TW201833078A - Positive photosensitive resin composition, display element thereof and method for forming patterns of display element thereof especially applied to the pixel define layer and column spacer for LCD or OLED with excellent sensitivity, transparency and improved adhesive force - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, and more particularly to a positive photosensitive resin composition including: a) a 1,2-quinonediazide of the following chemical formula 1 or chemical formula 2; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent; R1 of chemical formula 1 and R3 of chemical formula 2 each independently represent a hydrogen atom or a 1,2-quinonediazide sulfonate; R2 of chemical formula 1 and R4 of chemical formula 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R1 and R3 is a 1,2-quinonediazide sulfonate.

Description

Positive-type photosensitive resin composition, display element thereof, and pattern forming method of display element

The present invention relates to a positive photosensitive resin composition, a display element thereof, 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). Resolution, curing process range, heat discoloration resistance, heat resistance, etc., especially with excellent sensitivity, transparency, and significantly improved adhesion, suitable for forming manufacturing processes of liquid crystal displays (LCD) and organic light emitting diodes (OLED) And a photosensitive resin composition such as an interlayer insulating film, a Pixel Define Layer (PDL), and a column spacer.

Generally, a flat panel display, as a currently widely used display, includes various types such as a liquid crystal display (LCD) and an organic light emitting display (OLED).

In the manufacturing process of a thin film transistor (TFT) type liquid crystal display and an organic light emitting diode, an interlayer insulating film is used in order to insulate wirings disposed between the layers.

Especially, recently, with the development of high-speed response and high-resolution devices, wiring technology with high aperture ratio and low resistance is required. For this reason, there is a tendency that the height difference of the thin film transistor becomes large because the width of the circuit is reduced and a high thickness is formed. In this case, the thickness of the interlayer insulating film to be used for the flatness increases, but this causes a decrease in sensitivity and transparency, thereby reducing the productivity and quality of the panel. Therefore, there is an urgent need to develop an insulating film having excellent sensitivity and transparency.

Therefore, an object of the present invention is to provide an excellent resolution, a curing process range, heat discoloration resistance, and heat resistance, particularly excellent sensitivity and transparency, and significantly improve the adhesive force, which is suitable for forming liquid crystal displays and organic A photosensitive resin composition such as an interlayer insulating film, a pixel definition layer, and a column spacer in a manufacturing process of a light emitting diode.

Still 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.

Another object of the present invention is to provide a pattern forming method for a display substrate using the photosensitive resin composition.

In order to achieve the above-mentioned object, the present invention provides a) a 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2 below; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent Photosensitive resin composition. Chemical formula 1: R _{1 of} the chemical formula 1 is independently a hydrogen atom or a 1,2-quinonediazide-based sulfonate, R ₂ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least _one of R ₁ is One is 1,2-quinonediazide sulfonate. Chemical formula 2: R _{3 of} the chemical formula 2 is independently a hydrogen atom or a 1,2-quinonediazide sulfonate, R ₄ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ₃ is One is 1,2-quinonediazide sulfonate.

The positive-type photosensitive resin composition used in the present invention has excellent resolution, curing process range, heat discoloration resistance, heat resistance, and particularly excellent sensitivity and permeability, so it can provide significantly improved adhesion and is suitable for A photosensitive resin composition that forms an interlayer insulating film, a pixel definition layer, and a column spacer in a manufacturing process of a liquid crystal display and an organic light emitting diode. Further, a liquid crystal display and an organic light emitting diode substrate including a cured product of the photosensitive resin composition, and a pattern forming 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 Wetting display (EWD) and other materials such as passivation insulation film, gate insulation film, flattening film, column spacer, diaphragm, etc.

Hereinafter, the present invention will be described in detail.

The present invention relates to a combination of photosensitive resins that can be used in various fields such as interlayer insulating films, passivation insulating films, gate insulating films, protective films, column spacers, pixel definition layers, and separators, which can be arranged between layers of a liquid crystal display and an organic light emitting diode. Thing.

The positive photosensitive resin composition of the present invention includes: a) a 1,2-quinonediazide compound of the following Chemical Formula 1 or Chemical Formula 2; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent . Chemical formula 1: R _{1 of} the chemical formula 1 is independently a hydrogen atom or a 1,2-quinonediazide-based sulfonate, and R _{2 is} independently a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, preferably, An alkyl group having 1 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms, more preferably, an alkyl group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms, said R ₁ in at least one of 1,2-quinonediazide sulfonic acid ester type. Chemical formula 2: R _{3 in} the chemical formula 2 is independently a hydrogen atom or a 1,2-quinonediazide sulfonate, and R 4 is a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms. 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, and R ₃ At least one of them is a quinonediazide sulfonate.

