TWI748065B - Positive photosensitive resin composition, display element thereof and method for forming patterns of display element thereof - Google Patents

Abstract

所述化學式1的R₁ 、化學式2的R₃ 分別獨立地為氫原子或1,2-醌二疊氮類磺酸酯，化學式1的R₂ 、化學式2的R₄ 分別獨立地表示氫原子或碳數為1至20的烴基，所述R₁ 、R₃ 中的至少一個為1,2-醌二疊氮類磺酸酯。The present invention relates to a positive photosensitive resin composition. More specifically, it relates to a) a 1,2-quinonediazide compound of the following chemical formula 1 or 2; b) an acrylic copolymer; c) a silane coupling agent ; And d) the solvent-based positive photosensitive resin composition:

The chemical formula of R 1 _1, R 2 of formula ₃ are each independently a hydrogen atom or a 1,2-quinone diazide sulfonic acid ester type, the chemical formula R 1 ₂ of the formula R ₄ 2 are independently a hydrogen atom Or a hydrocarbon group having 1 to 20 carbon atoms _{, and at least one of R 1} and R ₃ is a 1,2-quinonediazide sulfonate.

Description

Positive photosensitive resin composition, its display element and its pattern forming method

The present invention relates to a positive photosensitive resin composition, a display element and a pattern forming method of the display element (POSITIVE PHOTOSENSITIVE RESIN COMPOSITION, DISPLAY ELEMENT THEREOF AND METHOD FOR FORMING PATTERNS OF DISPLAY ELEMENT THEREOF), and more specifically, it relates to an excellent Resolution, curing process range, heat discoloration resistance, heat resistance, etc., especially with excellent sensitivity, transparency, and significantly improved adhesion, suitable for forming liquid crystal displays (LCD) and organic light emitting diodes (OLED) manufacturing processes Photosensitive resin compositions such as the interlayer insulating film, Pixel Define Layer (PDL), and Column Spacer.

Generally, flat panel displays are currently widely used displays, including liquid crystal displays (LCD) and organic light emitting diodes (Organic light emitting display: OLED).

In the manufacturing process of thin-film transistor (TFT) type liquid crystal displays and organic light-emitting diodes, interlayer insulating films are used to insulate between wirings arranged between layers.

In particular, with the recent development of high-speed response, high-resolution devices (Device), wiring technology with high aperture ratio and low resistance is required. For this reason, there is a tendency to increase the height difference of thin film transistors by reducing the width of the circuit and forming a high thickness. In this case, the thickness of the interlayer insulating film applied for flatness increases, but this causes a decrease in sensitivity and transparency, and thus decreases the productivity and quality of the panel. Therefore, there is an urgent need to develop insulating films with excellent sensitivity and transparency.

Therefore, the purpose of the present invention is to provide excellent resolution, curing process range, heat discoloration resistance, heat resistance, especially excellent sensitivity, transparency, and significantly improved adhesion, suitable for forming liquid crystal displays and organic The photosensitive resin composition of the interlayer insulating film, the pixel defining layer, the column spacing, etc. in the manufacturing process of the light emitting diode.

Furthermore, another object of the present invention is to provide a liquid crystal display and an organic light emitting diode substrate including a cured product of the photosensitive resin composition.

In addition, another object of the present invention is a method for forming a pattern of a display substrate using the photosensitive resin composition.

所述化學式1的R₁ 分別獨立地為氫原子或1,2-醌二疊氮類磺酸酯，R₂ 分別獨立地表示氫原子、碳數為1至20的烴基，R₁ 中的至少一個為1,2-醌二疊氮類磺酸酯。 化學式2：

所述化學式2的R₃ 分別獨立地為氫原子或1,2-醌二疊氮類磺酸酯，R₄ 分別獨立地表示氫原子、碳數為1至20的烴基，R₃ 中的至少一個為1,2-醌二疊氮類磺酸酯。In order to achieve the above-mentioned object, the present invention provides a 1,2-quinonediazide compound of the following chemical formula 1 or 2; b) acrylic copolymer; c) silane coupling agent; and d) solvent The photosensitive resin composition. Chemical formula 1:

In the chemical formula 1, R _{1 is} each independently a hydrogen atom or 1,2-quinonediazide sulfonate, R _{2 is} each independently a hydrogen atom and a hydrocarbon group having 1 to 20 carbons, and at least _{R 1 is} One is 1,2-quinonediazide sulfonate. Chemical formula 2:

_{R 3 of} the chemical formula 2 is each independently a hydrogen atom or 1,2-quinonediazide sulfonate, R ₄ each independently represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 20, and at least _{R 3} One is 1,2-quinonediazide sulfonate.

The positive photosensitive resin composition used in the present invention has excellent resolution, curing process range, heat discoloration resistance, heat resistance, especially excellent sensitivity and permeability, so it can provide a significant increase in adhesion and is suitable for A photosensitive resin composition for forming the interlayer insulating film, the pixel defining layer, and the column spacing in the manufacturing process of liquid crystal displays and organic light emitting diodes. In addition, a liquid crystal display and an organic light-emitting diode substrate including a cured product of the photosensitive resin composition, and a pattern formation method of a display substrate using the photosensitive resin composition are provided. The pattern can be used as a thin film field effect transistor liquid crystal display (TFT-LCD), a touch screen panel (TSP, Touch Screen Panel), an organic light emitting diode, an organic thin film field effect transistor (O-TFT), an electrophoretic display (EPD), an electric Materials such as passivation insulating film, gate insulating film, planarization film, column spacer, diaphragm, etc. of wetted display (EWD).

Hereinafter, the present invention will be described in detail.

The present invention relates to a photosensitive resin composition that can be used in various fields such as interlayer insulating films, passivation insulating films, gate insulating films, protective films, column spacers, pixel defining layers, diaphragms, etc., arranged between layers of liquid crystal displays, organic light emitting diodes, etc. Things.

