KR102433199B1 - Positive photosensitive resin composition - Google Patents

Abstract

상기 화학식 1의 R₁, 화학식 2의 R₃는 각각 독립적으로 수소원자 또는 1,2-퀴논디아지드계 술폰산 에스테르이고 화학식 1의 R₂, 화학식 2의 R₄는 각각 독립적으로 수소원자 또는 탄소수 1 내지 20의 탄화수소기를 나타내며, 상기 R₁, R₃의 각각 적어도 하나는 1,2-퀴논디아지드계 술폰산 에스테르이다.The present invention relates to a positive photosensitive resin composition, and more particularly, in the photosensitive resin composition, a) a 1,2-quinonediazide compound represented by the following formula (1) or (2); b) an acrylic copolymer; c) a silane coupling agent; And d) a solvent; A positive photosensitive resin composition comprising:
[Formula 1] [Formula 2]

R ₁ of Formula 1 and R ₃ of Formula 2 are each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester, and R ₂ of Formula 1 and R ₄ of Formula 2 are each independently a hydrogen atom or a carbon number of 1 to 20 hydrocarbon groups, wherein at least one of R ₁ and R ₃ is a 1,2-quinonediazide-based sulfonic acid ester.

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive resin composition, and more particularly, an LCD and OLED manufacturing process that has excellent resolution, curing process margin, heat discoloration resistance, heat resistance, etc., and particularly has excellent sensitivity and transparency, and significantly improves adhesion. It relates to a photosensitive resin composition suitable for forming an interlayer insulating film, PDL (Pixel Define Layer), column spacer, and the like.

2. Description of the Related Art In general, flat panel displays are widely used display devices, and there are various types such as a liquid crystal display (LCD) and an organic light emitting display (OLED).

In the manufacturing process of TFT-type liquid crystal display (LCD) and organic light emitting display (OLED), an interlayer insulating film is used to insulate between wirings arranged between layers.

In particular, as high-speed response and high-resolution devices are recently developed, high aperture ratio and low resistance wiring technology are required. To this end, the width of the circuit is reduced and the thickness is formed to be high, so that the step difference of the TFT tends to be large. In this case, the thickness of the interlayer insulating film applied for flatness is increased, which causes a decrease in sensitivity and transparency, thereby reducing panel productivity and quality. Therefore, the development of an insulating film excellent in sensitivity and transparency is urgently required.

Therefore, an object of the present invention is to have excellent resolution, curing process margin, heat discoloration resistance, heat resistance, especially sensitivity and transparency, and remarkably improve adhesion to interlayer insulating film, PDL, column spacer, etc. It is to provide a photosensitive resin composition suitable for forming a.

Another object of the present invention is to provide an LCD and an OLED substrate including a cured product of the photosensitive resin composition.

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

In order to achieve the above object, the present invention, a) a 1,2-quinonediazide compound of Formula 1 or 2; b) an acrylic copolymer; c) a silane coupling agent; And d) a solvent; provides a photosensitive resin composition comprising:

[Formula 1]

In Formula 1, R ₁ is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester, R ₂ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ₁ is 1 ,2-quinonediazide-based sulfonic acid ester .

[Formula 2]

In Formula 2, R ₃ is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester, R ₄ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ₃ is 1 ,2-quinonediazide-based sulfonic acid ester .

The positive photosensitive resin composition used in the present invention has excellent resolution, curing process margin, heat discoloration resistance, and heat resistance, and particularly has excellent sensitivity and transmittance, and remarkably improves adhesion, so that the interlayer insulating film and PDL of the LCD and OLED manufacturing process, A photosensitive resin composition suitable for forming a column spacer or the like can be provided. In addition, it provides an LCD and an OLED substrate including a cured product of the photosensitive resin composition, and a pattern forming method of a display substrate using the photosensitive resin composition. The pattern may be used as a material for a passivation insulating film such as TFT-LCD, TSP (Touch Screen Panel), OLED, O-TFT, EPD, and EWD, a gate insulating film, a planarization film, a column spacer, a barrier rib, and the like.

Hereinafter, the present invention will be described in detail.

The present invention relates to a photosensitive resin that can be used in various fields such as an interlayer insulating film, a passivation insulating film, a gate insulating film, an overcoat, a column spacer, a PDL, and a barrier rib disposed between layers of a liquid crystal display (LCD) and an organic light emitting display (OLED). to the composition.

