and completed the present invention.

The present invention is an alkali-soluble acrylate resin; photopolymerizable compounds; photoinitiator; and a photosensitizer, wherein the photosensitizer provides a photosensitive resin composition comprising an aromatic or heteroaromatic compound in which an alkoxysilane or an alkylalkoxysilane is substituted at the terminal.

The photosensitizer of the present invention is an aromatic or heteroaromatic compound in which an alkoxysilane or alkylalkoxysilane functional group is introduced at the terminal, has excellent sensitivity to a long wavelength, and transfers energy to the photoinitiator through a faster photoinitiation reaction than the photoinitiator. While improving the initiation reaction rate, the alkoxysilane or alkylalkoxysilane functional group introduced at the end of the photosensitizer is chemically bonded to the surface of the substrate through a condensation reaction with the surface hydroxyl group of the substrate (SiNx, etc.) By increasing the concentration of the photosensitizer, the lower photocrosslinking degree is increased, so that the sensitivity and resolution can be remarkably improved.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer has a structure showing a light absorption peak in the 380-450 nm region.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer is tri (C1-C10) alkoxysilane, di (C1-C10) at the end of the anthracene-based, benzophenone-based or acridone-based photosensitizer. Alkoxy(C1-C10)alkylsilane or di(C1-C10)alkyl(C1-C10)alkoxysilane is substituted, and the introduction position of the alkoxysilane or alkylalkoxysilane is not limited.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer may be represented by the following formula (1).

[Formula 1]

In Formula 1,

L ₁ is C1-C10 alkylene or C3-C20 cycloalkylene;

R ₁ is C1-C10 alkyl or C1-C10 alkoxy;

R ₂ and R ₃ are each independently C1-C10 alkoxy;

R ₄ is hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl or halogen.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer of Formula 1 is L ₁ is C1-C10 alkylene; R ₁ is C1-C10 alkyl or C1-C10 alkoxy; R ₂ and R ₃ are each independently C1-C10 alkoxy; R ₄ may be hydrogen or halogen, more preferably L ₁ is C1-C7 alkylene; R ₁ is C 1 -C 7 alkyl or C 1 -C 7 alkoxy; R ₂ and R ₃ are each independently C1-C7 alkoxy; R ₄ may be hydrogen or halogen.

In the photosensitive resin composition according to an embodiment of the present invention, the photosensitizer may be one or more selected from the following structures.

In addition, the alkali-soluble acrylate resin of the photosensitive resin composition according to an embodiment of the present invention is not limited as long as it is commonly used in the art, but the resolution and developability of the organic insulating film prepared therefrom, high heat resistance, excellent balance In terms of satisfying the film ratio, it may be a copolymer of an ethylene-based monomer and a monomer selected from an ethylene-based monomer having an acidic group, and more preferably a copolymer of an ethylene-based monomer and an ethylene-based monomer having an acidic group.

In one embodiment, the ethylene-based monomer is an ethylene-based monomer having no acid group, methyl methacrylate, trimethoxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, alkyl acrylate , steacrylate, cyclohexyl acrylate, isobornyl acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylic an aliphatic ethylenic monomer selected from acrylate, 2-acryloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-phenoxypropyl acrylate, and methacrylates thereof; and styrene, benzyl methacrylate, benzyl acrylate, phenyl acrylate, phenyl methacrylate, nitrophenyl acrylate, nitrophenyl methacrylate, nitrobenzyl methacrylate, chlorophenyl acrylate and chlorophenyl methacrylate. an aromatic ethylenic monomer; and the like, but is not limited thereto.

In one embodiment, the ethylenic monomer having an acid group is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or an acid anhydride thereof, acrylooxyethyl hydrogen phthalate, acrylooxypropyl hydrogen phthalate, and acrylooxypropylhexahydrogenphthalate, but is not limited thereto.

In one embodiment, the polystyrene conversion weight average molecular weight of the alkali-soluble acrylate resin may be 5,000 to 200,000, but is not limited thereto.