所述化學式1的R₁ 分別獨立地為氫原子或1,2-醌二疊氮類磺酸酯，R₂ 分別獨立地為氫原子、碳數為1至20的烴基，較佳地，表示碳數為1至20的烷基或碳數為6至20的芳香族基，更佳地，表示碳數為1至15的烷基或碳數為6至15的芳香族基，所述R₁ 中的至少一個為1,2-醌二疊氮類磺酸酯。 化學式2：

所述化學式2的R₃ 分別獨立地為氫原子或1,2-醌二疊氮類磺酸酯，R4分別獨立地為氫原子、碳數為1至20的烴基，較佳地，表示碳數為1至20的烷基或碳數為6至20的芳香族基，更佳地，表示碳數為1至15的烷基或碳數為6至15的芳香族基，所述R₃ 中的至少一個為醌二疊氮類磺酸酯。The positive photosensitive resin composition of the present invention includes: a) a 1,2-quinonediazide compound of the following chemical formula 1 or 2; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent . Chemical formula 1:

In the chemical formula 1, R _{1 is} each independently a hydrogen atom or 1,2-quinonediazide sulfonate, and R _{2 is} each independently a hydrogen atom and a hydrocarbon group with a carbon number of 1 to 20, which preferably represents An alkyl group having 1 to 20 carbons or an aromatic group having 6 to 20 carbons, more preferably, an alkyl group having 1 to 15 carbons or an aromatic group having 6 to 15 carbons, said R ₁ in at least one of 1,2-quinonediazide sulfonic acid ester type. Chemical formula 2:

_{R 3 of} the chemical formula 2 is each independently a hydrogen atom or 1,2-quinonediazide sulfonate, and R4 is each independently a hydrogen atom and a hydrocarbon group with a carbon number of 1 to 20, and preferably represents carbon An alkyl group having 1 to 20 or an aromatic group having 6 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons or an aromatic group having 6 to 15 carbons, said R ₃ At least one of them is quinonediazide sulfonate.

The 1,2-quinonediazide compound represented by the chemical formula 1 or the chemical formula 2 of a) used in the present invention is used as a photosensitive compound (Photo Active Compound: PAC), as 1 of the chemical formula 1 or chemical formula 2 Specific examples of ,2-quinonediazide sulfonate include 1,2-quinonediazide-4-sulfonate, 1,2-quinonediazide-5-sulfonate, 1,2 -Quinonediazide-6-sulfonate etc., as a more specific example, is 1,2-quinonediazide-5-sulfonate having a structure of the following chemical formula 3 (* means a bonding portion). The 1,2-quinonediazide compound releases nitrogen molecules during exposure to generate carboxylic acid groups in the molecule, thereby improving the solubility of the photosensitive resin film in the alkali developer solution, and suppressing the alkalinity of the photosensitive resin film in the unexposed areas Solubility, thus, a positive pattern can be formed. Chemical formula 3:

For example, the 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2 is prepared by reacting a 1,2-quinonediazide-5-sulfonic acid halogen compound with a phenol compound under a weak base condition. become.

Relative to 100 parts by weight of b) acrylic copolymer, it contains 5 to 50 parts by weight of the 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2, preferably 10 to 40 parts by weight The 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2, more preferably, contains 15 to 30 parts by weight of the 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2. When its content is less than 5 parts by weight, it is difficult to form a pattern because the difference between the solubility of the exposed part and the solubility of the non-exposed part becomes small. When the content is more than 50 parts by weight, when light is irradiated in a short time , A large amount of unreacted 1,2-quinonediazide sulfonate compound remains, and there is a problem that it is difficult to develop due to the excessively low solubility in the alkaline aqueous solution as the developer.

The above-mentioned b) acrylic copolymer of the present invention is prepared by reacting as monomers i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or their mixture, ii) epoxy group-containing unsaturated compound, and iii) olefins The unsaturated compound is prepared by polymerization. For example, an acrylic copolymer can be prepared by radically reacting the above-mentioned monomers in the presence of a solvent and a polymerization initiator.

As the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or their mixture in i), unsaturated monocarboxylic acid such as acrylic acid and methacrylic acid; maleic acid , Fumaric acid, citraconic acid, methaconic acid, itaconic acid and other unsaturated dicarboxylic acids; or anhydrides of their unsaturated dicarboxylic acids, etc. It is used alone or in combination of two or more. In particular, acrylic acid, methacrylic acid, or anhydrous maleic acid is more preferable for copolymerization reactivity and solubility in an alkaline aqueous solution as a developer.

Relative to the total monomers, it contains 5 to 40 parts by weight of the unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, preferably, 10 to 30 parts by weight of the unsaturated carboxylic acid , Unsaturated carboxylic anhydrides or their mixtures. When the content is less than 5 parts by weight, there is a problem that it is difficult to dissolve in the alkali aqueous solution, and when the content is more than 40 parts by weight, there is a problem that the solubility in the alkali aqueous solution is too large.

As the epoxy group-containing unsaturated compound of ii), glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, and α-n-propyl glycidyl acrylate can be used. Ester, α-n-butyl glycidyl acrylate, acrylate-β-methyl glycidyl (acrylate-β-methyl glycidyl), methacrylic acid-β-methyl glycidyl ester, acrylic acid-β-ethyl glycidyl Ester, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate (3,4-epoxybutyl acrylate), 3,4-epoxybutyl methacrylate, acrylate-6, 7-epoxyheptyl ester, methacrylate-6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinyl benzyl glycidyl ether (o-vinyl benzyl glycidyl ether) ), m-vinyl benzyl glycidyl ether, or p-vinyl benzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylate (3,4-epoxy cyclohexyl methacrylate), etc. used alone or in combination of two or more For use, preferably, use glycidyl methacrylate, β-methyl glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, and Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. improve the copolymerization reactivity and the heat resistance of the obtained pattern.

Relative to the total monomers, the epoxy group-containing unsaturated compound is contained from 10 parts by weight to 70 parts by weight, and preferably, the epoxy group-containing unsaturated compound is contained from 20 parts by weight to 50 parts by weight. When the content is within the above range, the heat resistance of the organic insulating film and the storage stability of the photosensitive resin composition can be satisfied at the same time.