In the present invention, the 1,2-quinonediazide compound represented by Chemical Formula 1 or Chemical Formula 2 as a) is used as a photosensitive compound (Photo Active Compound: PAC), and is 1 of Chemical Formula 1 or Chemical Formula 2. Specific examples of 2,2-quinonediazide-based sulfonate include 1,2-quinonediazide-4-sulfonate, 1,2-quinonediazide-5-sulfonate, and 1,2 -Quinonediazide-6-sulfonate and the like, as more specific examples, 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 alkali developing solution of the photosensitive resin film and suppressing the alkali of the photosensitive resin film in the unexposed areas Solubility can form a positive pattern. Chemical formula 3:

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

With respect to 100 parts by weight of the b) acrylic copolymer, 5 to 50 parts by weight of the 1,2-quinonediazide compound of Chemical Formula 1 or Chemical Formula 2, and 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 the 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 Since a large amount of unreacted 1,2-quinonediazide-based sulfonate compound remains, there is a problem that it is difficult to develop because the solubility in an alkaline aqueous solution as a developing solution is too low.

According to the b) acrylic copolymer of the present invention, i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof as a monomer, ii) an unsaturated compound containing an epoxy group, and iii) an olefin The unsaturated compound is prepared by polymerization. For example, an acrylic copolymer can be prepared by performing a group reaction on the monomer as described above in the presence of a solvent and a polymerization initiator.

As the i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; maleic acid Unsaturated dicarboxylic acids such as fumaric acid, citraconic acid, methaconic acid, itaconic acid, etc .; or the anhydrides of their unsaturated dicarboxylic acids, etc. These are used singly or in combination of two or more kinds. In particular, it is more preferable to use acrylic acid, methacrylic acid, or anhydrous maleic acid for the solubility in copolymerization reactivity and the alkali aqueous solution as a developing solution.

5 to 40 parts by weight of the unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and preferably 10 to 30 parts by weight of the unsaturated carboxylic acid with respect to the total monomer , Unsaturated carboxylic anhydrides, or mixtures thereof. When the content is less than 5 parts by weight, there is a problem that it is difficult to dissolve in an alkaline aqueous solution. When the content is more than 40 parts by weight, there is a problem that the solubility in an alkaline aqueous solution is excessive.

As the ii) unsaturated compound containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate, and α-n-propyl acrylate can be used. Ester, α-n-butyl glycidyl acrylate, acrylate-β-methyl glycidyl, methacrylate-β-methyl glycidyl, acrylate-β-ethyl glycidyl Esters, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6, 7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether ), M-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylate, etc., alone or in combination of two or more To use, preferably using glycidyl methacrylate, methacrylic acid-β- Glycidyl glycidyl ester, methacrylic acid-6,7-epoxyheptyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether or 3,4-cyclo Oxycyclohexyl methacrylate and the like to improve the copolymerization reactivity and the heat resistance of the obtained pattern.

The epoxy group-containing unsaturated compound is contained in an amount of 10 to 70 parts by weight with respect to the total monomer, and preferably 20 to 50 parts by weight of the epoxy group-containing unsaturated compound is contained. 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 described in 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, methacrylate Dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, cyclohexyl 2-methacrylate, dicyclopentyloxyethyl acrylate, isobornyl acrylate Ester, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate (2-h ydroxy ethyl methacrylate), styrene, σ-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxythremonene, 1,3-butane Diene, isoprene, or 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, 4-hydroxycyclohexyl methacrylate, etc. These compounds are used singly or in combination of two or more.

The olefin-based unsaturated compound is contained in an amount of 5 to 70 parts by weight with respect to the total monomer, preferably, the olefin-based unsaturated compound is contained in an amount of 10 to 70 parts by weight, and more preferably 20 The olefin-based unsaturated compound is from 50 parts by weight to 50 parts by weight. When the content is within the above range, swelling does not occur after development, and the solubility of the alkaline aqueous solution as a developer can be maintained satisfactorily.

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

As a polymerization initiator used for the solution polymerization of the above-mentioned monomers, a group polymerization initiator can be used, and specifically, 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'-azobisisobutyronitrile (2,2'-azobisisobutylate), etc.