In one embodiment, the alkali-soluble acrylate resin preferably has a weight average molecular weight of 5,000 to 150,000 by polymerizing styrene, glycidyl methacrylate and methacrylic acid monomer, more preferably styrene: glycidyl It may be a copolymer having a weight average molecular weight of 7,000 to 50,000 by polymerization of methacrylate: methacrylic acid in a ratio of 40:30:30.

The photopolymerizable compound of the photosensitive resin composition according to an embodiment of the present invention may be a polyfunctional monomer having an ethylenically unsaturated bond, and may be used without particular limitation as long as it is commonly used in the art.

In one embodiment, the photopolymerizable compound is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol diacrylate Methacrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol diacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic Rate, polyethylene glycol di(meth)acrylate, pentaerythritol hexaacrylate, pentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate (DPHA) , dipentaerythritol pentaacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, trimethylpropane triacrylate, pentaerythritol hexa (meth) acrylate, pentaerythritol penta (meth) acrylate , pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta It may be at least one selected from erythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, sorbitol tri(meth)acrylate, and trimethylpropane tri(meth)acrylate.

The photoinitiator according to an embodiment of the present invention may be used without particular limitation as long as it is commonly used in the art, and specifically, for example, an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, It may be at least one selected from a dazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime-based compound.

In one embodiment, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-( 2-Hydroxyethoxy)-phenyl (2-hydroxy)propyl ketone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl-(4-methylthiophenyl )-2-morpholino-1-propan-1-one (Irgacure-907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2 -acetophenone compounds such as dichloro-4-phenoxyacetophenone and 2,2-diethoxyacetophenone; benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone; 4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2,4-trichloromethyl -(Piflonyl)-6-triazine, 2,4-trichloromethyl-(3',4'-dimethoxyphenyl)-6-triazine, 3-{4-[2,4-bis(trichloro) Rhomethyl)-s-triazin-6-yl]phenylthio}propanoic acid, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl Triazines such as -4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, and 2,4-trichloromethyl-4-methylnaphthyl-6-triazine compound; benzoin compounds such as benzoin, benzoin methyl ether, benzoin i-propyl ether, and benzoin i-butyl ether; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5 imidazole compounds such as ,5'-tetraphenylbiimidazole; xanthone-based compounds such as xanthone, thioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, bis(2,6-dichlorobenzoyl)propyl phosphine phosphine-based compounds such as oxides; and 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (eg, IRGACURE OXE-01; trade name; BASF Japan Corporation), ethanone, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9-carbazol-3-yl]-,1-(O-acetyloxime) (eg, IRGACURE OXE-02; brand name; BASF Japan Co., Ltd.), OXE-03 ( Brand name: BASF Japan Co., Ltd.), 1-(O-acetyloxime), 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O- oxime compounds such as acetyloxime); and the like, but is not limited thereto.

The photosensitive resin composition according to an embodiment of the present invention is based on 100 parts by weight of the alkali-soluble acrylate resin, 10 to 300 parts by weight of the photopolymerizable compound, 0.1 to 10 parts by weight of the photopolymerization initiator, and 0.01 to 10 parts by weight of the photosensitizer. including parts by weight. The photosensitive resin composition satisfying the above content may simultaneously satisfy the sensitivity, resolution, taper, adhesion, flatness, developability, heat resistance, etc. desired in the present invention. Preferably, based on 100 parts by weight of the alkali-soluble acrylate resin, 10 to 200 parts by weight of the photopolymerizable compound, 0.1 to 5 parts by weight of the photopolymerization initiator, and 0.1 to 10 parts by weight of the photosensitizer may be included, more preferably Preferably, based on 100 parts by weight of the alkali-soluble acrylate resin, 50 to 150 parts by weight of the photopolymerizable compound, 0.5 to 5 parts by weight of the photopolymerization initiator, and 0.1 to 5 parts by weight of the photosensitizer may be included, but is not limited thereto. .

Of course, the photosensitive resin composition according to an embodiment of the present invention may further include any additives commonly used in the art. In this case, the optional additives may be silane coupling agents, surfactants, fillers, curing agents, leveling agents, adhesion aids, antioxidants, ultraviolet absorbers, aggregation inhibitors, chain transfer agents, solvents, etc., preferably silane coupling agents, surfactants and It may be one or more selected from solvents.