As the olefin-based unsaturated compound of iii), methylmethacrylate, methyl ethacrylate, methyl n-butyl acrylate, methyl sec-butyl acrylate, methyl tert-butyl acrylate, Methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, methyl 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentyl Acrylate, dicyclopentenyl methacrylate, dicyclopentyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyl methacrylate Dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-cyclohexyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isobornyl acrylate Ester, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxy ethyl methacrylate (2-hydroxy ethyl methacrylate), styrene, σ-methyl Styrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxythrene, 1,3-butadiene, isoprene, or 2,3 -Dimethyl-1,3-butadiene (2,3-dimethyl-1,3-butadiene), 2-[methacryloxy]ethyl 6-hydroxyhexanoate, 4-vinylphenol , 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, [[4-hydroxymethyl]cyclohexyl] methyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 2 -Oxotetrahydrofuran-3-yl methacrylate (2-oxotetrahydrofuran-3-yl methacrylate), 4-hydroxycyclohexyl methacrylate, etc., the compounds can be used alone or in combination of two or more.

Relative to the total monomers, the olefinic unsaturated compound contains 5 parts to 70 parts by weight, preferably 10 parts to 70 parts by weight of the olefinic unsaturated compound, and more preferably 20 parts by weight. Parts by weight to 50 parts by weight of the olefinic unsaturated compound. When the content is within the above range, swelling does not occur after development, and the solubility of the alkaline aqueous solution as the developer can be maintained ideally.

As a solvent used for solution polymerization of the above-mentioned monomer, methanol, tetrahydrofuran, toluene, dioxane, etc. can be used.

As the polymerization initiator used for solution polymerization of the above-mentioned monomers, a radical polymerization initiator can be used. Specifically, 2,2-azobisisobutyronitrile (2,2-azobisisobutyronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-Azo Azobis (cyclohexane-1-nitrile) or dimethyl 2,2'-azobisisobutylate (2,2'-azobisisobutylate), etc.

Preferably, in the presence of a solvent and a polymerization initiator, the above-mentioned monomers are subjected to group reaction, precipitation and filtration are carried out, and the unreacted monomers are removed by a vacuum drying process to obtain acrylic acid. The polystyrene conversion weight average molecular weight (Mw) of this type of copolymer is 3000 to 20000. In the case of an interlayer insulating film (organic insulating film) with a polystyrene-converted weight average molecular weight of less than 3000, there are problems such as a decrease in developability, a decrease in residual rate, or a decrease in pattern development and heat resistance. In the case of an interlayer insulating film having a molecular weight of more than 20,000, there is a problem that the pattern development decreases.

In addition, the silane coupling agent of c) used in the present invention is used in order to increase the adhesion to the lower substrate, and as the silane coupling agent of c) used in the present invention, ( 3-glycidoxypropyl) trimethoxysilane ((3-glycidoxypropyl) trimethoxysilane), (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyl Dimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyl ester Trimethoxysilane (3,4-epoxy butyl trimethoxysilane), 3,4-epoxybutyl triethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 2-( 3,4-Epoxycyclohexyl) ethyl triethoxysilane, aminopropyltrimethoxysilane (aminopropyltrimethoxysilane), aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1, 3-Dimethyl-butylidene) propylamine (3-triethoxysilly-n- (1,3 dimethyl-butylidene) propylamine), N-2 (aminoethyl) 3-aminopropyl trimethoxysilane, N-2 ( Aminoethyl) 3-aminopropyl triethoxy silane, N-2 (aminoethyl) 3-aminopropyl methyl dimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane , (3-isocyanatepropyl) triethoxysilane ((3-isocyanatepropyl) triethoxysilane), (3-isocyanatepropyl) trimethoxysilane, etc., the silane coupling agent can be used alone or in combination of two Use the above.

Preferably, relative to 100 parts by weight of the a) acrylic copolymer, the silane coupling agent is contained in an amount of 0.1 to 30 parts by weight. When the content is less than 0.1 parts by weight, the adhesion to the lower substrate is reduced, and when the content is more than 30 parts by weight, there are problems in storage stability and developability, and resolution is reduced.

In addition, the solvent of d) used in the present invention is used for coating the photosensitive resin composition on a substrate or the like. As a specific example, diethylene glycol dimethyl ether (Diethylene glycol dimethyl ether) can be used. , Diethylene Glycol Methyl Ether, Propylene Glycol Methyl Ether Acetate, Propylene Glycol Methyl Ether Acetate, Propylene Glycol Methyl Ether Acetate, Propylene Glycol Methyl Ether Propionate, Propylene Glycol Methyl Ether Propionate, Propylene Glycol Methyl Ether Propionate Ester, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether (butylene glycol monomethyl ether), butylene Glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, Diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether and dipropylene glycol methyl Hexyl ether and the like can be used alone or in combination of two or more.

Preferably, the solvent in the d) contains 10% to 50% by weight of the solid content of the positive photosensitive resin composition. When the solid content is less than 10% by weight, the coating thickness becomes thinner and coating uniformity is reduced. When the solid content is more than 50% by weight, the coating thickness becomes thicker and the coating uniformity is reduced. The problem that affects the coating equipment. In the case where the solid content of the total composition is 10% to 25% by weight, it is beneficial to use in a slit coater (Slit Coater), and the solid content of the total composition is 25% by weight. When the weight percentage is to 50 weight percentage, it is beneficial to use in a slit coater or a slit spin coater (Slit & Spin Coater).

Preferably, the concentration of the solid content of the positive photosensitive resin composition of the present invention as described above is 10% to 50% by weight, and the filtration is performed using a 0.1-0.2 μm Millipore Filter or the like. After use.

In addition, the method of forming an insulating film pattern in a display manufacturing process of the present invention is characterized by using the positive photosensitive resin composition. Specifically, the method of using the positive photosensitive resin composition to form a pattern in the display manufacturing process is as follows.

First, the positive photosensitive resin composition of the present invention is applied to the surface of the substrate by spin coating, slit spin coating, slit coating, roll coating, etc., and the solvent is removed by a prebaker to form a coating film. At this time, preferably, the pre-bake machine is performed at a temperature of 100 to 120° C. for 1 to 3 minutes.

Then, the formed coating film is irradiated with visible rays, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, etc. according to the pre-prepared pattern, and developed with a developer to remove unnecessary parts, thereby forming a prescribed pattern.