Preferably, the acrylic acid obtained by performing a group reaction on the above-mentioned monomers in the presence of a solvent and a polymerization initiator, performing precipitation and filtration, and removing unreacted monomers by a Vacuum Drying process The polystyrene-based copolymer has a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 20,000. In the case of an interlayer insulating film (organic insulating film) having a polystyrene-equivalent weight-average molecular weight of less than 3000, there is a problem that the developability, the residual rate, etc., or the pattern development and heat resistance, etc. decrease. 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 improve the adhesion with the lower substrate. 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-glycidyloxypropyl) methyldiethoxysilane, (3-glycidyloxypropyl) dimethylethoxysilane, 3,4-epoxybutyl 3,4-epoxy butyl trimethoxysilane, 3,4-epoxybutyl ester triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, 3-triethoxysilane-N- (1, 3-triethoxysilly-n- (1,3 dimethyl-butylidene) propylamine, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane , N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, (3-isocyanatepropyl) triethoxysilane, (3-isocyanatepropyl) triethoxysilane, and the like Agents or two or more of them.

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

In addition, the solvent of d) used in the present invention is used for coating a photosensitive resin composition on a substrate or the like. As a specific example, 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 Acid ester, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol monomethyl ether, butyl ether Diethylene glycol monoethyl ether, dibutyl glycol dimethyl ether, dibutyl 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 diethylene glycol Methyl hexyl ether glycol, a solvent may be used alone or in combination of two or more.

Preferably, the solvent in the step d) comprises 10% by weight to 50% by weight of the solid content of the positive photosensitive resin composition. When the solid content is less than 10% by weight, there is a problem that the coating thickness becomes thinner and the coating uniformity decreases. When the solid content is more than 50% by weight, there is a problem that the coating thickness becomes thick and the Problems affecting coating equipment. In the case where the solid content of the total composition is from 10% by weight to 25% by weight, it is advantageous to use a slit coater (Slit Coater), and the solid content of the total composition is 25 In the case of a weight percentage to 50 weight percentage, it is advantageous to use it in a slit coater or a slit spin coater (Slit & Spin Coater).

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

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

First, the positive photosensitive resin composition of the present invention is applied to the surface of a substrate by spin coating, slit spin coating, slit coating, roll coating, or the like, and the solvent is removed by a prebaking machine to form a coating film. At this time, preferably, the pre-baking 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 light, ultraviolet rays, extreme ultraviolet rays, electron rays, X-rays, etc. according to a pattern prepared in advance, and development is performed using a developing solution to remove unnecessary portions, thereby forming a predetermined pattern.

As the developing solution, an alkaline aqueous solution is preferably used. Specifically, inorganic bases such as sodium hydroxide, calcium hydroxide, and calcium carbonate can be used; primary amines such as ethylamine and n-propylamine; and secondary amines such as ethylamine and n-propylamine. Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; or tetramethylammonium hydroxide, An aqueous solution of a quaternary ammonium salt such as tetraethylammonium hydroxide. At this time, the developing solution is used by dissolving a basic compound at a concentration of 0.1 to 10 parts by weight, and a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added in an appropriate amount.

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

The photosensitive resin composition of the present invention has excellent flatness, transmittance, and outgassing properties, and in particular has excellent sensitivity, and has remarkable adhesion, contrast, and chemical resistance under high temperature and high humidity conditions. It is improved to be suitable for forming an interlayer insulating film, a pixel definition layer, a pillar interval, and the like in a manufacturing process of a liquid crystal display and an organic light emitting diode. The present invention may further include a display element including a cured product of the positive photosensitive resin composition.

In the following, preferred embodiments are provided to help understand the present invention, 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) was subjected to a condensation reaction with 2.0 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare 4,4 ', 4 "-[cyclohexan Alkane-1,1,4-triyl] triphenol1,2-diazidenaphthoquinone-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] tri [2-methylphenol] (4,4', 4 ''-(cyclohexane-1,1,4-triyl) tris (2-methylphenol)) is subjected to a condensation reaction with 2.0 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to Preparation of 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] tri [2-methylphenol] 1,2-diazidenaphthoquinone-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] tri [2,6-dimethylphenol] (4, 4 ', 4''-(cyclohexane-1,1,4-triyl) tris (2,6-dimethylphenol)) and 2.0 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride ] Condensation reaction to prepare 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] tri [2,6-dimethylphenol] 1,2-diazidenaphthoquinone- 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 -Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3-diol 1 , 2-Diazidonaphthoquinone-5-sulfonate. Chemical formula 7:

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

By making 1 mole 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-diazidenaphthoquinone-5- Sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- [1- [3-cyclohexyl-4-hydroxy-5-methylphenyl] cyclohexyl] -6-toluene-1,3-diol1,2 -Diazonaphthoquinone-5-sulfonate. Chemical formula 8:

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

By making 1 mole 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) was subjected to a condensation reaction with 2.0 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare 4- [1- [4-hydroxy-3-methyl-5- [4 -Methylcyclohexyl] phenyl] -4-methylcyclohexyl] -6-toluene-1,3-diol] 1,2-diazidenaphthoquinone-5-sulfonate. Chemical formula 9:

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

By synthesizing 1,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol represented by Chemical Formula 4 in Synthesis Example 1 with 1 mole, and 1.0 mole of 1,2- Diazonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triol Amino naphthoquinone-5-sulfonate.

