TWI617887B - Photosensitive resin composition and insulating layer prepared from the same - Google Patents

Abstract

A photosensitive resin composition and an insulating layer prepared using the photosensitive resin composition are disclosed. The photosensitive resin composition includes a binder resin polymerized by containing a monomer represented by Formula 1, and thus has excellent sensitivity and degradation ability, improved fluidity, which can be easily processed and controlled accordingly. The angle of the formed pattern.

Description

Photosensitive resin composition and insulating layer prepared from the same

The invention relates to a photosensitive resin composition having excellent sensitivity and degradation ability, and capable of controlling the angle of a pattern formed, and an insulating layer prepared by using the photosensitive resin composition.

Regarding display devices, such as thin-film transistor (TFT) liquid crystal display devices, inorganic protective layers (such as silicon nitride) have been traditionally used as protective films for protecting and insulating TFT circuits, however, due to their high dielectric constant This has involved difficulties in improving the aperture ratio. To overcome the above problems, there is a trend toward increasing the demand for organic insulating films having a low dielectric constant. As for the above-mentioned organic insulating film, a photosensitive resin formed of a polymer compound is generally used, and the polymer compound undergoes a chemical reaction by exposure to light or an electron beam to have different solubility for a specific solvent. In addition, the fine processing of the circuit pattern is performed by a change in polarity ("polar inversion") and a cross-linking reaction, which has occurred through a photoreaction of the organic insulating film. In particular, regarding the material used for the aforementioned organic insulating film, regarding a solvent, such as an alkaline solution, the solubility change after exposure can be used. The above-mentioned organic insulating films are generally classified into positive and negative films depending on the solubility of the photosensitive portion for development. The positive photoresist has a process of dissolving the exposed portion in the developer, and the negative photoresist has a process of dissolving the unexposed portion while the exposed portion is not dissolved in the developer to form a pattern. Among these, the positive type organic insulating film uses an alkaline solution and excludes the use of an organic developer typically used for a negative type organic insulating film. Therefore, it has an advantage in the working environment, and theoretically prevents unexposed The portion of UV becomes swelled to thereby improve the degradation ability. In addition, after the organic film is formed, the film can be easily removed using a release agent, and has the advantage of removing the organic film from the panel when a defective panel is generated during processing, thereby significantly improving the recoverability of the substrate. And reusability. Specifically, regarding the use of such an organic insulating film to form an insulating layer of a liquid crystal display device or the like, the aforementioned organic insulating layer must not only have excellent insulation, but also have relatively low thermal expansion, so that when it is coated Reduce the stress at the interface when layering the substrate. In addition, strong physical properties are required. In addition, the insulating layer or protective layer must form an interface between it and the metal or silicon compound. In this example, considering the reliability of the device, excellent interface adhesion is a very important factor. The insulating layer is micro-patterned to provide an interconnection path between circuits, and if the insulating layer is given photosensitivity, the traditional process of applying a replacement photoresist to the insulating layer to form a pattern can be ignored, Therefore, a micro pattern is easily formed. For this reason, as for the aforementioned positive-type organic insulating film composition, there has been intensive and active research on a composition to which a photosensitive compound (PAC) is added. The photosensitive compound provides a photosensitive adhesive including an acrylic fluorene-based photosensitive resin. Agent resin, the acryl fluorene-based photosensitive resin is represented by the binder resin, phenol resin, polyimide, siloxane, or the like. In addition, recently reached a stage where such an insulating film as described above has been commercially available, and this has led to the publication of various devices using the insulating film. An important feature required for the aforementioned organic insulating film is sensitivity. The improvement in sensitivity has led to a significant reduction in production time in the industrial process of the display device. In fact, in the current situation where the demand for liquid crystal display devices has increased significantly, sensitivity is considered to be one of the most important features of such organic insulating films as described above. However, most of the conventional organic insulating film compositions prepared using acrylic fluorene-based photosensitive resins and PACs lack sensitivity, and in particular, they often have shortcomings due to small differences in solubility between UV-irradiated parts and non-UV-irradiated parts. Degradability. For example, U.S. Patent No. 4,139,391 discloses a photosensitive resin-based organic insulating film composition that uses a copolymer of an acrylic fluorenyl compound and an acrylate compound as a binder resin, and uses an alternative acrylic An ester compound is prepared as a multifunctional monomer. However, since the difference in solubility between the exposed portion and the non-exposed portion is not large enough, the developing characteristics are relatively poor. In addition, the binder resin does not remain during development but is partially dissolved in the developer, thus causing a problem that it is difficult to obtain a micropattern having a size of 15 μm or less. Therefore, the conventional organic insulating film is insufficient to solve the problem about sensitivity. Although the sensitivity may be improved by increasing the solubility of the alkaline developer in the polymer used in the organic insulating film, or extending the development time, this method has limitations, and may cause the non-exposed portion to dissolve together with the exposed portion, causing Reduction of overall film residual rate. This result has caused problems in thin film coating and pattern damage in the substrates of large-scale displays. In addition, the organic insulating film composition requires various characteristics such as excellent processing resistance such as heat resistance, solvent resistance, resistance to prolonged heat burn, and the like; suitable adhesion to the support layer; The purpose of use is a wide range of process patterns that can be patterned under different processing conditions; and in addition, high sensitivity, high permeability, reduced film expansion after development, and loss caused by the developer, or the like.