The positive photosensitive resin composition of the present invention,

a) a 1,2-quinonediazide compound of Formula 1 or 2;

b) an acrylic copolymer;

c) a silane coupling agent; and

d) a solvent;

[Formula 1]

In Formula 1, R ₁ is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester, and R ₂ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 20 carbon atoms. An alkyl group 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, wherein at least one of R ₁ is a 1,2-quinonediazide-based sulfonic acid ester.

[Formula 2]

In Formula 2, R ₃ is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester, and R ₄ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 20 carbon atoms. An alkyl group 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, wherein at least one of R ₃ is a quinonediazide-based sulfonic acid ester.

The 1,2-quinonediazide compound represented by Formula 1 or 2 of a) used in the present invention is a photosensitive compound (Photo Active Compound: PAC),

Specific examples of the 1,2-quinonediazide-based sulfonic acid ester of Formula 1 or 2 include 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide. Zide 6-sulfonic acid ester, etc., and a more specific example is 1,2-quinonediazide 5-sulfonic acid ester 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 an alkali developer, and suppressing the alkali solubility of the photosensitive resin film in unexposed areas, to form a positive pattern.

[Formula 3]

The 1,2-quinonediazide compound of Formula 1 or 2 may be prepared by, for example, reacting 1,2-quinonediazide 5-sulfonic acid halogen compound with a phenol compound under a weak base.

The 1,2-quinonediazide compound of Formula 1 or 2 is b) 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer. it is preferable When the content is less than 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part is small, making it difficult to form a pattern. When it exceeds 50 parts by weight, unreacted 1,2-quinonediazide-based sulfonic acid ester when irradiated with light for a short time. Since a large amount of the compound remains, solubility in an aqueous alkali solution, which is a developer, is too low, so that development is difficult.

The acrylic copolymer of b) of the present invention is a monomer comprising: i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, ii) an unsaturated compound containing an epoxy group; and iii) an olefin-based unsaturated compound. For example, the acrylic copolymer may be prepared by radically reacting these monomers in the presence of a solvent and a polymerization initiator.

The unsaturated carboxylic acid of i), the unsaturated carboxylic acid anhydride, or a mixture thereof is an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, methaconic acid, and itaconic acid; Alternatively, the anhydrides of these unsaturated dicarboxylic acids may be used alone or in combination of two or more. In particular, it is more preferable to use acrylic acid, methacrylic acid, or maleic anhydride in terms of copolymerization reactivity and solubility in aqueous alkali solution as a developer. do.

The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is preferably included in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on the total total monomers. When the content is less than 5 parts by weight, there is a problem in that it is difficult to dissolve in the aqueous alkali solution, and when it exceeds 40 parts by weight, there is a problem that the solubility in the aqueous alkali solution becomes excessively large.

The epoxy group-containing unsaturated compound of ii) is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butylacrylate Cydyl, acrylate-β-methyl glycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl , acrylic acid-3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl, acrylic acid-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, methacrylic acid 3,4-epoxy cyclohexyl (3,4-epoxy cyclohexyl methacrylate) may be used alone or in a mixture of two or more, preferably glycidyl methacrylate, methacrylic acid-β-methylglycidyl, 6,7-epoxyheptyl methacrylic acid, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylic acid, etc. It is more preferable to use in order to improve the copolymerization reactivity and heat resistance of the pattern obtained.

The epoxy group-containing unsaturated compound is preferably included in an amount of 10 to 70 parts by weight, preferably 20 to 50 parts by weight, based on the total monomers. 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 may be simultaneously satisfied.

The olefinically unsaturated compound of iii) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate , isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, Dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isoboronyl methacrylate Rate (isoboronyl methacrylate), cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboronyl acrylate, phenyl methacrylate (phenyl methacrylate), phenyl acrylate, benzyl acrylate (benzyl acrylate), 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p- Methoxy styrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3-butadiene (2,3-dimethyl-1,3-butadiene), 2- [methacryloyloxy] ethyl 6-hydroxyhexanate, 4-vinylphenol, 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, [[4-hydroxymethyl] cyclohexyl] methyl methacrylate, 3-hydroxy-1 -Methacryloyloxyadamantane, 2-oxotetrahydrofuran-3-yl methacrylate, 4-hydroxycyclohexyl methacrylate, etc. can be used. and the above compounds may be used alone or in combination of two or more.