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

By synthesizing 1,4 ', 4 "-[cyclohexane-1,1,4-triyl] triol represented by Chemical Formula 4 in Synthesis Example 1 with 1 mole, and 1.2 mole of 1,2- Diazonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triol Amino naphthoquinone-5-sulfonate.

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

By synthesizing 1,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol represented by Chemical Formula 4 in Synthesis Example 1 with 1 mole and 1.5 mole of 1,2- Diazonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triol Amino naphthoquinone-5-sulfonate.

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

By synthesizing 1,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol represented by Chemical Formula 4 in Synthesis Example 1 with 1 mole and 2.5 moles of 1,2- Diazidenaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 ', 4 "-[cyclohexane-1-triphenol-1,2-diazidenaphthoquinone-5 -Sulfonate.

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

By synthesizing 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 of 1 mole with 1.0 mole of 1,2-Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3- Diol 1,2-diazidenaphthoquinone-5-sulfonate.

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

By synthesizing 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 with 1 mole, and 1.5 moles 1,2-Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3- Diol 1,2-diazidenaphthoquinone-5-sulfonate.

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

By synthesizing 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3-diol represented by Chemical Formula 7 in Synthesis Example 4 with 1 mole, and 2.5 moles 1,2-Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- [1- [3-cyclohexyl-4-hydroxyphenyl] cyclohexyl] benzene-1,3- Diol 1,2-diazidenaphthoquinone-5-sulfonate.

Synthesis Example 14: Preparation of acrylic copolymer (A)

Into a flask having a cooler and a stirrer, 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 were charged. And 30 parts by weight of a mixed solution of glycidyl methacrylate. After the liquid-phase composition was sufficiently mixed in a mixing container at 600 rpm, 15 parts by weight of 2,2'-bisazo- (2,4-dimethylvaleronitrile) was added. After slowly raising the polymerization mixed solution to 55 ° C. and maintaining the temperature for 24 hours, it was cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content concentration of 25% by weight. The acrylic copolymer had a weight average molecular weight of 6000. At this time, the weight average molecular weight is a polystyrene equivalent 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 charged into a flask having a cooler and a stirrer. After the liquid-phase composition was sufficiently mixed in a mixing container at 600 rpm, 10 parts by weight of 2,2'-bisazo- (2,4-dimethylvaleronitrile) was added. After slowly raising the polymerization mixed solution to 55 ° C. and maintaining the temperature for 24 hours, it was cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content concentration of 30% by weight.

In order to remove unreacted monomers of the polymer solution, 100 parts by weight of the polymer solution was precipitated with respect to 1,000 parts by weight of n-Hexane. After the precipitation, the poor solvent (Poor solvent) in which unreacted substances are dissolved is removed by a filtering process using a mesh. Thereafter, in order to remove the solvent containing unreacted monomers remaining after the filtration process, the acrylic copolymer was prepared by completely removing it by vacuum drying at a temperature of 30 ° C. or lower.

The acrylic copolymer had a weight average molecular weight of 10,000. At this time, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured using a gel permeation chromatography.

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 charged into a flask having a cooler and a stirrer. After the liquid-phase composition was sufficiently mixed in a mixing container at 600 rpm, 5 parts by weight of 2,2'-bisazo- (2,4-dimethylvaleronitrile) was added. After slowly raising the polymerization mixed solution to 55 ° C. and maintaining the temperature for 24 hours, it was cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content concentration of 30% by weight.

In order to remove unreacted monomers of the polymer solution, 100 parts by weight of the polymer solution was precipitated with respect to 1,000 parts by weight of n-hexane. After the precipitation, the poor solvent in which unreacted substances are dissolved is removed by a filtration process using a filter. Thereafter, in order to remove the solvent containing unreacted monomers remaining after the filtration process, the acrylic copolymer was prepared by completely removing it by vacuum drying at a temperature of 30 ° C. or lower.

The acrylic copolymer had a weight average molecular weight of 16,000. At this time, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured using a gel permeation chromatography.