Therefore, an object of the present invention is to provide a photosensitive resin having excellent sensitivity and degradation ability, and capable of controlling the angle (ie, the slope) of the pattern formed. Another object of the present invention is to provide a resin composition having appropriate chemical resistance and heat resistance required for post-treatment. Another object of the present invention is to provide an insulating layer prepared using the aforementioned photosensitive resin composition. To achieve the above object, the present invention provides the following. (1) A photosensitive resin composition including a binder resin polymerized by containing a monomer represented by Formula 1:

(Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R _{4 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or Can be coupled to form a ring having 3 to 8 carbon atoms; and m is an integer ranging from 1 to 6). (2) The composition according to the above item (1), wherein the binder resin is polymerized by further including at least one of the monomers represented by the molecular formulas 2 to 5:

(Where R is an alkyl group having 1 to 6 carbon atoms, the 1 to 6 carbon atoms being substituted or unsubstituted by an alkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or An alkyl group of 1 to 6 carbon atoms, the 1 to 6 carbon atoms being substituted or unsubstituted by an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms);

(Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms);

(Where R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 8 carbon atoms, R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms );

(Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkylene group having 1 to 6 carbon atoms or a cyclic alkylene group having 4 to 8 carbon atoms, and R ₃ is an alkane having 1 to 6 carbon atoms Or a cycloalkyl group having 4 to 8 carbon atoms). (3) The composition according to the above item (1), wherein the binder resin is polymerized with a monomer represented by Formula 1 containing 5 to 60 mole%. (4) The composition according to the above item (1), wherein the binder resin has a weight average molecular weight of 5,000 to 30,000. (5) The composition according to the above item (1), wherein the binder resin is included in an amount of 5 to 60% by weight relative to the total weight of the composition. (6) The composition according to the above item (1), further comprising a photoacid generator, a photosensitizer, and a solvent. (7) The composition according to the above item (6), wherein the photoacid generator is Selected from the group consisting of diazonium salts, sulfonium salts, sulfonium salts, iodonium salts, sulfonium imines, sulfonic acid oximes, dihydrazones, dihydrazones, o-nitrobenzylbenzenesulfonates and triazine compounds Make up at least one of the groups. (8) The composition according to the above item (6), wherein the photoacid generator is included in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the binder resin. (9) The composition according to the above item (6), wherein the photosensitizer is selected from the group consisting of a polynuclear aromatic, xanthan, xanthone, cyanine, oxacyanine, thiazine, acridine, acryl At least one of the group consisting of pyridone, anthraquinone, squalenium, styryl, base styryl, coumarin and anthracene compounds. (10) The composition according to the above item (6), wherein the photosensitizer is included in an amount of 0.01 to 60 parts by weight relative to 100 parts by weight of the binder resin. (11) The composition according to the above item (6), wherein the solvent is at least one selected from the group consisting of ether, acetate, ester, ketone, amidine, and lactone. (12) The composition according to the above item (6), wherein the solvent is propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof. (13) The composition according to the above item (6), wherein the solvent is included in an amount of 40 to 90% by weight relative to the total weight of the composition. (14) The composition according to the above item (1), further comprising a member selected from the group consisting of a basic compound, a surfactant, an adsorption enhancer, a thermal crosslinking agent, a light stabilizer, a light curing enhancer, and an anti-halation agent And at least one of the groups of antifoaming agents. (15) An insulating layer prepared by curing the photosensitive resin composition according to any one of the items (1) to (14) above. (16) A liquid crystal display device including the insulating layer according to the above item (15). The photosensitive resin composition of the present invention has excellent sensitivity and degradability, and improved fluidity, thereby allowing easy handling and controlling the angle of the formed pattern. The photosensitive resin composition of the present invention has excellent electrical characteristics, as well as superior chemical resistance and thermal resistance.