As the developer, an aqueous alkali solution is preferably used. Specifically, inorganic bases such as sodium hydroxide, calcium hydroxide, and calcium carbonate; primary amines such as ethylamine and n-propylamine; and secondary amines such as ethylamine and n-propylamine can be used. Class; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alcoholamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine, etc.; or tetramethylammonium hydroxide, Aqueous solutions of quaternary ammonium salts such as tetraethylammonium hydroxide. At this time, the developer is used by dissolving the alkaline compound at a concentration of 0.1 parts by weight to 10 parts by weight, and water-soluble organic solvents such as methanol and ethanol and surfactants may also be added in an appropriate amount.

In addition, after developing with the developer as described above, washing with ultrapure water for 30 to 90 seconds to remove unnecessary parts, drying to form a pattern, and irradiating the formed pattern with light such as ultraviolet rays, The final pattern can be obtained by heat-treating the pattern at a temperature of 150-400°C for 30-90 minutes with the aid of a heating device such as an oven.

The photosensitive resin composition of the present invention has excellent flatness, transmittance, outgassing properties (Outgas), especially has excellent sensitivity, and has outstanding adhesion, contrast, and chemical resistance under high temperature and high humidity conditions. Improved, so as to be suitable for forming interlayer insulating films, pixel defining layers, column spacing, etc. in the manufacturing process of liquid crystal displays and organic light emitting diodes. In addition, the present invention may also include a display element containing a cured product of the positive photosensitive resin composition.

Hereinafter, in order to facilitate the understanding of the present invention, preferred embodiments are presented, but the following embodiments are only used to illustrate the present invention, and the scope of the present invention is not limited to the following embodiments.

Synthesis Example 1: Preparation of 1,2-quinonediazide compound (A)

By making 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol (4,4',4"-[cyclohexane- 1,1,4-triyl]triphenol) and 2.0 moles of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] are condensed to prepare 4,4',4”-[cyclohexane Alkyl-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 4:

Synthesis Example 2: Preparation of 1,2-quinonediazide compound (B)

By making 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]tris[2-methylphenol](4,4', 4”-(cyclohexane-1,1,4-triyl)tris(2-methylphenol)) and 2.0 moles of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] are condensed to Preparation of 4,4',4"-[cyclohexane-1,1,4-triyl]tris[2-methylphenol]1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 5:

Synthesis Example 3: Preparation of 1,2-quinonediazide compound (C)

By making 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]tris[2,6-dimethylphenol] represented by the following chemical formula 6 (4, 4',4''-(cyclohexane-1,1,4-triyl)tris(2,6-dimethylphenol)) and 2.0 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride ] Conduct condensation reaction to prepare 4,4',4"-[cyclohexane-1,1,4-triyl]tris[2,6-dimethylphenol]1,2-diazide naphthoquinone- 5-sulfonate. Chemical formula 6:

Synthesis Example 4: Preparation of 1,2-quinonediazide compound (D)

By making 1 mol of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by the following chemical formula 7 and 2.0 mol of 1,2 -Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol 1 ,2-Diazide naphthoquinone-5-sulfonate. Chemical formula 7:

Synthesis Example 5: Preparation of 1,2-quinonediazide compound (E)

By making 1 mol of 4-[1-[3-cyclohexyl-4-hydroxy-5-methylphenyl]cyclohexyl]-6-toluene-1,3-diol represented by the following chemical formula 8 (4-(1-(3-cyclohexyl-4-hydroxy-5-methylphenyl)cyclohexyl)-6-methylbenzene-1,3-diol) and 2.0 mol of 1,2-diazide naphthoquinone-5- Sulfonic acid [chloride] undergoes condensation reaction to prepare 4-[1-[3-cyclohexyl-4-hydroxy-5-methylphenyl]cyclohexyl]-6-toluene-1,3-diol1,2 -Diazide naphthoquinone-5-sulfonate. Chemical formula 8:

Synthesis Example 6: Preparation of 1,2-quinonediazide compound (F)

By making 1 mol of 4-[1-[4-hydroxy-3-methyl-5-[4-methylcyclohexyl]phenyl]-4-methylcyclohexyl] represented by the following chemical formula 9 -6-Toluene-1,3-diol](4-(1-(4-hydroxy-3-methyl-5-(4-methylcyclohexyl)phenyl)-4-methylcyclohexyl)-6-methylbenzene-1,3- diol) and 2.0 moles of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] are condensed to prepare 4-[1-[4-hydroxy-3-methyl-5-[4 -Methylcyclohexyl]phenyl]-4-methylcyclohexyl]-6-toluene-1,3-diol]1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 9:

Synthesis Example 7: Preparation of 1,2-quinonediazide compound (A-1)

By using 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Chemical Formula 4 in Synthesis Example 1 and 1.0 mol of 1,2- Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-dimide N-Naphthoquinone-5-sulfonate.

Synthesis Example 8: Preparation of 1,2-quinonediazide compound (A-2)

By using 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Chemical Formula 4 in Synthesis Example 1 and 1.2 mol of 1,2- Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-dimide N-Naphthoquinone-5-sulfonate.

Synthesis Example 9: Preparation of 1,2-quinonediazide compound (A-3)

By using 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Chemical Formula 4 in Synthesis Example 1 and 1.5 mol of 1,2- Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-dimide N-Naphthoquinone-5-sulfonate.

Synthesis Example 10: Preparation of 1,2-quinonediazide compound (A-4)

By using 1 mol of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Chemical Formula 4 in Synthesis Example 1 and 2.5 mol of 1,2- Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4',4"-[cyclohexane-1-triphenol-1,2-diazide naphthoquinone-5 -Sulfonate.

Synthesis Example 11: Preparation of 1,2-quinonediazide compound (D-1)

By making 1 mol of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 and 1.0 mol of 1,2-Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3- Diol 1,2-diazide naphthoquinone-5-sulfonate.

Synthesis Example 12: Preparation of 1,2-quinonediazide compound (D-2)

By making 1 mol of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 and 1.5 mol of 1,2-Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3- Diol 1,2-diazide naphthoquinone-5-sulfonate.

Synthesis Example 13: Preparation of 1,2-quinonediazide compound (D-3)

By making 1 mol of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 and 2.5 mol of 1,2-Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3- Diol 1,2-diazide naphthoquinone-5-sulfonate.