Synthesis Example 17: Preparation of acrylic copolymer (D)

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

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

By making 1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] represented by the following Chemical Formula 10 Bisphenol is subjected to a condensation reaction with 2.0 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare 4,4 '-[1- [4- [1- [4-hydroxybenzene Group] -1-methylethyl] phenyl] ethylene] bisphenol 1,2-diazidenaphthoquinone-5-sulfonate. Chemical formula 10:

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

By making 1 mole of 4,4 '-[1,3-phenylenebis [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-diazidenaphthoquinone-5 -Sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 '-[1,3-phenylenebis [propane-2,2-diyl]] bis [benzene-1,3-diol] 1, 2-Diazidonaphthoquinone-5-sulfonate. Chemical formula 11:

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

By making 1 mol of [4- [2-phenylpropane-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-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare [4- [2-phenylpropane-2-yl] Benzene-1,3-diol] 1,2-diazidenaphthoquinone-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-diazidenaphthoquinone-5-sulfonic acid [chloride] To prepare 4- (7-hydroxy-2,4,4-trimethylchroman-2-yl) benzene-1,3-diol 1,2-diazidenaphthoquinone-5-sulfonate. Chemical formula 13:

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

By using 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 Preparation of 4- (7-hydroxy-2,4,4-trimethylchroman-2- by condensation reaction with 2.0 mol of 1,2-diazidonaphthoquinone-5-sulfonic acid [chloride] ) Benzene-1,3-diol 1,2-diazidenaphthoquinone-5-sulfonate. Chemical formula 14:

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

By making 1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] represented by the chemical formula 10 Bisphenol is subjected to a condensation reaction with 1.5 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare 4,4 '-[1- [4- [1- [4-hydroxybenzene Group] -1-methylethyl] phenyl] ethylene] bisphenol 1,2-diazidenaphthoquinone-5-sulfonate.

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

By making 1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] represented by the chemical formula 10 Bisphenol reacts with 2.5 mol of 1,2-diazidenaphthoquinone-5-sulfonic acid [chloride] to prepare 4,4 '-[1- [4- [1- [4-hydroxybenzene Group] -1-methylethyl] phenyl] ethylene] bisphenol 1,2-diazidenaphthoquinone-5-sulfonate.

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

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

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

By making 1 mol of 4,4 '-[1,3-phenylene di [propane-2,2-diyl]] represented by the chemical formula 11 and 2.5 mol of 1,2-dipyrimid Nitronaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4,4 '-[1,3-phenylenebis [propane-2,2-diyl]] bis [benzene-1,3 -Diol] 1,2-diazidenaphthoquinone-5-sulfonate.

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

By making 1 mol of [4- [2-phenylpropane-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] is subjected to a condensation reaction to prepare [4- [2-phenylpropane-2-yl] benzene-1,3-diol] 1,2-diazidenaphthoquinone- 5-sulfonate.

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

By making 1 mole of [4- [2-phenylpropane-2-yl] benzene-1,3-diol] represented by the chemical formula 12 and 2.5 mole of 1,2-diazide Naphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare [4- [2-phenylpropane-2-yl] benzene-1,3-diol] 1,2-diazidenaphthoquinone- 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-Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- (7-hydroxy-2,4,4-trimethylchroman-2-yl) benzene-1 , 3-diol 1,2-diazidenaphthoquinone-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-Diazidonaphthoquinone-5-sulfonic acid [chloride] is subjected to a condensation reaction to prepare 4- (7-hydroxy-2,4,4-trimethylchroman-2-yl) benzene-1 , 3-diol 1,2-diazidenaphthoquinone-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-diazidenaphthoquinone-5 -Sulfonic acid [chloride] is subjected to a 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 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-diazidenaphthoquinone-5 -Sulfonic acid [chloride] is subjected to a 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 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 charged into a flask having a cooler and a stirrer. After the liquid-phase composition was thoroughly mixed in a mixing container at 600 rpm, 18 parts by weight of 2,2'-bisazo- (2,4-dimethylvaleronitrile) was added. After slowly raising the polymerization mixed solution to 55 ° C. and maintaining the temperature for 24 hours, it was cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content concentration of 30% by weight.

In order to remove unreacted monomers of the polymer solution, 100 parts by weight of the polymer solution was precipitated with respect to 1,000 parts by weight of n-hexane. After the precipitation, the poor solvent in which unreacted substances are dissolved is removed by a filtration process using a filter. Thereafter, in order to remove the solvent containing unreacted monomers remaining after the filtration process, the acrylic copolymer was prepared by completely removing it by vacuum drying at a temperature of 30 ° C. or lower.