The invention discloses a photosensitive resin composition and an insulating layer prepared from the photosensitive resin composition. The photosensitive resin composition includes a binder resin polymerized by including a monomer represented by Formula 1, and therefore has excellent sensitivity. As well as degradability and improved fluidity, it can then be easily handled, and the angle of the formed pattern can be controlled. Hereinafter, the present invention will be described in more detail. The photosensitive resin composition of the present invention may include a binder resin polymerized by including a monomer represented by Formula 1. This binder resin can be polymerized by containing a monomer represented by the following molecular formula 1.

Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R _{4 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or may be Coupled to form a ring having 3 to 8 carbon atoms; and m is an integer ranging from 1 to 6). The monomer represented by Formula 1 has an oxygen atom adjacent to R _2. If the oxygen atom is contained in a chain, the rotation radius of the single bond becomes larger to reduce the glass transition temperature and improve the fluidity, so it can be easily To deal with. In Formula 1, the length of the monomer can be controlled by adjusting "m", so the angle of the formed pattern is controlled. In this example, reducing the angle of the formed pattern can prevent separation or cracking of the cured film from occurring during the deposition of the transparent electrode. Regarding the binder resin according to the present invention, depending on the specific monomer type, since the monomer represented by Formula 1 can be mixed and copolymerized with other monomers as desired, its content and mixing ratio are not particularly limited. However, in terms of improving transparency and easy handling, and controlling the pattern angle to maximize the effect of preventing cracks in the cured film during the deposition of the transparent electrode, the monomer represented by Formula 1 preferably includes and is polymerized at 5 to 60%. The amount of ears. The binder resin according to the present invention can be prepared by copolymerizing a monomer represented by Formula 1 and any other monomer known in the art and used for the binder resin. For example, the copolymerization may be performed by further including at least one of the monomers represented by the following formulae 2 to 5. The compound represented by the molecular formula 2 may act to improve the hardness, and the compound represented by the molecular formulas 3 to 5 may improve the permeability. [Molecular Formula 2]

(Where R is an alkyl group having 1 to 6 carbon atoms, the 1 to 6 carbon atoms being substituted or unsubstituted by an alkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or, having 1 to 6 Alkyl group of 1 to 6 carbon atoms, the 1 to 6 carbon atoms being substituted or unsubstituted by an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms).

(Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms).

(Where R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 8 carbon atoms, R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms ). [Molecular Formula 5]

(Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkylene group having 1 to 6 carbon atoms or a cyclic alkylene group having 4 to 8 carbon atoms, and R ₃ is an alkane having 1 to 6 carbon atoms Or a cycloalkyl group having 4 to 8 carbon atoms). Alternatively, the binder resin of the present invention may be copolymerized by further including an acrylate monomer generally used in the technical field. If acrylate monomers are known and generally used in the art, their kind is not particularly limited, however, they may include, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethyl alcohol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Ester, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, Cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, dodecyl (meth) acrylate, Octadecyl (meth) acrylate, Ethoxyethyl (meth) acrylate, Phenyl (meth) acrylate, 2-Hydroxyethyl (meth) propylene Ester, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate , 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (methyl ) Acrylate, Diethylene glycol monophenyl ether (meth) acrylate, Triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, β-phenoxy Ethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, cyclofentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl Alkenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromo Phenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, or the like, which is used alone or in combination of two or more thereof. The adhesive resin of the present invention may have a weight average molecular weight in a range of 5,000 to 30,000 in maintaining excellent resolution and / or pattern flow characteristics during pattern formation. If the binder resin is within the range in which it can function as desired, the content of the binder resin is not particularly limited, but may range from 5 to 60% by weight relative to the total weight of the composition, and is preferably 10 to 40% by weight. With respect to the total weight of the composition, when the binder resin is included in an amount of 5% to 60% by weight, the effect of improving sensitivity and degrading ability can be maximized while having appropriate viscosity. In addition to the aforementioned binder resin, the photosensitive resin composition of the present invention may further include a photoacid generator ("PAG"), a photosensitizer, and a solvent, which are generally used in the application of a chemical radiation-increasing photoresist resin composition. PAG is a compound that emits excitation light or radiation to produce an acid. The kind of PAG is not particularly limited, but may include, for example, a diazonium salt, a sulfonium salt, a sulfonium salt, an iodonium salt, a sulfonyliminobenzenesulfonate, an oxime benzenesulfonate, a diazonium, dihydrazone, An o-nitrobenzylbenzenesulfonate or triazine compound, or the like, is used alone or in combination of two or more thereof. The content of PAG is not particularly limited if PAG is within a range in which it can function as desired, but it may range from 0.1 to 20 parts by weight, and preferably from 0.5 to 10, relative to 100 parts by weight of the binder resin. Weight points. When the PAG is included in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the binder resin, the chemical modification due to the catalytic reaction of the acid can be completely performed, and when the composition is applied, the composition Can be spread evenly. The photosensitizer can absorb the excitation light or radiation under the condition that the electrons become excited, and contact the PAG to cause energy and electron transfer, heat generation, or the like, thereby accelerating the degradation of the PAG to thereby improve sensitivity. . If photosensitizers can accelerate the degradation of PAGs, their types are not particularly limited, but may include, for example, selected from polynuclear aromatics, ox shallots, xanthones, cyanine pigments, oxacyanines, thiazines, acridines , Acridone, anthraquinone, squalenyl, styryl, base styryl, coumarin, anthracene compounds, alone or in combination of two or more While using. Among the aforementioned compounds, the photosensitizer may be a compound having an absorption wavelength in a bandwidth range of 350 to 450 nm. The type of the polynuclear aromatic compound is not particularly limited, but may include, for example, pyrene, pyrene, triphenylene, anthracene, or the like. The kind of xanthan compounds is not particularly limited, but may include, for example, luciferin, eosin, erythromycin, rose red B, bengal rose red, or the like. The kind of xanthone compound is not particularly limited, but may include, for example, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, or the like. The kind of cyanine pigment compound is not particularly limited, but may include, for example, thiocyanine, oxacyanine, merocyanin, mesocyanin, rhodamine, or the like. The kind of the thiazine compound is not particularly limited, but may include, for example, thiazide, methylene blue, toluidine blue, or the like. The kind of acridine compound is not particularly limited, but may include, for example, acridine orange, chloroflavin, acridine flavin, or the like. The kind of acridone compound is not particularly limited, but may include, for example, acridone, 10-butyl-2-chloroacridone, or the like. The kind of the coumarin compound is not particularly limited, but may include, for example, 7-diethylamino-4-methylcoumarin. If the photosensitizer is within a range in which it can act as desired, the content of the photosensitizer is not particularly limited, but it may be in the range of 0.01 to 60 parts by weight relative to 100 parts by weight of the binder resin, and is preferably 0.02 to 40 weight points. When the photosensitizer is included in an amount of 0.01 to 60 parts by weight relative to 100 parts by weight of the binder resin, the binder resin may have appropriate sensitivity and transparency at the same time. If the solvent can dissolve the aforementioned ingredients, the kind of solvent used herein is not particularly limited, but any solvent having a suitable drying rate and forming a uniform and smooth coating film after the solvent is volatilized can be used. Specific examples of the solvent may include ethers, acetates, esters, ketones, fluorimines, and lactones, which are used alone or in a combination of two or more. Specific examples of ethers may include: ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like; ethylene glycol two Alkyl ethers, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, etc .; propylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, etc .; propylene glycol dialkyl ethers, such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .; diethylene glycol dialkyl ether, Such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .; dipropylene glycol monoalkyl ethers, such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoether Propylene ether, dipropylene glycol monobutyl ether, and the like; and dipropylene glycol dialkyl ethers, such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, and the like. Specific examples