Synthesis Example 14: Preparation of acrylic copolymer (A)

Put 400 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of methacrylic acid, and 20 parts by weight of styrene into a flask equipped with a cooler and a stirrer. And 30 parts by weight of a mixed solution of glycidyl methacrylate. After thoroughly mixing the liquid phase composition at 600 rpm in a mixing vessel, 15 parts by weight of 2,2'-bisazo-(2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly heated to 55° C. and maintained at this temperature for 24 hours, then cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution with a solid content concentration of 25% by weight. The weight average molecular weight of the acrylic copolymer is 6000. At this time, the weight average molecular weight is a polystyrene conversion weight average molecular weight measured using a gel permeation chromatography (GPC).

Synthesis Example 15: Preparation of acrylic copolymer (B)

A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methyl acrylate was put into a flask equipped with a cooler and a stirrer. After thoroughly mixing the liquid phase composition in a mixing vessel at 600 rpm, 10 parts by weight of 2,2'-bisazo-(2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly heated to 55° C. and maintained at this temperature for 24 hours, then cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution with a solid content concentration of 30% by weight.

In order to remove unreacted monomers in the polymer solution, 100 parts by weight of the polymer solution were precipitated with respect to 1000 parts by weight of n-Hexane. After precipitation, the Poor solvent with unreacted substances dissolved in it is removed by a filtering process using a mesh (Mesh). Afterwards, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, the acrylic copolymer is prepared by completely removing the solvent by vacuum drying at a temperature below 30°C.

The weight average molecular weight of the acrylic copolymer is 10,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using a gel permeation chromatograph.

Synthesis Example 16: Preparation of acrylic copolymer (C)

A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methyl acrylate was put into a flask equipped with a cooler and a stirrer. After thoroughly mixing the liquid phase composition in a mixing vessel at 600 rpm, 5 parts by weight of 2,2'-bisazo-(2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly heated to 55° C. and maintained at this temperature for 24 hours, then cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution with a solid content concentration of 30% by weight.

In order to remove unreacted monomers in the polymer solution, 100 parts by weight of the polymer solution were precipitated with respect to 1000 parts by weight of n-hexane. After precipitation, the poor solvent dissolving unreacted substances is removed by a filtration process using a filter. Afterwards, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, the acrylic copolymer is prepared by completely removing the solvent by vacuum drying at a temperature below 30°C.

The weight average molecular weight of the acrylic copolymer is 16,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using a gel permeation chromatograph.

Synthesis Example 17: Preparation of acrylic copolymer (D)

Except that the weight average molecular weight of the acrylic copolymer was adjusted to 4000 by adjusting the reaction time, the acrylic copolymer was prepared in the same manner as in Synthesis Example 14. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using a gel permeation chromatograph.

Comparative Synthesis Example 1: Preparation of 1,2-quinonediazide compound (G)

By making 1 mol of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene] represented by the following chemical formula 10 Condensation reaction between bisphenol and 2.0 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] to prepare 4,4'-[1-[4-[1-[4-hydroxybenzene Yl]-1-methylethyl]phenyl]ethylene]bisphenol 1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 10:

Comparative Synthesis Example 2: Preparation of 1,2-quinonediazide compound (H)

By making 1 mol of 4,4'-[1,3-phenylene bis[propane-2,2-diyl]]bis[benzene-1,3-diol] represented by the following chemical formula 11 (4,4'-(1,3-phenylenebis(propane-2,2-diyl))bis(benzene-1,3-diol)) and 2.0 mol of 1,2-diazide naphthoquinone-5 -Sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4'-[1,3-phenylene bis[propane-2,2-diyl]]bis[benzene-1,3-diol]1, 2-Diazide naphthoquinone-5-sulfonate. Chemical formula 11:

Comparative Synthesis Example 3: Preparation of 1,2-quinonediazide compound (I)

By making 1 mole of [4-[2-phenylpropan-2-yl]benzene-1,3-diol] (4-(2-phenylpropan-2-yl)benzene represented by the following chemical formula 12 -1,3-diol) and 2.0 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] for condensation reaction to prepare [4-[2-phenylpropane-2-yl] Benzene-1,3-diol] 1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 12:

Comparative Synthesis Example 4: Preparation of 1,2-quinonediazide compound (J)

By making 1.0 mol of 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol (4-(7 -hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol) and 2.0 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] for condensation reaction To prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 13:

Comparative Synthesis Example 5: Preparation of 1,2-quinonediazide compound (K)

By making 1.0 mol of 4,4'-[cyclohexane-1,1-diyl]diphenol (4,4'-(cyclohexane-1,1-diyl)diphenol) represented by the following chemical formula 14 Condensation reaction with 2.0 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] to prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2- Benzene-1,3-diol 1,2-diazide naphthoquinone-5-sulfonate. Chemical formula 14:

Comparative Synthesis Example 6: Preparation of 1,2-quinonediazide compound (G-1)

By making 1 mol of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene] represented by the chemical formula 10 Condensation reaction of bisphenol with 1.5 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] to prepare 4,4'-[1-[4-[1-[4-hydroxybenzene Yl]-1-methylethyl]phenyl]ethylene]bisphenol 1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 7: Preparation of 1,2-quinonediazide compound (G-2)

By making 1 mol of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene] represented by the chemical formula 10 Condensation reaction of bisphenol with 2.5 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] to prepare 4,4'-[1-[4-[1-[4-hydroxybenzene Yl]-1-methylethyl]phenyl]ethylene]bisphenol 1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 8: Preparation of 1,2-quinonediazide compound (H-1)

By making 1 mol of 4,4'-[1,3-phenylene bis[propane-2,2-diyl]]bis[benzene-1,3-diol] represented by the chemical formula 11 Condensation reaction with 1.5 mol of 1,2-diazide naphthoquinone-5-sulfonic acid [chloride] to prepare 4,4'-[1,3-phenylene bis[propane-2,2- Diyl]]bis[benzene-1,3-diol]1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 9: Preparation of 1,2-quinonediazide compound (H-2)

By making 1 mol of 4,4'-[1,3-phenylene bis[propane-2,2-diyl]] represented by the chemical formula 11 and 2.5 mol of 1,2-dimide Amino naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4,4'-[1,3-phenylene bis[propane-2,2-diyl]] bis[benzene-1,3 -Diol] 1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 10: Preparation of 1,2-quinonediazide compound (I-1)

By making 1 mol of [4-[2-phenylpropan-2-yl]benzene-1,3-diol] represented by the chemical formula 12 and 1.5 mol of 1,2-diazide Naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare [4-[2-phenylpropane-2-yl]benzene-1,3-diol] 1,2-diazide naphthoquinone- 5-sulfonate.