The acrylic copolymer has a weight average molecular weight of 2500. At this time, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured using a gel permeation chromatography.

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 charged into a flask having a cooler and a stirrer. After the liquid-phase composition was sufficiently mixed in a mixing container at 600 rpm, 1.5 parts by weight of 2,2'-bisazo- (2,4-dimethylvaleronitrile) was added. After slowly raising the polymerization mixed solution to 55 ° C. and maintaining the temperature for 24 hours, it was cooled to normal temperature, and 500 ppm of hydroxybenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content concentration of 30% by weight.

In order to remove unreacted monomers of the polymer solution, 100 parts by weight of the polymer solution was precipitated with respect to 1,000 parts by weight of n-hexane. After the precipitation, the poor solvent in which unreacted substances are dissolved is removed by a filtration process using a filter. Thereafter, in order to remove the solvent containing unreacted monomers remaining after the filtration process, the acrylic copolymer was prepared by completely removing it by vacuum drying at a temperature of 30 ° C. or lower.

The acrylic copolymer had a weight average molecular weight of 22,000. At this time, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured using a gel permeation chromatography.

Example 1: Preparation of a 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 was dissolved in 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol 1,2-diazidenaphthoquinone-5-sulfonate prepared in Example 1 and 3 parts by weight as After (3-glycidyloxypropyl) trimethoxysilane of a silane coupling agent, it filtered with a 0.1 micrometer micropore filter, and prepared the photosensitive resin composition.

Example 2: Preparation of a 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 (B) of Synthesis Example 1. A) Except for use, a photosensitive resin composition was prepared in the same manner as in Example 1.

Example 3: Preparation of a 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 use, a photosensitive resin composition was prepared in the same manner as in Example 1.

Example 4: Preparation of a 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 (D) of Synthesis Example 1 ( A) Except for use, a photosensitive resin composition was prepared in the same manner as in Example 1.

Example 5: Preparation of a 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 use, a photosensitive resin composition was prepared in the same manner as in Example 1.

Example 6: Preparation of a photosensitive resin composition

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

Example 7: Preparation of a photosensitive resin composition

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

Example 8: Preparation of a photosensitive resin composition

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

Example 9: Preparation of a photosensitive resin composition

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

Example 10: Preparation of a photosensitive resin composition

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

Example 11: Preparation of a photosensitive resin composition

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

Example 12: Preparation of a photosensitive resin composition

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

Example 13: Preparation of a photosensitive resin composition

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

Example 14: Preparation of a photosensitive resin composition

In order to make 100% by weight of the acrylic copolymer (D) prepared in Synthesis Example 17 so that the solid content of the mixture is 20% by weight, 30 parts by weight of propylene glycol monomethyl ether acetate was dissolved in 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol 1,2-diazidenaphthoquinone-5-sulfonate prepared in Example 1 and 3 parts by weight as After (3-glycidyloxypropyl) trimethoxysilane of a silane coupling agent, it filtered with a 0.1 micrometer micropore filter, and prepared the photosensitive resin composition.

Example 15: Preparation of a photosensitive resin composition

In order to make the solid content of the mixture 20% by weight based on 100 parts by weight of the acrylic copolymer (B) prepared in Synthesis Example 15, 30 parts by weight of propylene glycol monomethyl ether acetate was dissolved. 4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol 1,2-diazidenaphthoquinone-5-sulfonate and 3 parts by weight of ( After 3-glycidyloxypropyl) trimethoxysilane was filtered through a 0.1 μm microporous filter, a photosensitive resin composition was prepared.

Example 16: Preparation of a photosensitive resin composition

In order to make the solid content of the mixture 20% by weight based on 100 parts by weight of the acrylic copolymer (C) prepared in Synthesis Example 16, 30 parts by weight of propylene glycol monomethyl ether acetate was dissolved. 4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol 1,2-diazidenaphthoquinone-5-sulfonate and 3 parts by weight of ( After 3-glycidyloxypropyl) trimethoxysilane was filtered through a 0.1 μm microporous filter, a photosensitive resin composition was prepared.

Comparative Example 1: Preparation of a photosensitive resin composition

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

Comparative Example 2: Preparation of a 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) A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was used.

Comparative Example 3: Preparation of a 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) A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was used.

Comparative Example 4: Preparation of a 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) A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was used.