of acetate may include: ethylene glycol monoalkyl ether acetate, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether Ether acetates, etc .; propylene glycol monoalkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc .; diethylene glycol Monoalkyl ether acetates, such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, and the like; And dipropylene glycol monoalkyl ether acetates, such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, and the like. Specific examples of esters may include: lactates such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, Etc .; aliphatic carboxylic acid esters, such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propionate Propyl, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, butyl Isobutyl ester, etc .; other esters, such as ethyl glycolate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate Ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxy Butyl butyrate, methyl ethyl acetate, ethyl ethyl acetate, cellulose methyl ester, cellulose Retyl ethyl ester, diethylene glycol methyl ethyl ester, or the like. Specific examples of ketones may include methyl ethyl ketone, methyl acetone, methyl n-butanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, or the like. Specific examples of amidine may include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone , Or whatever. Specific examples of lactones may include gamma-butyrolactone, or the like. Regarding the applicability and uniformity of the film thickness of the insulating coating film, the solvent may be propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof. The content of the solvent is not particularly limited if the solvent is within a range in which it can function as desired, but may range from 40 to 90% by weight, and preferably from 50 to 80, relative to the total weight of the composition. weight%. When the solvent is included in an amount of 40% to 90% by weight relative to the total weight of the composition, the solid content and the viscosity can be maintained to a desired level, thereby improving the coating efficiency. The photosensitive resin composition of the present invention may further include additives in an appropriate amount without departing from the purpose of the present invention, such as a basic compound, a surfactant, an adsorption enhancer, a thermal crosslinking agent, a light stabilizer, a light curing enhancer, Anti-halo agents (leveling agents) or defoamers, or the like. The kind of the basic compound is not particularly limited, but may include any one selected from the group consisting of compounds for use as a chemically amplified photoresist. Specific examples of the basic compound may include an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, or the like, alone or in combination of two or more thereof. use. Specific examples of the aliphatic amine may include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexane Amine, dicyclohexylmethylamine, or the like. Specific examples of the aromatic amine may include aniline, benzylamine, N, N-dimethylaniline, diphenylamine, or the like. Specific examples of heterocyclic amines may include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, tobacco Alkaline acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1 , 5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, or the like. Specific examples of the quaternary ammonium hydroxide may include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, or the like. Specific examples of the quaternary ammonium carboxylic acid salt may include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, or the like. If the basic compound is within a range in which it can function as desired, the content of the basic compound is not particularly limited, but it may be in the range of 0.0001 to 1 part by weight relative to 100 parts by weight of the binder resin, and more It is preferably 0.004 to 0.5 weight part. When the basic compound is included in an amount of 0.0001 to 1 part by weight relative to 100 parts by weight of the binder resin, an interlayer insulating layer having appropriate sensitivity and maintaining stability can be formed. The surfactant is a composition that improves the adhesion between the matrix and the photosensitive resin composition. The type of surfactant is not particularly limited, but may include various surfactants, such as fluorine-containing surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, and silicon surfactants, or the like, They are used alone or in combination of two or more thereof. Specific examples of fluorine-containing surfactants may include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (trade names, by DIC Corporation), FLUORAD FC430, FC431, and FC171 (trade names, manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC- 383, S393, and KH-40 (trade names, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE 20000 (trade names, manufactured by Lubrizol Japan Limited), or the like. Specific examples of non-ionic surfactants may include glycerol, trimethylolpropane, and trimethyloleane, and their ethoxylates or propoxylates (eg, glycerol propoxylate or glycerol ethoxylate) ); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Alcohol distearate, sorbitan fatty acid esters, such as PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2, and TETRONIC 304, 701, 704, 901, 904, and 150R1 (trade names, by BASF Manufacturing), or whatever. Specific examples of the cationic surfactant may include a titanium cyanine-modified compound such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), an organosiloxane polymer such as KP341 (trade name, manufactured by Shin- (Made by Etsu Chemical Co., Ltd.), (meth) acrylic (co) polymers, for example, POLYFLOW No. 75, No. 90, No. 95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (trade name , Manufactured by Yusho Co., Ltd.), or the like. Specific examples of the anionic surfactant may include W004, W005, W017 (trade names, manufactured by Yusho Co., Ltd.), or the like. Specific examples of silicon surfactants may include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 (trade names, manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, 323, and 330 (trade names, manufactured by BYK Chemie Manufacturing), or whatever. If the surfactant is within the range in which it can function as desired, the content of the surfactant is not particularly limited, but it may be in the range of 0.001 to 3 parts by weight relative to 100 parts by weight of the binder resin. It is preferably 0.001 to 2 parts by weight. When the surfactant is included in an amount of 0.001 to 3 parts by weight relative to 100 parts by weight of the binder resin, the effect of improving the adhesion between the substrate and the resin composition and / or the coating effect can be maximized. Effect. Adsorption enhancers can improve the adhesion between the insulating layer and the inorganic materials of the substrate, such as silicon compounds such as silicon, silicon oxide, silicon nitride, etc., or metals such as gold, copper, aluminum, etc., and There may be a taper angle for adjusting to the substrate. The