The olefinically unsaturated compound is preferably included in an amount of 10 to 70 parts by weight, preferably 20 to 50 parts by weight, based on the total total monomers. When the content is within the above range, swelling does not occur after development, and the solubility of an aqueous alkali solution as a developer can be ideally maintained.

The solvent used for solution polymerization of the above monomers may be methanol, tetrahydroxyfuran, toluene, dioxane, or the like.

The polymerization initiator used for solution polymerization of the above monomers may be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile (2,2-azobisisobutyronitrile), 2,2-azobis (2 ,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis(cyclohexane-1-carbonitrile), or dimethyl 2, 2'-azobisisobutylate (2,2'-azobisisobutylate), etc. can be used.

The acrylic copolymer obtained by radically reacting the above monomers in the presence of a solvent and a polymerization initiator, and removing unreacted monomers through precipitation, filtration, and vacuum drying processes, has a polystyrene conversion weight average molecular weight (Mw) of 3,000 to It is preferably 20,000. In the case of an interlayer insulating film (organic insulating film) having a polystyrene equivalent weight average molecular weight of less than 3,000, there is a problem in that developability and residual film rate, etc., or pattern development and heat resistance, etc. are inferior. In the case of an interlayer insulating film exceeding 20,000, pattern development There is a problem with this being behind.

In addition, the silane coupling agent of c) used in the present invention is used to improve adhesion with the lower substrate, (3-glycidoxypropyl) trimethoxysilane ((3-glycidoxypropyl) trimethoxysilane), (3-glycidoxypropyl) Cidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3, 3,4-epoxy butyl trimethoxysilane, 3,4-epoxybutyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-( 3,4-Epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3 dimethyl-butylidene) ) Propylamine (3-triethoxysilly-n- (1,3 dimethyl-butylidene) propylamine), N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriene Toxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl)triethoxysilane (3-isocyanatepropyl)triethoxysilane ), (3-isocyanatepropyl)trimethoxysilane, etc. may be used, and may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 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, adhesion to the lower substrate is reduced, and when it exceeds 30 parts by weight, storage stability and developability are deteriorated, and resolution is deteriorated.

In addition, the solvent of d) used in the present invention is used to coat the photosensitive resin composition on a substrate, and specific examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl. Ether acetate (propylene glycol methyl ether acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate Cypionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diphoropylene glycol diethyl ether, butylene glycol monomethyl ether; butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and 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 tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether, etc. and may be used alone or in combination of two or more.

The solvent of d) is preferably included so that the solid content of the positive photosensitive resin composition is 10 to 50 wt%. When the solid content is less than 10% by weight, the coating thickness becomes thin, and there is a problem that the coating uniformity is lowered. There is a problem that it can. When the solid content of the total composition is 10 to 25% by weight, it is easy to use in a slit coater, and when it is 25 to 50% by weight, a spin coater or a slit & spin coater (Slit & Spin) Coater) is easy to use.

The positive photosensitive resin composition of the present invention as described above is preferably used after filtering with a Millipore filter of 0.1 to 0.2 μm, etc. with a solids concentration of 10 to 50% by weight.

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

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

Then, a predetermined pattern is formed by irradiating visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, etc. to the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.

It is preferable to use an aqueous alkali solution as the developer, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; Alternatively, an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving an alkaline compound at a concentration of 0.1 to 10 parts by weight, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. By heat treatment at a temperature of 150 to 400 for 30 to 90 minutes, the final pattern can be obtained.

The photosensitive resin composition according to the present invention has excellent flatness, transmittance, outgas, and particularly excellent sensitivity, and remarkably improves adhesion at high temperature and high humidity, contrast ratio, and chemical resistance, so that the interlayer of LCD and OLED manufacturing process It is suitable for forming an insulating film, a PDL, a column spacer, and the like.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

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

4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by the following formula (4) (4,4',4"-[cyclohexane-1,1,4-triyl]triphenol ) 1 mol and 2.0 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] are condensed to react with 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1 ,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 4]

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

4,4',4"-[cyclohexane-1,1,4-triyl]tris[2-methylphenol](4,4',4''-(cyclohexane-1,1) represented by the following formula (5) 1 mol of ,4-triyl)tris(2-methylphenol)) and 2.0 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] were condensed to react 4,4',4"-[cyclohexane-1 ,1,4-triyl]tris[2-methylphenol]1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 5]