The silane coupling agent is not limited as long as it is commonly used in the art as a configuration for improving adhesion to the substrate, but non-limiting examples thereof include 3-(meth)cryloxypropyltrimethoxysilane, 3- (meth)acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxy-ethoxy)-silane, 2-(acryloxyethoxy)trimethylsilane, N- (3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methyl bis-(trimethylsiloxy)silane , (3-acryloxypropyl)methyldimethoxysilane, 3-(N-arylamino)propyltrimethoxysilane, butenyltriethoxysilane, [2-(3-cyclohexenyl)ethyl]trimethoxysilane , 5-(bicycloheptenyl)triethoxysilane, (3-cyclopentadienylpropyl)triethoxysilane, 1,1-diethoxy-1-silyl acrylophen-3ene, (furfuryloxy Methyl) triethoxysilane, N-(3-(meth)acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, ((meth)acryloxymethyl)bis(trimethylsiloxy)methyl Silane, ((meth)acryloxymethyl)dimethylethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethyltrimethoxysilane, 3-(meth)acryloxypropyl bis(trimethylsiloxy) ) Methylsilane, (meth)acryloxypropyldimethylmethoxysilane, (meth)acryloxypropyldimethylmethoxysilane, (meth)acryloxypropylmethyldiethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, (3) -Acryloxypropyl)trimethoxysilane, (meth)acryloxypropyl tris(methoxyethoxy)silane, (meth)acryloxypropyltris(vinyldimethoxysiloxy)silane, 3-(N-styrylmethyl- 2-Aminoethylamino)-propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl -Butylidene) propylamine, N-phenyl-3-aminopropyltri Methoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycy Dyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane , 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyl It may be one selected from diethoxysilane, 3-aminopropylmethyldiethoxysilane and 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane.

In this case, the silane coupling agent may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble acrylate resin of the photosensitive resin composition. may be included, but not limited to.

In addition, the surfactant is a composition for improving the coating property of the photosensitive resin composition according to the present invention on a substrate and imparting a defect prevention effect, and may be selected from a fluorine-based surfactant, a silicone-based surfactant, a polyoxyethylene-based surfactant, and the like. can At this time, non-limiting examples of the surfactant include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, FZ-2100, FZ-2110, FZ-2122, FZ-2222 and FZ-2233 of Dow Corning Toray Silicone Co., GE Toshiba Silicone silicone-based surfactants such as TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 manufactured by the Company; and polyoxyethylene alkyl ether surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ether surfactants such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl ester surfactants such as polyoxyethylene dilaurate and polyoxyethylene distearate; and the like, but is not limited thereto.

In this case, the surfactant may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble acrylate resin of the photosensitive resin composition. may be included, but is not limited thereto.

The filler according to an embodiment of the present invention may specifically include glass, silica, alumina, and the like.

The curing agent according to an embodiment of the present invention is used to increase deep curing and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like, and as a specific example of the epoxy compound in the curing agent, Bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl ester resins Cydylamine-based resins or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used 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 together with the curing agent. As said hardening auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, etc. are mentioned, for example.

As the carboxylic acid anhydride, a commercially available one can be used as an epoxy resin curing agent. Examples of the epoxy resin curing agent include a brand name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), a trade name (MH-700) ( Manufactured by New Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent according to an embodiment of the present invention, commercially available surfactants may be used, for example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, etc. surfactants. and these can be used individually or in combination of 2 or more types, respectively.

The antioxidant according to an embodiment of the present invention is specifically, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1 -(2-Hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy -5-methylphenyl)propoxy]-2,4,8,10-tetra-tert butyldibenz[d,f][1,3,2]dioxaphospepine, 3,9-bis[2-{3 -(3-tert-Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2 '-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-(butane-1,1-diyl)bis(2-(tert-butyl)-5-methylphenol), 4, 4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6- tert-Butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate , pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri Azine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a'' -(Mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and the like, and preferably 4,4'-(butane-1,1-diyl)bis(2-(tert-butyl)-5-methyl phenol).