kind of the adsorption enhancer is not particularly limited, and specific examples thereof may include a silane coupling agent or a thiol compound, and a silane coupling agent is preferred. The type of the silane coupling agent is not particularly limited, but may include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriane Oxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacrylfluorenyloxypropyltrialkoxysilane, γ-methacrylfluorenyloxypropylane Dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, ethylene Trialkoxysilane, or the like, is preferably γ-glycidoxypropyltrialkoxysilane or γ-methacrylmethyloxypropyltrialkoxysilane, and more preferably , Γ-glycidoxypropyltrialkoxysilane. These may be used alone or in combination of two or more thereof. If the adsorption enhancer is within the range in which it can function as desired, the content of the adsorption enhancer is not particularly limited, but may range from 0.1 to 20 parts by weight relative to 100 parts by weight of the binder resin, preferably It is 0.5 to 10 parts by weight. When the adsorption enhancer is included in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the binder resin, the adhesion to the insulating layer can be maximized. When the insulating layer is formed using the foregoing composition, a thermal crosslinking agent may make it possible to actively perform a crosslinking reaction via UV irradiation and heat treatment, and is a component for improving thermal resistance. The type of the thermal cross-linking agent is not particularly limited, but may include, for example, polyacrylate resin, epoxy resin, phenol resin, melamine resin, organic acid, amine compound, anhydrous compound, or the like, alone or in combination Or more in combination. If the thermal cross-linking agent is within the range in which it can function as desired, the content of the thermal cross-linking agent is not particularly limited, but it may be in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the binder resin. More preferably, it is 0.1 to 3 parts by weight. When the thermal cross-linking agent is included in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the binder resin, the improvement in thermal resistance can be 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, but may include, for example, benzotriazole, triazine, diphenylmethanone, hindered amino ether or hindered amine compound, or the like, which may be used alone or in combination with two or more thereof. Use in combination. The content of the light stabilizer is not particularly limited if the light stabilizer is within a range in which it can function as desired, but it may be in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the binder resin. It is preferably 0.1 to 3 parts by weight. When the light stabilizer is included in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the binder resin, the improvement in light resistance can be maximized. As described above, the photosensitive resin composition formed according to the present invention has excellent sensitivity and degradation ability, and can control the angle of the formed pattern. The present invention can further provide an insulating layer prepared using the above composition. The method for preparing an insulating layer according to the present invention may include applying the photosensitive resin composition of the present invention to a top side of a substrate for a display device or a source / drain or a silicon nitride layer provided on the substrate. The top side of the substrate; pre-baking the photosensitive resin composition; selectively exposing and developing the photosensitive resin composition to form a pattern; and fully exposing and heating, or heating only the photosensitive resin composition. The substrate may be prepared using glass or transparent plastic resin as a main material. The glass or transparent plastic resin is generally used for manufacturing a liquid crystal display device, an organic EL display, or the like. However, this material is not particularly limited, but may depend on the characteristics of the display device to be used. For example, a metal thin film may be provided to form a gate electrode on an insulating substrate, such as a glass plate, and the metal thin film may form a surface layer thereof. The method of applying the photosensitive resin composition to the top side of a substrate or the like is not particularly limited, but may include, for example, a spray coating, a roll coating, a slit nozzle coating, such as a spray nozzle type coating, a spin Coating, such as spin-on-center application, extrusion coating, stick coating, or the like. In addition, two or more of the aforementioned coating processes may be combined and used. The thickness of the applied film varies depending on the coating method, the solid content of the composition, the viscosity, or the like, however, coating is generally performed to achieve a film thickness of 0.5 to 100 μm after drying. As a subsequent process, pre-baking is a process of volatilizing a solvent by applying vacuum, infrared, or heat to obtain a coating film having no fluidity after forming the coating film. The heating conditions differ depending on the type of individual components or a combination thereof. For example, a heating plate may be heated at 60 to 130 ° C for 5 to 500 seconds, and a heating oven may be heated at 60 to 140 ° C for 20 to 1,000 seconds. Next, when irradiating excimer laser, far UV light, UV light, visible light, electron beam, X-ray or g-ray (with a wavelength of 436 nm), i-ray (with a wavelength of 365 nm), h-ray (with 405 nm Wavelength) or a combination thereof, selective exposure can be performed. The exposure may be performed by a contact, proximity, or projection exposure process or the like. According to the present invention, after the alkaline development, the photosensitive resin composition may be completely exposed and heated (high-temperature firing) or only heated (high-temperature firing). In the case of high-temperature firing, the photosensitive resin composition may have a composition configuration including a thermal crosslinking agent or the like. Heating may be performed using a heating device such as a hot plate or an oven at 150 to 350 ° C for 10 minutes to 3 hours. After heating, a complete cross-linking and curing pattern can be created. Hereinafter, preferred embodiments will be described in order to understand the present invention more specifically. However, it will be apparent to those skilled in the art that this specific embodiment is provided for the purpose of illustration, and there are no specific restrictions on the accompanying patent application model, and various modifications and alternatives are possible without Such modifications and alternatives deviate from the scope and spirit of the invention and are fully included in the invention as defined by the scope of the accompanying patent application. EXAMPLES Examples 1 to 8 and comparative examples prepared spin coating compositions with their corresponding contents (% by weight) by using the ingredients listed in Table 1.