Comparative Example 5: Preparation of a photosensitive resin composition

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

Comparative Example 6: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 7: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 8: Preparation of a 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 compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 9: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

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

Comparative Example 11: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 12: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

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

Comparative Example 14: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 15: Preparation of a 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 used instead of the 1,2-quinonediazide-5-sulfonic acid compound of Synthesis Example 1. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the ester compound (A) was used.

Comparative Example 16: Preparation of a photosensitive resin composition

In order to make the solid content of the mixture 20% by weight with respect 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 was dissolved 4,4 ', 4 "-[cyclohexane-1,1,4-triyl] triphenol 1,2-diazidenaphthoquinone-5-sulfonate prepared in Synthesis Example 1 and 3 parts by weight of (3-Glycidyloxypropyl) trimethoxysilane, which is a silane coupling agent, was filtered through a 0.1 μm microporous filter to prepare a photosensitive resin composition.

Comparative Example 17: Preparation of a photosensitive resin composition

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

The physical properties such as sensitivity, resolution, curing process range, transmittance, heat discoloration resistance, adhesion, heat resistance and the like of Examples 1 to 4 and Comparative Examples 1 to 5 were measured and shown in Table 1. The photosensitive resin compositions of Examples 1 to 15 and Comparative Examples 1 to 17 were coated on a glass substrate using a spin coater, and then prebaked at a temperature of 100 ° C on a hot plate. It took 2 minutes to form a film having a thickness of 4.0 μm.

A) Sensitivity: In a film formed in the manner described above, a prescribed pattern mask is used, and the intensity in a Broadband at a standard dose of 10 μm Contact Hole CD (Dose) is After 20 mW / cm ² of ultraviolet light, development was carried out with an aqueous solution of 2.38 weight percent of tetramethylammonium hydroxide 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: The minimum size of the contact hole pattern (Pattern) of 10 μm formed when measuring the sensitivity of the above 1) is measured.

(3) Curing process range: a pattern film is formed in the same method as in the measurement of the sensitivity described in (1) above, and a dimensional change rate before and after curing is measured according to a contact hole size standard of 10 μm. At this time, a case where the change rate is 0 to 10% is marked as ○, a case where the change rate is 10 to 20% is marked as Δ, and a case where the change rate is more than 20% is marked as ×.

(4) Permeability: The evaluation of the permeance is determined by measuring the transmittance of the pattern film at 400 nm using a spectrophotometer in the pattern film formed when the sensitivity of the above-mentioned one) is measured. At this time, a case where the transmittance is 90% or more is marked as ○, a case where the transmittance is 85 to 90% is marked as Δ, and a case where the transmittance is less than 80% is marked as x.

5) Heat discoloration resistance: The substrate measured during the evaluation of the above 4) permeability was further cured in an oven at 230 ° C. for 30 minutes, and the transmittance of the pattern film before and after curing was 400 nm. Change to evaluate heat discoloration resistance. At this time, a case where the change rate is less than 3% is marked as ○, a case where the change rate is 3 to 5% is marked as Δ, and a case where the change rate is greater than 5% is marked as ×.

(6) Adhesive force: The adhesive force of the pattern film formed when the sensitivity of the pattern (1) is measured by using the scope and according to whether the pattern is lost or not.

The case where the cohesion is ensured at a pre-baking temperature above 95 ° C is marked as ○, and the case where the pre-baking temperature is 100 to 105 ° C is used to ensure the cohesive force is marked as △. The pre-baking temperature above 105 ° C is used to ensure the cohesive force or The case where the pattern is lost is marked with ×.

7) Heat resistance: TGA is used to measure heat resistance. After the pattern film formed when the sensitivity of the above-mentioned one) is measured is sampled, the temperature is raised to 900 ° C. at a temperature of 10 ° C. per minute by using TGA. The case where the temperature of 5 weight percent loss is greater than 300 ° C is marked as ○, the case where the temperature of 5 weight percent loss is 280 to 300 ° C is marked as △, and the case where the temperature of 5 weight percent loss is greater than 280 ° C is marked as × .