Specific examples of the ultraviolet absorber according to an embodiment of the present invention include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate, and specific examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

The content of additives such as fillers, curing agents, leveling agents, antioxidants, ultraviolet absorbers, aggregation inhibitors, and chain transfer agents may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the composition.

The solvent is not limited as long as it dissolves or mixes all components of the photosensitive resin composition according to an embodiment of the present invention, and non-limiting examples thereof include propylene glycol monoethyl propionate, propylene glycol methyl ether propio propylene glycol alkyl ether propionates such as nitrate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alkyl cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate ethyl, methyl hydroxyacetate, hydroxyacetic acid Ethyl, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy Methyl hydroxy-3-methylbutanoate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, pro Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 2-methoxymethyl propionate, 2-methoxy Ethyl propionate, 2-methoxypropyl propionate, 2-methoxybutyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-ethoxypropionate propyl, 2-ethoxy butyl propionate, 2-part Methyl oxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-ethoxy Methyl propionate, 3-ethoxypropionate ethyl, 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate ethyl, 3-propoxypropionate propyl, 3-propoxypropionic acid It may be at least one selected from esters such as butyl, 3-methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

At this time, the amount of the solvent is not limited to implement the desired viscosity, but preferably based on 100 parts by weight of the alkali-soluble acrylate resin of the photosensitive resin composition, preferably 10 to 2,000 parts by weight, more Preferably, it may be included in an amount of 100 to 1,000 parts by weight.

In addition, the present invention provides a cured film obtained by curing the photosensitive resin composition and an electronic device including the same.

Of course, the cured film according to the present invention and a method for manufacturing an electronic device including the same can be any known method within the range recognized by those skilled in the art.

Hereinafter, a method of forming a cured film using the photosensitive resin composition according to the embodiment will be described.

Specifically, the cured film using the photosensitive resin composition according to an embodiment of the present invention is formed by applying the photosensitive resin composition according to the present invention on a substrate and removing the solvent by pre-baking to form a coating film: and It may be manufactured by a manufacturing method comprising a; photocuring by irradiation with light.

According to an embodiment of the present invention, the application may use a conventional coating method, and may include a spray method, a roll coater method, a rotation coating method, etc. as an example, but is not limited thereto.

In addition, the pre-bake may be performed under normal temperature conditions using a heating device such as a hot plate or an oven, and in one embodiment, may be performed at a temperature of 50 to 200° C. for 1 to 5 minutes, but is not limited thereto.

According to an embodiment of the present invention, the film thickness after prebaking may be 0.1 μm to 15 μm.

According to an embodiment of the present invention, the light may be selected from visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., and of course, a predetermined pattern may be formed using a pattern prepared in advance on the coating film. .

In one embodiment, the ultraviolet rays may use g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc., and it goes without saying that the irradiation amount of these ultraviolet rays may be appropriately selected as necessary. .

According to an embodiment of the present invention, after prebaking, 10 mJ in a wavelength range of 200 nm to 450 nm using a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), etc. Exposure may be performed at an exposure dose of /cm 2 to 500 mJ/cm 2 .

In addition, silicon, quartz, glass, silicon wafers, polymers, metals, metal oxides, etc. may be used as the substrate, but is not limited thereto. The polymer substrate is triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, Polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, poly A film substrate such as methyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polycarbonate may be used, but is not limited thereto.

In addition, after the photocuring step, the step of developing with a developer may be further included. This developing step is a process for removing the non-exposed part after photocuring through a mask for forming a target pattern, which can be performed by immersing in a developer by a conventional method such as a liquid addition method, a dipping method, and a spray method. can

In one embodiment, the step of developing according to the present invention may be performed by dipping the substrate in a developer by tilting the substrate at an arbitrary angle.

At this time, the developer is not limited as long as it is an aqueous alkali solution, but non-limiting examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate; primary amines such as n-propylamine and monoethanolamine; secondary amines such as diethylamine, n-propyldiamine, and diethanolamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, and diethylaminoethanol; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; It may be an aqueous solution of one or more alkaline compounds selected from the like. In this case, the developer may be an aqueous solution containing the above-described alkaline compound in an amount of 0.1 to 10% by weight, but is not limited thereto.