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

4,4',4"-[cyclohexane-1,1,4-triyl]tris[2,6-dimethylphenol](4,4',4''-(cyclohexane-1) represented by the following formula (6) 4,4',4"-[ by condensation reaction of 1 mol of ,1,4-triyl)tris(2,6-dimethylphenol)) Cyclohexane-1,1,4-triyl]tris[2,6-dimethylphenol]1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 6]

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

1 mole of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by the following formula (7) and 1,2-naphthoquinonediazide-5-sulfonic acid [ Chloride] by a condensation reaction of 2.0 moles to obtain 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol 1,2-naphthoquinonediazide-5-sulfonic acid ester prepared.

[Formula 7]

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

4-[1-[3-cyclohexyl-4-hydroxy-5-methylphenyl]cyclohexyl]-6-methylbenzene-1,3-diol (4-(1-(3-cyclohexyl) represented by the following formula (8) 1 mole of -4-hydroxy-5-methylphenyl)cyclohexyl)-6-methylbenzene-1,3-diol) and 2.0 moles of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] were condensed to react with 4-[ 1-[3-cyclohexyl-4-hydroxy-5-methylphenyl]cyclohexyl]-6-methylbenzene-1,3-diol 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 8]

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

4-[1-[4-hydroxy-3-methyl-5-[4-methylcyclohexyl]phenyl]-4-methylcyclohexyl]-6-methylbenzene-1,3-diol represented by the following formula (9) 1 mole of ](4-(1-(4-hydroxy-3-methyl-5-(4-methylcyclohexyl)phenyl)-4-methylcyclohexyl)-6-methylbenzene-1,3-diol) and 1,2-naphtho By condensation reaction of 2.0 moles of quinonediazide-5-sulfonic acid [chloride], 4-[1-[4-hydroxy-3-methyl-5-[4-methylcyclohexyl]phenyl]-4-methylcyclohexyl]- 6-methylbenzene-1,3-diol] 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 9]

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

1 mole of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Formula 4 in Synthesis Example 1 and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] ] 1.0 moles were subjected to a condensation reaction to prepare 4,4',4"-[cyclohexane-1 triphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester.

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

1 mole of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Formula 4 in Synthesis Example 1 and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] ] 1.2 moles were subjected to a condensation reaction to prepare 4,4',4"-[cyclohexane-1 triphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester.

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

1 mole of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Formula 4 in Synthesis Example 1 and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] ] 1.5 moles were subjected to a condensation reaction to prepare 4,4',4"-[cyclohexane-1 triphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester.

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

1 mole of 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol represented by Formula 4 in Synthesis Example 1 and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] ] 2.5 moles were subjected to a condensation reaction to prepare 4,4',4"-[cyclohexane-1 triphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester.

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

1 mole of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Formula 7 in Synthesis Example 3 and 1,2-naphthoquinonediazide-5 -Condensation reaction of 1.0 mol of sulfonic acid [chloride] to 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol 1,2-naphthoquinonediazide-5- A sulfonic acid ester was prepared.

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

1 mole of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Formula 7 in Synthesis Example 3 and 1,2-naphthoquinonediazide-5 -Condensation reaction of 1.5 moles of sulfonic acid [chloride] to 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol 1,2-naphthoquinonediazide-5- A sulfonic acid ester was prepared.

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

1 mole of 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol represented by Formula 7 in Synthesis Example 3 and 1,2-naphthoquinonediazide-5 -Condensation reaction of 2.5 moles of sulfonic acid [chloride] to 4-[1-[3-cyclohexyl-4-hydroxyphenyl]cyclohexyl]benzene-1,3-diol 1,2-naphthoquinonediazide-5- A sulfonic acid ester was prepared.

[Synthesis Example 14] Preparation of acrylic copolymer (A)

In a flask equipped with a cooler and a stirrer, 400 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of hydroxyethyl methacrylate, 20 parts by weight of methacrylic acid, 20 parts by weight of styrene, and 30 parts by weight of glycidyl methacrylate The mixed solution was added. After the liquid composition was sufficiently mixed at 600 rpm in a mixing vessel, 15 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 25 wt%. The weight average molecular weight of the acrylic copolymer was 6,000. In this case, the weight average molecular weight is the average molecular weight in terms of polystyrene measured using 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 and 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. After sufficiently mixing the liquid composition at 600 rpm in a mixing vessel, 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55 °C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 30 wt%.