Comparative Synthesis Example 11: Preparation of 1,2-quinonediazide compound (I-2)

By making 1 mol of [4-[2-phenylpropan-2-yl]benzene-1,3-diol] represented by the chemical formula 12 and 2.5 mol of 1,2-diazide Naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare [4-[2-phenylpropane-2-yl]benzene-1,3-diol] 1,2-diazide naphthoquinone- 5-sulfonate.

Comparative Synthesis Example 12: Preparation of 1,2-quinonediazide compound (J-1)

By making 1.0 mol of 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol represented by the chemical formula 13 and 1.5 mol of 1,2-Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1 ,3-diol 1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 13: Preparation of 1,2-quinonediazide compound (J-2)

By making 1.0 mol of 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol represented by the chemical formula 13 and 2.5 mol of 1,2-Diazide naphthoquinone-5-sulfonic acid [chloride] undergoes condensation reaction to prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1 ,3-diol 1,2-diazide naphthoquinone-5-sulfonate.

Comparative Synthesis Example 14: Preparation of 1,2-quinonediazide compound (K-1)

By making 1.0 mol of 4,4'-[cyclohexane-1,1-diyl]biphenol represented by the chemical formula 14 and 1.5 mol of 1,2-diazide naphthoquinone-5 -Sulfonic acid [chloride] undergoes condensation reaction to prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-diazide Glynaphthoquinone-5-sulfonate.

Comparative Synthesis Example 15: Preparation of 1,2-quinonediazide compound (K-2)

By making 1.0 mol of 4,4'-[cyclohexane-1,1-diyl]biphenol represented by the chemical formula 14 and 2.5 mol of 1,2-diazide naphthoquinone-5 -Sulfonic acid [chloride] undergoes condensation reaction to prepare 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-diazide Glynaphthoquinone-5-sulfonate.

Comparative Synthesis Example 16: Preparation of acrylic copolymer (E)

A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methyl acrylate was put into a flask equipped with a cooler and a stirrer. After thoroughly mixing the liquid phase composition in a mixing vessel at 600 rpm, 18 parts by weight of 2,2'-bisazo-(2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly heated to 55° C. and maintained at this temperature for 24 hours, then cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution with a solid content concentration of 30% by weight.

In order to remove unreacted monomers in the polymer solution, 100 parts by weight of the polymer solution were precipitated with respect to 1000 parts by weight of n-hexane. After precipitation, the poor solvent dissolving unreacted substances is removed by a filtration process using a filter. Afterwards, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, the acrylic copolymer is prepared by completely removing the solvent by vacuum drying at a temperature below 30°C.

The weight average molecular weight of the acrylic copolymer is 2500. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using a gel permeation chromatograph.

Comparative Synthesis Example 17: Preparation of acrylic copolymer (F)

A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid, 30 parts by weight of styrene, and 40 parts by weight of glycidyl methyl acrylate was put into a flask equipped with a cooler and a stirrer. After thoroughly mixing the liquid phase composition at 600 rpm in a mixing vessel, 1.5 parts by weight of 2,2'-bisazo-(2,4-dimethylvaleronitrile) was added. The polymerization mixed solution was slowly heated to 55° C. and maintained at this temperature for 24 hours, then cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution with a solid content concentration of 30% by weight.

In order to remove unreacted monomers in the polymer solution, 100 parts by weight of the polymer solution were precipitated with respect to 1000 parts by weight of n-hexane. After precipitation, the poor solvent dissolving unreacted substances is removed by a filtration process using a filter. Afterwards, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, the acrylic copolymer is prepared by completely removing the solvent by vacuum drying at a temperature below 30°C.

The weight average molecular weight of the acrylic copolymer is 22,000. At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using a gel permeation chromatograph.

Example 1: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 14, 30 parts by weight of propylene glycol monomethyl ether acetate were used to dissolve 30 parts by weight of the 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate prepared in Example 1 and 3 parts by weight as After the (3-glycidoxypropyl) trimethoxysilane of the silane coupling agent, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Example 2: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (B) of Synthesis Example 2 was used instead of the 1,2-quinonediazide-5-sulfonate compound ( A) Except for using, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 3: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (C) of Synthesis Example 3 was used instead of the 1,2-quinonediazide-5-sulfonate compound (C) of Synthesis Example 1 A) Except for using, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 4: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (D) of Synthesis Example 4 was used instead of the 1,2-quinonediazide-5-sulfonate compound ( A) Except for using, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 5: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (E) of Synthesis Example 5 was used instead of the 1,2-quinonediazide-5-sulfonate compound (E) of Synthesis Example 1 A) Except for using, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 6: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (F) of Synthesis Example 6 was used instead of the 1,2-quinonediazide-5-sulfonate compound (F) of Synthesis Example 1 ( A) Except for using, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 7: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (A-1) of Synthesis Example 7 was substituted for the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 8: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (A-2) of Synthesis Example 8 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 9: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (A-3) of Synthesis Example 9 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 10: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (A-4) of Synthesis Example 10 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 11: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (D-1) of Synthesis Example 11 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 12: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (D-2) of Synthesis Example 12 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 13: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (D-3) of Synthesis Example 13 was used instead of the 1,2-quinonediazide-5-sulfonate of Synthesis Example 1. Except that the compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Example 14: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (D) prepared in Synthesis Example 17, 30 parts by weight of propylene glycol monomethyl ether acetate were used to dissolve 30 parts by weight of the 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate prepared in Example 1 and 3 parts by weight as After the (3-glycidoxypropyl) trimethoxysilane of the silane coupling agent, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Example 15: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (B) prepared in Synthesis Example 15, 30 parts by weight of 4, were dissolved with propylene glycol monomethyl ether acetate, 4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate and 3 parts by weight as a silane coupling agent ( After 3-glycidoxypropyl) trimethoxysilane, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Example 16: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (C) prepared in Synthesis Example 16, 30 parts by weight of 4, were dissolved with propylene glycol monomethyl ether acetate, 4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate and 3 parts by weight as a silane coupling agent ( After 3-glycidoxypropyl) trimethoxysilane, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Comparative example 1: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (G) of Comparative Synthesis Example 1 was substituted for the 1,2-quinonediazide-5-sulfonate compound of Synthesis Example 1 (A) Except for using, the photosensitive resin composition was prepared by the same method as Example 1.