In addition, after the developing step, washing with ultrapure water for 30 to 300 seconds and drying in a range of 50 to 150° C. with a heating device such as a hot plate or an oven may be further performed.

In addition, after the washing and drying step, the step of thermosetting in the range of 200 to 300 ℃ using a heating device such as an oven may be further performed.

The cured film according to an embodiment of the present invention can be effectively used in electronic devices such as display devices, semiconductor devices, or optical waveguide materials, and specifically, a thin film transistor (TFT) substrate such as a liquid crystal display device or an organic EL display device. It can be used as a core or clad material of an optical waveguide such as a planarization film for use, a protective film or insulating film for touch panel sensor elements, etc., an interlayer insulating film for semiconductor elements, a planarization film for a solid-state imaging element, a microlens array pattern, or an optical semiconductor element. .

In this case, the thickness of the cured film may be suitably changed according to the purpose, but may preferably be formed to a thickness of 100 nm to 50 µm, and more preferably be formed to a thickness of 500 nm to 10 µm.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

(Assessment Methods)

After applying the photosensitive resin composition prepared in the following Examples and Comparative Examples using a spin coater on a glass substrate of width × length and 4 inches, pre-baking at 105° C. for 100 seconds using a hot plate to have a thickness of 3.6 μm. A film was formed.

The prebaked substrate was cooled to room temperature and then irradiated with light at an exposure dose of 40 mJ/cm 2 (based on 365 nm) using an exposure machine (UX-1100SM; manufactured by Ushio Co., Ltd.).

After light irradiation, the coating film was developed by immersing it in 2.38% tetramethylammonium hydroxide aqueous solution at 25° C. for 60 seconds, followed by washing and drying.

Then, an organic insulating film having a thickness of 3.0 μm was obtained by thermal curing at 230° C. for 30 minutes using an oven.

1. Sensitivity: The film obtained above was irradiated with ultraviolet rays having an intensity of 10 mW/cm 2 at 365 nm using a predetermined pattern mask at 1 second intervals for 1 to 30 seconds. Sensitivity was measured based on the exposure amount at which the residual film rate was saturated based on the 10㎛ Line & Space CD using SEM.

2. Resolution: The minimum pattern size of the organic insulating film formed during the sensitivity measurement was evaluated.

3. Taper: The cross section of the 10 μm pattern of the organic insulating film formed during the sensitivity measurement was measured for pattern slope using SEM.

[Examples 1 to 3 and Comparative Examples 1 to 4]

After mixing with the composition shown in Table 1 below, mixed and dissolved at room temperature (25° C.), filtered through a 0.2 μm Millipore filter to prepare a photosensitive resin composition, and the content unit of each component is parts by weight. After forming an organic insulating film by the method described in the evaluation method using each photosensitive resin composition, the sensitivity, resolution, and taper of each organic insulating film were evaluated, and the results are shown in Table 2 below.

photosensitive resin
composition Example comparative example One 2 3 4 5 6 One 2 3 4 Alkali Soluble Acrylate Resin 100 100 100 100 100 100 100 100 100 100 photopolymerizable compound 80 80 80 80 80 80 80 80 80 80 photopolymerization initiator 2 2 2 2 2 2 2 2 2 2 photosensitizer compound 1 0.5 One 2 One One One - - - - compound A - - - - - - - 0.5 One 2 Silane Coupling Agent 0.6 0.6 0.6 - 0.6 - 0.6 0.6 0.6 0.6 Surfactants 0.2 0.2 0.2 0.2 - - 0.2 0.2 0.2 0.2 menstruum 300 300 300 300 300 300 300 300 300 300

Alkali-soluble acrylate resin: styrene: methacrylic acid: glycidyl methacrylate is polymerized in a ratio of 40: 30: 30, a copolymer having a weight average molecular weight of 8,000

Photopolymerizable compound: Dipentaerythritolhexaacrylate (DPHA)

Photoinitiator: OXE-01 (manufactured by BASF)

Compound 1: 10-(3-(trimethoxysilyl)propyl)-2-chloroacridin-9(10H)-one

Compound A: 10-Butyl-2-chloroacridin-9 (10H) -one

Silane coupling agent: (3-acryloxypropyl) trimethoxysilane (manufactured by Shin-Etsu Silicone)

Surfactant: FZ-2122 (Dow Corning Toray Silicone Co.)