In order to remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution is precipitated with respect to 1000 parts by weight of n-hexane. After precipitation, a poor solvent in which unreacted substances are dissolved is removed through a filtration process using a mesh. Thereafter, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, it was completely removed through vacuum drying at 30 degrees or less to prepare an acrylic copolymer.

The weight average molecular weight of the acrylic copolymer was 10,000. In this case, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

[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 and 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. After sufficiently mixing the liquid composition at 600 rpm in a mixing vessel, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55 °C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 30 wt%.

In order to remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution is precipitated based on 1000 parts by weight of n-hexane. After precipitation, the poor solvent in which the unreacted material is dissolved is removed through a filtration process using a mesh. Thereafter, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, it was completely removed through vacuum drying at 30 degrees or less to prepare an acrylic copolymer.

The weight average molecular weight of the acrylic copolymer was 16,000. In this case, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

[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 reaction time was adjusted so that the weight average molecular weight of the acrylic copolymer was 4,000. In this case, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

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

1 mole of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol represented by the following formula (10) and 1,2-naphthoquinonedia Condensation reaction of 2.0 moles of zid-5-sulfonic acid [chloride] to 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2 -Naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 10]

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

4,4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol](4,4'-(1,3) represented by the following formula (11) -phenylenebis(propane-2,2-diyl))bis(benzene-1,3-diol)) 1 mol and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] 2.0 mol 4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol] 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 11]

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

1 mole of [4-[2-phenylpropan-2-yl]benzene-1,3-diol](4-(2-phenylpropan-2-yl)benzene-1,3-diol) represented by the following formula (12) and [4-[2-phenylpropan-2-yl]benzene-1,3-diol] 1,2-naphthoquinone by condensing 2.0 moles of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] A diazide-5-sulfonic acid ester was prepared.

[Formula 12]

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

4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol (4-(7-hydroxy-2,4,4-trimethylchroman) represented by the following formula 13 -2-yl)benzene-1,3-diol) 1.0 moles and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] 2.0 moles were condensed to react 4-(7-hydroxy-2,4, 4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[Formula 13]

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

1.0 mole and 1,2-naphtho of 4,4'-[cyclohexane-1,1-diyl]diphenol (4,4'-(cyclohexane-1,1-diyl)diphenol) represented by the following formula (14) By condensation reaction of 2.0 moles of quinonediazide-5-sulfonic acid [chloride], 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naph Toquinonediazide-5-sulfonic acid ester was prepared.

[Formula 14]

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

1 mole of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol represented by Formula 10 and 1,2-naphthoquinonedia Condensation reaction of 1.5 moles of zid-5-sulfonic acid [chloride] to 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2 -Naphthoquinonediazide-5-sulfonic acid ester was prepared .

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

1 mole of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol represented by Formula 10 and 1,2-naphthoquinonedia 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2 by condensation reaction of 2.5 moles of zid-5-sulfonic acid [chloride] -Naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1 mole of 4,4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol] represented by Formula 11 and 1,2-naphthoquinone Condensation reaction of 1.5 moles of diazide-5-sulfonic acid [chloride] to 4,4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol] 1 ,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1 mole of 4,4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol] represented by Formula 11 and 1,2-naphthoquinone 4,4'-[1,3-phenylenebis[propane-2,2-diyl]]bis[benzene-1,3-diol] 1 by condensation reaction of 2.5 moles of diazide-5-sulfonic acid [chloride] ,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1 mole of [4-[2-phenylpropan-2-yl]benzene-1,3-diol] represented by the above formula (12) and 1.5 moles of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] are condensed By reaction, [4-[2-phenylpropan-2-yl]benzene-1,3-diol] 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1 mole of [4-[2-phenylpropan-2-yl]benzene-1,3-diol] represented by the above formula (12) and 2.5 moles of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] are condensed By reaction, [4-[2-phenylpropan-2-yl]benzene-1,3-diol] 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1.0 mole of 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol represented by Formula 13 and 1,2-naphthoquinonediazide-5- Condensation reaction of 1.5 moles of sulfonic acid [chloride] to 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naphthoquinonediazide-5 -Sulphonic acid ester was prepared.