[Table 1]

Experimental Examples Regarding the resin compositions prepared according to the examples and comparative examples, the following experiments for evaluation have been performed, and the results are shown in Table 2 below. (1) Sensitivity Each photosensitive resin composition according to Examples 1 to 8 and Comparative Examples was coated on a glass substrate (Corning 1737, manufactured by Corning Co.) having a thickness of 0.7 mm, and then on a hot plate on The glass substrate was heated at 100 ° C. for 125 seconds to evaporate the solvent, and thus a photosensitive resin composition layer having a thickness of 4.0 μm was formed. Thereafter, in order to obtain a contact hole pattern having a diameter of 10 μm, exposure was performed by using a mask having a square pattern opening having a size of 10 μm and using an i-ray stepper (NSR-205i11D, manufactured by Nikon Co.). . After exposure, the substrate was subjected to immersion development at 23 ° C for 40 seconds using a 2.38% tetramethylammonium hydroxide solution as a developer, and then the substrate was heated in an oven at 230 ° C for 30 minutes, thereby obtaining a cured film. The obtained pattern of the contact hole was cut vertically, and the exposure value (EV) at which a 10 μm contact hole was obtained was defined as the sensitivity in each constituent composition. (2) Pattern angle After cutting the obtained pattern vertically, the angle from the pattern to the substrate is calculated from the corresponding optical photograph. (3) Transparency Using a spectrometer, measure the transparency at 400 nm.