Comparative Example 2: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (H) of Comparative Synthesis Example 2 was used instead of the 1,2-quinonediazide-5-sulfonate compound of Synthesis Example 1 (A) Except for using, the photosensitive resin composition was prepared by the same method as Example 1.

Comparative Example 3: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (I) of Comparative Synthesis Example 3 was used instead of the 1,2-quinonediazide-5-sulfonate compound of Synthesis Example 1 (A) Except for using, the photosensitive resin composition was prepared by the same method as Example 1.

Comparative Example 4: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (J) of Comparative Synthesis Example 4 was used instead of the 1,2-quinonediazide-5-sulfonate compound of Synthesis Example 1 (A) Except for using, the photosensitive resin composition was prepared by the same method as Example 1.

Comparative Example 5: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonate compound (K) of Comparative Synthesis Example 5 was substituted for the 1,2-quinonediazide-5-sulfonate compound of Synthesis Example 1 (A) Except for using, the photosensitive resin composition was prepared by the same method as Example 1.

Comparative Example 6: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (G-1) of Comparative Synthesis Example 6 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 7: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (G-2) of Comparative Synthesis Example 7 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 8: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (H-1) of Comparative Synthesis Example 8 was used instead of the 1,2-quinonediazide-5-sulfonic acid in Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 9: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (H-2) of Comparative Synthesis Example 9 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 10: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (I-1) of Comparative Synthesis Example 10 was used instead of 1,2-quinonediazide-5-sulfonic acid in Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 11: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (I-2) of Comparative Synthesis Example 11 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 12: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (J-1) of Comparative Synthesis Example 12 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 13: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (J-2) of Comparative Synthesis Example 13 was used instead of 1,2-quinonediazide-5-sulfonic acid in Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 14: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (K-1) of Comparative Synthesis Example 14 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 15: Preparation of photosensitive resin composition

Except that in Example 1, the 1,2-quinonediazide-5-sulfonic acid ester compound (K-2) of Comparative Synthesis Example 15 was substituted for the 1,2-quinonediazide-5-sulfonic acid of Synthesis Example 1. Except that the ester compound (A) was used, the photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Example 16: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (E) prepared in Comparative Synthesis Example 16, 30 parts by weight of propylene glycol monomethyl ether acetate were dissolved in 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate prepared in Synthesis Example 1 and 3 parts by weight After (3-glycidoxypropyl) trimethoxysilane as a silane coupling agent, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Comparative Example 17: Preparation of photosensitive resin composition

In order to make the solid content of the mixture 20% by weight relative to 100 parts by weight of the acrylic copolymer (F) prepared in Comparative Synthesis Example 17, 30 parts by weight of propylene glycol monomethyl ether acetate were dissolved in 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2-diazide naphthoquinone-5-sulfonate prepared in Synthesis Example 1 and 3 parts by weight After (3-glycidoxypropyl) trimethoxysilane as a silane coupling agent, it was filtered with a 0.1 μm microporous filter to prepare a photosensitive resin composition.

The sensitivity, resolution, curing process range, transmittance, heat discoloration resistance, adhesion force, heat resistance and other physical properties of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 5 were measured and shown in Table 1. After coating the photosensitive resin compositions of Examples 1 to 15 and Comparative Examples 1 to 17 on a glass substrate using a spin coater, they were prebaked at a temperature of 100°C on a hot plate 2 minutes to form a film with a thickness of 4.0 μm.

1) Sensitivity: Use a predetermined pattern mask in the film formed as described above, and the intensity of exposure to the broadband (Broadband) with the standard dose (Dose) of the contact hole size (Contact Hole CD) of 10μm is ^{After ultraviolet rays of 20} mW/cm 2, an aqueous solution containing 2.38 weight percent of tetramethylammonium hydroxide was developed at a temperature of 23° C. for 1 minute, and then washed with ultrapure water for 1 minute.

Then, in the case of 365nm is irradiated to the imaging 400mJ / cm ² of ultraviolet intensity of 20mW / cm ^2, and at a temperature of 230 deg.] C and cured in an oven for 30 minutes to obtain a pattern film thickness of 3.0μm .

2) Resolution: Measure the smallest size of the 10 μm contact hole pattern (Pattern) formed when measuring the sensitivity of the above 1).

3) Curing process range: the patterned film is formed by the same method as when measuring the sensitivity of 1), and the dimensional change rate before and after curing is measured according to the 10μm contact hole size standard. At this time, the case where the rate of change is 0 to 10% is marked as ○, the case where the rate of change is 10 to 20% is marked as △, and the case where the rate of change is greater than 20% is marked as x.

4) Permeability: The permeability is evaluated by measuring the 400 nm transmittance of the patterned film with a spectrophotometer in the patterned film formed when measuring the sensitivity of the above 1). At this time, the case where the transmittance is 90% or more is marked as ○, the case where the transmittance is 85 to 90% is marked as △, and the case where the transmittance is less than 80% is marked as x.

5) Heat discoloration resistance: The substrate was cured for 30 minutes in an oven at 230°C during the evaluation of the permeability of the 4), and the test was performed twice, and the transmittance of the patterned film before and after curing was determined by 400nm transmittance. Change to evaluate the heat discoloration resistance. At this time, the case where the rate of change is less than 3% is marked as ○, the case where the rate of change is 3 to 5% is marked as △, and the case where the rate of change is greater than 5% is marked as x.

6) Adhesive force: The adhesive force of the pattern film formed when measuring the sensitivity of the one) is evaluated by the scope and according to whether the pattern is lost or not.

Mark the case where the bonding strength is ensured at a pre-baking temperature above 95℃ as ○, and the case where the bonding force is guaranteed at a pre-baking temperature of 100～105℃ is marked as △, and the bonding force will be ensured at a pre-baking temperature above 105℃ or If the pattern is lost, mark it as ×.