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

1.0 mole of 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol represented by Formula 13 and 1,2-naphthoquinonediazide-5- 4-(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naphthoquinonediazide-5 by condensation reaction of 2.5 moles of sulfonic acid [chloride] -Sulphonic acid ester was prepared.

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

1.0 mol of 4,4'-[cyclohexane-1,1-diyl]diphenol represented by the above formula (14) and 1.5 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] were subjected to a condensation reaction to 4 -(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

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

1.0 mol of 4,4'-[cyclohexane-1,1-diyl]diphenol represented by Formula 14 and 2.5 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] were condensed to 4 -(7-hydroxy-2,4,4-trimethylchroman-2-yl)benzene-1,3-diol 1,2-naphthoquinonediazide-5-sulfonic acid ester was prepared.

[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 and 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. After the liquid composition was sufficiently mixed at 600 rpm in a mixing vessel, 18 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55 °C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 30 wt%.

In order to remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution is precipitated with respect to 1000 parts by weight of n-hexane. After precipitation, the poor solvent in which the unreacted material is dissolved is removed through a filtration process using a mesh. Thereafter, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, it was completely removed through vacuum drying at 30° C. or less to prepare an acrylic copolymer.

The weight average molecular weight of the acrylic copolymer was 2,500. In this case, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

[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 and 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. After sufficiently mixing the liquid composition at 600 rpm in a mixing vessel, 1.5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 55 °C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 30 wt%.

In order to remove unreacted monomers from the polymer solution, 100 parts by weight of the polymer solution is precipitated based on 1000 parts by weight of n-hexane. After precipitation, the poor solvent in which the unreacted material is dissolved is removed through a filtration process using a mesh. Thereafter, in order to remove the solvent containing the unreacted monomer remaining after the filtration process, it was completely removed through vacuum drying at 30° C. or less to prepare an acrylic copolymer.

The weight average molecular weight of the acrylic copolymer was 22,000. In this case, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

[Example 1] Preparation of photosensitive resin composition

Based on 100 parts by weight of the acrylic copolymer (A) prepared in Synthesis Example 14, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2 prepared in Synthesis Example 1 - Naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and (3-glycidoxypropyl) trimethoxysilane 3 parts by weight as a silane coupling agent Propylene glycol monomethyl ether so that the solid content of the mixture is 20% by weight After dissolving in acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

[Example 2] Preparation of photosensitive resin composition

Except for using the 1,2-quinonediazide 5-sulfonic acid ester compound (B) of Synthesis Example 2 in place of the 1,2-quinonediazide 5-sulfonic acid ester compound (A) of Synthesis Example 1 in Example 1 prepared a photosensitive resin composition in the same manner as in Example 1.

[Example 3] Preparation of photosensitive resin composition

Except for using the 1,2-quinonediazide 5-sulfonic acid ester compound (C) of Synthesis Example 3 in place of the 1,2-quinonediazide 5-sulfonic acid ester compound (A) of Synthesis Example 1 in Example 1 prepared a photosensitive resin composition 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-sulfonic acid ester compound (D) of Synthesis Example 4 was used instead of the 1,2-quinonediazide 5-sulfonic acid ester compound (A) of Synthesis Example 1 prepared a photosensitive resin composition in the same manner as in Example 1.

[Example 5] Preparation of photosensitive resin composition

Except for using the 1,2-quinonediazide 5-sulfonic acid ester compound (E) of Synthesis Example 5 instead of the 1,2-quinonediazide 5-sulfonic acid ester compound (A) of Synthesis Example 1 in Example 1 prepared a photosensitive resin composition in the same manner as in Example 1.

[Example 6] Preparation of photosensitive resin composition

Except for using the 1,2-quinonediazide 5-sulfonic acid ester compound (F) of Synthesis Example 6 in place of the 1,2-quinonediazide 5-sulfonic acid ester compound (A) of Synthesis Example 1 in Example 1 prepared a photosensitive resin composition in the same manner as in Example 1.