[Table 2]

Referring to Table 2 above, it was confirmed that the insulating layer prepared using each photosensitive resin composition according to Examples 1 to 8 had excellent sensitivity and high transparency. In addition, because of the low pattern angle (that is, the low slope of the pattern), the occurrence of separation or cracking of the cured film can be prevented during the deposition of the transparent electrode as a subsequent process. On the other hand, it was found that the insulating layer prepared using the composition according to the comparative example has poor sensitivity, low transparency, and high pattern angle, and therefore, may cause defects during the deposition of the transparent electrode.

no

The above and other objects, features, and other advantages of the present invention will be more clearly understood from the following detailed description in conjunction with accompanying drawings, in which: Figure 1 shows the preparation using the photosensitive resin composition in Example 3 Photograph of the pattern angle of the insulating layer to the substrate; Figure 2 is a photograph showing the pattern angle of the insulating layer to the substrate prepared using the photosensitive resin composition in Example 4; Figure 3 is a photograph showing the photosensitivity in Example 8 Photograph of pattern angle of insulating layer to substrate prepared by resin composition; FIG. 4 is a photograph showing pattern angle of insulating layer to substrate prepared using photosensitive resin composition in Comparative Example 1. FIG.

no

Claims (16)

A positive-type photosensitive resin composition comprising: a binder resin polymerized by including a monomer represented by Formula 1; a photoacid generator; and a solvent, (Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrocarbon group having 1 to 6 carbon atoms; R ₃ and R _{4 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms Or may be coupled to form a ring having 3 to 8 carbon atoms; and m is an integer ranging from 1 to 6). The composition according to item 1 of the scope of patent application, wherein the binder resin is polymerized by further including at least one of the monomers represented by the molecular formulas 2 to 5: (Wherein R is a monoalkyl group having 1 to 6 carbon atoms, the 1 to 6 carbon atoms being substituted or unsubstituted by a monoalkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or, having An alkyl group of 1 to 6 carbon atoms, which is substituted or unsubstituted by an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms; (Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is a monoalkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms); (Where R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrocarbylene group having 3 to 8 carbon atoms, R ₃ is an alkyl group having 1 to 6 carbon atoms or having 4 to 8 carbon atoms Cycloalkyl); (Where R ₁ is a hydrogen atom or a methyl group, and R ₂ is a monoalkylene group having 1 to 6 carbon atoms or a cyclic alkylene group having 4 to 8 carbon atoms, and R ₃ is a group having 1 to 6 carbon atoms Monoalkyl or cycloalkyl having 4 to 8 carbon atoms). The composition according to item 1 of the patent application range, wherein the binder resin is polymerized by containing 5 to 60 mol% of a monomer represented by Formula 1. The composition according to item 1 of the patent application range, wherein the binder resin has a weight average molecular weight of 5,000 to 30,000. The composition according to item 1 of the patent application range, wherein the binder resin is included in an amount of 5 to 60% by weight relative to the total weight of the composition. The composition according to item 1 of the patent application scope further comprises a photosensitizer. The composition according to item 1 of the scope of patent application, wherein the photoacid generator is selected from the group consisting of a diazonium salt, a sulfonium salt, a sulfonium salt, an iodonium salt, a sulfonimide sulfonate, an oxime benzenesulfonate, At least one of the group consisting of aziridine, dihydrazone, o-nitrobenzylbenzenesulfonate and triazine compound. The composition according to item 1 of the scope of patent application, wherein the photoacid generator is included in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the binder resin. The composition according to item 6 of the scope of patent application, wherein the photosensitizer is selected from the group consisting of polynuclear aromatic, xanthan, xanthone, cyanine, oxacyanine, thiazine, acridine, acridone, At least one of the group consisting of anthraquinone, squalinium, styryl, base styryl, coumarin, and anthracene compound. The composition according to item 6 of the patent application range, wherein the photosensitizer is included in an amount of 0.01 to 60 parts by weight relative to 100 parts by weight of the binder resin. The composition of claim 1, wherein the solvent is at least one selected from the group consisting of ether, acetate, ester, ketone, amidine, and lactone. The composition according to item 1 of the application, wherein the solvent is propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof. The composition according to item 1 of the patent application range, wherein the solvent is included in an amount of 40 to 90% by weight relative to a total weight of the composition. The composition according to item 1 of the scope of patent application, further comprising a member selected from the group consisting of a basic compound, a surfactant, an adsorption enhancer, a thermal cross-linking agent, a light stabilizer, a light curing enhancer, an anti-halation agent, and a consumer. At least one of the groups of foaming agents. An insulating layer is prepared by curing the photosensitive resin composition according to any one of claims 1 to 14 of the patent application scope. A liquid crystal display device includes the insulating layer according to item 15 of the scope of patent application.