Solvent: propylene glycol monomethyl ether acetate (PGMEA, manufactured by Chemtronics)

photosensitive resin
composition Example comparative example One 2 3 4 5 6 One 2 3 4 Sensitivity (mJ/cm2) 18 17 17 17 17 17 23 21 25 27 Resolution (㎛) 4 3 3 3 3 3 7 6 5 7 taper 60 64 72 66 65 66 52 57 59 63

As shown in Table 2, the photosensitive resin composition of the present invention formed an insulating film having improved sensitivity and resolution and a high taper compared to Comparative Example 1 which did not contain a photosensitizer, and in particular, the photosensitive resin composition of the present invention was formed of an alkoxy High sensitivity of 17 to 18 by significantly increasing the photoinitiation efficiency of the initiator under the organic insulating film compared to Comparative Examples 2 to 4 using the other photosensitizer compound A due to the specific photosensitizer compound 1 in which silane is substituted at the terminal, 3 It was confirmed that it had a high resolution of 4 to 4 and a high taper of 60 or more. From this, it can be seen that the photosensitive resin composition of the present invention has superior sensitivity, resolution, and tapered pattern shape compared to Comparative Examples 1 to 4.

Therefore, the photosensitive resin composition of the present invention can produce a cut-off film with a remarkably increased aperture ratio by using a specific compound substituted with alkoxysilane at the terminal as a photosensitizer to exhibit high sensitivity, high resolution, and high taper, thereby making a clearer display can help

The present invention is not limited by the above-described embodiments and the accompanying drawings, and it is common in the art to which the present invention pertains that various substitutions, modifications and changes are possible within the scope without departing from the technical spirit of the present invention. It will be clear to those who have knowledge.

Claims (12)

1) alkali-soluble acrylate resin;
2) photopolymerizable compounds;
3) a photopolymerization initiator; and
4) a photosensitizer; and, wherein the photosensitizer is an aromatic or heteroaromatic compound substituted with an alkoxysilane or an alkylalkoxysilane at the terminal, the photosensitive resin composition. The method of claim 1,
The photosensitizer will have a structure showing a light absorption peak in the 380-450nm region, the photosensitive resin composition. 3. The method of claim 2,
The photosensitizer is tri (C1-C10) alkoxysilane, di (C1-C10) alkoxy (C1-C10) alkylsilane or di (C1-C10) at the end of the anthracene-based, benzophenone-based or acridone-based photosensitizer. ) Alkyl (C1-C10) alkoxysilane will be substituted, the photosensitive resin composition. 4. The method of claim 3,
The photosensitizer is represented by the following formula (1), the photosensitive resin composition.
[Formula 1]

In Formula 1,
L ₁ is C1-C10 alkylene or C3-C20 cycloalkylene;
R ₁ is C1-C10 alkyl or C1-C10 alkoxy;
R ₂ and R ₃ are each independently C1-C10 alkoxy;
R ₄ is hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl or halogen. 5. The method of claim 4,
The photosensitizer is selected from the following structures, the photosensitive resin composition.

The method of claim 1,
The alkali-soluble acrylate resin is a photosensitive resin composition which is a copolymer of an ethylene-based monomer and a monomer selected from an ethylene-based monomer having an acidic group. The method of claim 1,
The photopolymerizable compound is a polyfunctional monomer having an ethylenically unsaturated bond, the photosensitive resin composition. The method of claim 1,
The photopolymerization initiator is at least one photosensitive resin composition selected from an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, an imidazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime-based compound. The method of claim 1,
The photosensitive resin composition further comprising at least one selected from a silane coupling agent, a surfactant, and a solvent. The method of claim 1,
The photosensitive resin composition is based on 100 parts by weight of the alkali-soluble acrylate resin, 10 to 300 parts by weight of the photopolymerizable compound, 0.1 to 10 parts by weight of the photopolymerization initiator, and 0.01 to 10 parts by weight of the photosensitizer A photosensitive resin composition comprising . A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. An electronic device comprising the cured film according to claim 11 .