[Example 7] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 8] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 9] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 10] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 11] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 12] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 13] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except for that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 14] Preparation of photosensitive resin composition

Based on 100 parts by weight of the acrylic copolymer (D) prepared in Synthesis Example 17, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2 prepared in Synthesis Example 1 - Naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and (3-glycidoxypropyl) trimethoxysilane 3 parts by weight as a silane coupling agent Propylene glycol monomethyl ether so that the solid content of the mixture is 20% by weight After dissolving in acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

[Example 15] Preparation of photosensitive resin composition

Based on 100 parts by weight of the acrylic copolymer (B) prepared in Synthesis Example 15, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2 prepared in Synthesis Example 1 - Naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and (3-glycidoxypropyl) trimethoxysilane 3 parts by weight as a silane coupling agent Propylene glycol monomethyl ether so that the solid content of the mixture is 20% by weight After dissolving in acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

[Example 16] Preparation of photosensitive resin composition

Based on 100 parts by weight of the acrylic copolymer (C) prepared in Synthesis Example 16, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1,2 prepared in Synthesis Example 1 - Naphthoquinonediazide-5-sulfonic acid ester 30 parts by weight and (3-glycidoxypropyl) trimethoxysilane 3 parts by weight as a silane coupling agent Propylene glycol monomethyl ether so that the solid content of the mixture is 20% by weight After dissolving in acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

[Comparative Example 1] Preparation of photosensitive resin composition

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

[Comparative Example 2] Preparation of photosensitive resin composition

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

[Comparative Example 3] Preparation of photosensitive resin composition

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

[Comparative Example 4] Preparation of photosensitive resin composition

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

[Comparative Example 5] Preparation of photosensitive resin composition

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

[Comparative Example 6] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 7] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 8] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 9] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 10] Preparation of photosensitive resin composition

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 compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 11] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 12] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 13] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 14] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 15] Preparation of photosensitive resin composition

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 ester compound (A) of Synthesis Example 1 Except that, a photosensitive resin composition was prepared in the same manner as in Example 1.

[Comparative Example 16] Preparation of photosensitive resin composition

With respect to 100 parts by weight of the acrylic copolymer (E) prepared in Comparative Synthesis Example 16, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1 prepared in Synthesis Example 1, 30 parts by weight of 2-naphthoquinonediazide-5-sulfonic acid ester and 3 parts by weight of (3-glycidoxypropyl)trimethoxysilane as a silane coupling agent so that the solid content of the mixture is 20% by weight of propylene glycol monomethyl After dissolving in ether acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

[Comparative Example 17] Preparation of photosensitive resin composition

With respect to 100 parts by weight of the acrylic copolymer (F) prepared in Comparative Synthesis Example 17, 4,4',4"-[cyclohexane-1,1,4-triyl]triphenol 1 prepared in Synthesis Example 1, 30 parts by weight of 2-naphthoquinonediazide-5-sulfonic acid ester and 3 parts by weight of (3-glycidoxypropyl)trimethoxysilane as a silane coupling agent so that the solid content of the mixture is 20% by weight of propylene glycol monomethyl After dissolving in ether acetate, it was filtered through a 0.1 μm Millipore filter to prepare a photosensitive resin composition.

For Examples 1 to 4 and Comparative Examples 1 to 5, physical properties such as sensitivity, resolution, curing process margin, transmittance, heat discoloration resistance, adhesive strength, and heat resistance were measured and shown in Table 1 below. The photosensitive resin compositions in Examples 1 to 15 and Comparative Examples 1 to 17 were coated on a glass substrate using a spin coater, and then prebaked on a hot plate at 100 for 2 minutes to form a film having a thickness of 4.0 μm. .

A) Sensitivity - Using a predetermined pattern mask on the film formed as above, after irradiating an ultraviolet light with an intensity of 20 mW/cm2 in broadband with a sensitivity of 10 ㎛ Contact Hole CD-based dose, tetramethyl ammonium hydroxide After developing for 1 minute at 23 with an aqueous solution of 2.38 wt % of the seed, it was washed with ultrapure water for 1 minute.

Then, 400 mJ/cm2 of ultraviolet light having an intensity of 20 mW/cm2 at 365 nm was irradiated to the developed pattern above, and cured in an oven at 230°C for 30 minutes to obtain a pattern film having a thickness of 3.0 µm.

B) Resolution - The minimum size of the 10 μm contact hole pattern (Pattern) formed when measuring the sensitivity of A) was measured.

C) Curing process margin - A pattern film was formed in the same way as in the sensitivity measurement in A) above, but the CD change rate before and after curing was measured based on 10 ㎛ Contact Hole CD. At this time, the case where the rate of change was 0 to 10% was denoted by ○, the case where the rate of change was 10 to 20% was denoted by △, and the case where the change rate exceeded 20% was denoted by ×.