Table 1

According to the Table 1, according to the present invention, the positive photosensitive insulating film composition prepared in Examples 1 to 16 has excellent resolution, curing process range, transmittance, heat discoloration resistance, and heat resistance. . In addition, compared to Examples 1 to 16, the transmittance and heat discoloration resistance of Comparative Examples 1 to 15 were lowered, and the heat resistance was lower than that of Comparative Examples 5, Comparative Example 14, Comparative Example 15, and Comparative Example 16. Excellent, especially compared with Comparative Example 1 to Comparative Example 17, excellent sensitivity, which can shorten the tact of the process, ensure excellent panel light characteristics and reliability with 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. From this, it can be seen that the photosensitive resin composition can be applied to various display fields.

no

no

Claims (13)

A positive photosensitive resin composition comprising: a) a 1,2-quinonediazide compound of the following Chemical Formula 1 or Chemical Formula 2; b) an acrylic copolymer; c) a silane coupling agent; and d) a solvent , Chemical formula 1: R _{1 of} this Chemical Formula 1 is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonate, R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ₁ Is 1,2-quinonediazide sulfonate, chemical formula 2: R _{3 of} the chemical formula 2 is each independently a hydrogen atom or a 1,2-quinonediazide sulfonate, R _{4 is} each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ₃ is It is 1,2-quinonediazide sulfonate. The positive photosensitive resin composition according to item 1 of the patent application scope, comprising: 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 an acrylic copolymer; c) 0.1 to 30 parts by weight of a silane coupling agent; and d) a solvent so that the solid content in the positive photosensitive resin composition reaches 10% by weight To 50 weight percent. The positive-type photosensitive resin composition according to item 1 of the scope of patent application, wherein the 1,2-quinonediazide-based sulfonate is selected from the group consisting of 1,2-quinonediazide-4-sulfonate, One or more of the group consisting of 1,2-quinonediazide-5-sulfonate and 1,2-quinonediazide-6-sulfonate. The positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the 1,2-quinonediazide-based sulfonate is 1,2-quinonediazide-5-sulfonate. The positive-type photosensitive resin composition according to item 2 of the patent application range, wherein the acrylic copolymer is prepared by i) 5 to 40 parts by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof. Ii) 10 to 70 parts by weight of an unsaturated compound containing an epoxy group and iii) 5 to 70 parts by weight of an olefinic unsaturated compound are prepared by copolymerization. The positive photosensitive resin composition according to item 5 of the scope of the patent application, wherein the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride or a mixture thereof of ii) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, rich One or more of the group consisting of maleic acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of their unsaturated dicarboxylic acids. The positive-type 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-ethyl acrylic acid. Glycidyl ester, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, acrylic acid-β-methyl glycidyl ester, methacrylic acid-β-methyl glycidyl ester, acrylic acid-β- Ethyl glycidyl ester, β-ethyl glycidyl methacrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6,7-epoxy Heptyl ester, -6,7-epoxyheptyl methacrylate, α-ethylacrylic acid-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, One or more of the group consisting of vinyl benzyl glycidyl ether and 3,4-epoxycyclohexyl methacrylate. The positive-type photosensitive resin composition according to item 5 of the application, wherein the olefinic unsaturated compound of iii) is selected from the group consisting of methyl methacrylate, methyl ethyl acrylate, methyl n-butyl acrylate, and secondary Butyl methyl 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, dicyclopentyloxy methacrylate Ester, 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, vinyltoluene, p-methoxythremonene, 1,3-butane Ene, isoprene, 2,3-dimethyl-1,3-butadiene, 2 -[Methacryloxy] ethyl 6-hydroxyhexanoate, 4-vinylphenol, 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, [[4-hydroxymethyl] ring Hexyl] Group consisting of methyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 2-oxotetrahydrofuran-3-yl methacrylate, and 4-hydroxycyclohexyl methacrylate More than one of them. The positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the acrylic copolymer of b) is 3,000 to 20,000. The positive-type photosensitive resin composition according to item 1 of the scope of patent application, wherein the silane coupling agent of c) is selected from the group consisting of (3-glycidyloxypropyl) trimethoxysilane and (3-glycidyloxy) Propyl) triethoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, (3-glycidyloxypropyl) methyldiethoxysilane, (3-glycidyloxypropyl) Glyceryloxypropyl) dimethylethoxysilane, 3,4-epoxybutyl ester trimethoxysilane, 3,4-epoxybutyl ester triethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-trimethylsilane Ethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-amino Propyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl) One or more of the group consisting of triethoxysilane. The positive-type 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 ether, propylene glycol methyl ether acetate, and propylene glycol 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 ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Propylene glycol diethyl ether, butanediol monomethyl ether, butylene glycol monoethyl ether, dibutyl glycol dimethyl ether, dibutyl glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ether, triethylene glycol Glyme, 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 of the group consisting of dipropylene glycol ethylhexyl ether and dipropylene glycol methylhexyl ether. A display element includes a cured product of the positive-type photosensitive resin composition according to item 1 of the scope of patent application. A pattern forming method for a display element includes a step of forming a pattern for an interlayer insulating film manufactured by applying a positive-type photosensitive resin composition as described in item 1 of the scope of patent application.