7) Heat resistance: Use TGA to measure heat resistance. After sampling the patterned film formed when measuring the sensitivity of the above 1), the temperature was raised to 900° C. at a temperature of 10° C. per minute at room temperature by TGA. The case where the temperature loss of 5 weight percent is greater than 300°C is marked as ○, the case where the temperature loss of 5 weight% is 280-300°C is marked as △, and the temperature loss of 5 weight percent is marked as × .

Table 1

According to the table 1, according to the present invention, the positive photosensitive insulating film composition prepared in Example 1 to Example 16 has excellent properties such as resolution, curing process range, transmittance, heat discoloration resistance, and heat resistance. . In addition, compared with Examples 1 to 16, the transmittance and heat discoloration resistance of Comparative Examples 1 to 15 were lower, and compared with Comparative Example 5, Comparative Example 14, Comparative Example 15, and Comparative Example 16, the heat resistance Excellent, especially compared with Comparative Example 1 to Comparative Example 17, the sensitivity is excellent, so that the process tact can be shortened, and the outstanding light characteristics and reliability of the panel can be ensured by the outstanding transmittance and heat discoloration resistance. Compared with the comparative example Compared with 16, the resolution, adhesion, and heat resistance are good, which can ensure an excellent process range. This shows that the photosensitive resin composition can be applied to various display fields.

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Claims (13)

A positive photosensitive resin composition comprising: a) a 1,2-quinonediazide compound of the following chemical formula 1 or 2; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent , Chemical formula 1:

In the chemical formula 1, R _{1 is} each independently a hydrogen atom or 1,2-quinonediazide sulfonate, R _{2 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbons, and at least one of _{R 1} It is 1,2-quinonediazide sulfonate, chemical formula 2:

In the chemical formula 2, R _{3 is} each independently a hydrogen atom or 1,2-quinonediazide sulfonate, R _{4 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbons, and at least one of _{R 3} It is 1,2-quinone diazide sulfonate. The positive photosensitive resin composition as described in item 1 of the scope of the patent application, which comprises: a) 5 to 50 parts by weight of the 1,2-quinonediazide compound of the chemical formula 1 or the chemical formula 2; b ) 100 parts by weight of acrylic copolymer; c) 0.1 to 30 parts by weight of silane coupling agent; and d) solvent so that the solid content in the positive photosensitive resin composition reaches 10% by weight To 50 weight percent. The positive photosensitive resin composition as described in item 1 of the scope of patent application, wherein the 1,2-quinonediazide sulfonate is selected from 1,2-quinonediazide-4-sulfonate, One or more types of 1,2-quinonediazide-5-sulfonate and 1,2-quinonediazide-6-sulfonate. The positive photosensitive resin composition as described in claim 1, wherein the 1,2-quinonediazide sulfonate is 1,2-quinonediazide-5-sulfonate. The positive photosensitive resin composition as described in item 2 of the scope of the patent application, wherein the acrylic copolymer is prepared by i) 5 parts by weight to 40 parts by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride or their mixture Ii) 10 parts by weight to 70 parts by weight of an epoxy group-containing unsaturated compound and iii) 5 parts by weight to 70 parts by weight of an olefinic unsaturated compound are prepared by copolymerization. The positive photosensitive resin composition as described in item 5 of the scope of patent application, wherein i) the unsaturated carboxylic acid, the unsaturated carboxylic anhydride, or their mixture is selected from acrylic acid, methacrylic acid, maleic acid, rich One or more of the group consisting of maleic acid, citraconic acid, meconic acid, itaconic acid, and anhydrides of their unsaturated dicarboxylic acids. The positive photosensitive resin composition according to item 5 of the scope of patent application, wherein the epoxy group-containing unsaturated compound of ii) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and α-ethacrylic acid Glycidyl ester, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-acrylic acid Ethyl glycidyl ester, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxy acrylate Heptyl ester, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- One or more of the group consisting of vinyl benzyl glycidyl ether and 3,4-epoxycyclohexyl methacrylate. The positive photosensitive resin composition according to item 5 of the scope of patent application, wherein the olefinic unsaturated compound in iii) is selected from methyl methacrylate, methyl ethacrylate, n-butyl methyl acrylate, and secondary Methyl butyl acrylate, methyl tert-butyl acrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, methyl 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentan Methacrylate, dicyclopentenyl methacrylate, dicyclopentyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyl methacrylate, dicyclopentyl methacrylate Esters, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl 2-methacrylate, dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate Ester, 2-hydroxyethyl methacrylate, styrene, σ-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxythrene, 1,3-butane Ene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-[methacryloxy]ethyl 6-hydroxyhexanoate, 4-vinylphenol, 4- Vinyl cyclohexanol, 4-hydroxybenzyl methacrylate, [[4-hydroxymethyl]cyclohexyl] methyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 2-oxo One or more of the group consisting of tetrahydrofuran-3-yl methacrylate and 4-hydroxycyclohexyl methacrylate. The positive photosensitive resin composition according to the first item of the scope of patent application, wherein the acrylic copolymer of b) has a polystyrene conversion weight average molecular weight (Mw) of 3000 to 20000. The positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the silane coupling agent of c) is selected from (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl) Propyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl) Glyceryloxypropyl) dimethyl ethoxysilane, 3,4-epoxybutyl trimethoxysilane, 3,4-epoxybutyl triethoxysilane, 2-(3,4-epoxy Cyclohexyl) ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-tris Ethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-ammonia Propyl triethoxy silane, N-2 (aminoethyl) 3-aminopropyl methyl dimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, (3-isocyanate propyl Group) one or more of the group consisting of triethoxysilane. The positive photosensitive resin composition according to item 1 of the scope of patent application, wherein the solvent of d) is selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetic acid Ester, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, two Propylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutyl glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene two Diethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tert-butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, One or more types of dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether. A display element comprising a cured product of the positive photosensitive resin composition as described in the first item of the scope of patent application. A method for forming a pattern of a display element includes a step of patterning an interlayer insulating film manufactured by applying the positive photosensitive resin composition as described in the first item of the patent application.