D) Transmittance - For the evaluation of transmittance, the transmittance of the pattern film formed during the sensitivity measurement of A) was measured at 400 nm using a spectrophotometer. At this time, the case where the transmittance was 90% or more was denoted by ○, the case of 85 to 90% was denoted by △, and the case of less than 80% was denoted by ×.

E) Heat discoloration resistance - Heat discoloration resistance by 400 nm transmittance change of the pattern film before and after curing by curing twice in an oven at 230°C for 30 minutes in addition to the measurement substrate at the time of evaluation of transparency of the above D). evaluated. At this time, the case where the change rate was less than 3% was denoted by ○, the case of 3 to 5% was denoted by △, and the case exceeding 5% was denoted by ×.

F) Adhesion - The adhesive strength was evaluated by whether the pattern was lost through the scope of the pattern film formed during the measurement of the sensitivity of A).

The case in which the pre-bake temperature is 95 ° C. or higher indicates that the adhesion is secured by ○, the case in which the adhesion is secured at 100-105 ° C is indicated by △, and the case in which the adhesion is secured over 105 ° C. or the pattern is lost is indicated by ×.

G) Heat resistance - Heat resistance was measured using TGA. After sampling the pattern film formed during the sensitivity measurement of (a) above, the temperature was raised from room temperature to 900°C at a rate of 10°C per minute using TGA. A case where the 5 wt% loss temperature was greater than 300 °C was indicated by ○, the case where the 5 wt% loss temperature was 280-300 °C was indicated by △, and the case where the 5 wt% loss temperature was less than 280 °C was indicated by ×.

division PAC substitution
number of moles Resin
Molecular Weight Sensitivity
(mJ/cm ² ) resolution
(um) hardening process
margin permeability heat resistance
discoloration adhesion heat resistance Example 1 A 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 2 B 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 3 C 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 4 D 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 5 E 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 6 F 2.0 6,000 100 3 ○ ○ ○ ○ ○ Example 7 A-1 1.0 6,000 100 3 ○ ○ ○ ○ ○ Example 8 A-2 1.2 6,000 100 3 ○ ○ ○ ○ ○ Example 9 A-3 1.5 6,000 100 3 ○ ○ ○ ○ ○ Example 10 A-4 2.5 6,000 100 3 ○ ○ ○ ○ ○ Example 11 D-1 1.0 6,000 100 3 ○ ○ ○ ○ ○ Example 12 D-2 1.5 6,000 100 3 ○ ○ ○ ○ ○ Example 13 D-3 2.5 6,000 100 3 ○ ○ ○ ○ ○ Example 14 A 2.0 4,000 100 3 ○ ○ ○ ○ ○ Example 15 A 2.0 10,000 100 3 ○ ○ ○ ○ ○ Example 16 A 2.0 16,000 100 3 ○ ○ ○ ○ ○ Comparative Example 1 G 2.0 6,000 150 3 ○ × × ○ ○ Comparative Example 2 H 2.0 6,000 135 3 ○ × × ○ ○ Comparative Example 3 I 2.0 6,000 135 3 ○ × × ○ ○ Comparative Example 4 J 2.0 6,000 140 3 ○ × × ○ ○ Comparative Example 5 K 2.0 6,000 140 3 ○ × × ○ × Comparative Example 6 G-1 1.5 6,000 150 3 ○ × × ○ ○ Comparative Example 7 G-2 2.5 6,000 150 3 ○ × × ○ ○ Comparative Example 8 H-1 1.5 6,000 145 3 ○ × × ○ ○ Comparative Example 9 H-2 2.5 6,000 145 3 ○ × × ○ ○ Comparative Example 10 I-1 1.5 6,000 135 3 ○ × × ○ ○ Comparative Example 11 I-2 2.5 6,000 135 3 ○ × × ○ ○ Comparative Example 12 J-1 1.5 6,000 140 3 ○ × × ○ ○ Comparative Example 13 J-2 2.5 6,000 140 3 ○ × × ○ ○ Comparative Example 14 K-1 1.5 6,000 140 3 ○ × × ○ × Comparative Example 15 K-2 2.5 6,000 140 3 ○ × × ○ × Comparative Example 16 A 2.0 2,500 135 5 ○ ○ ○ × × Comparative Example 17 A 2.0 22,000 170 3 ○ ○ ○ ○ ○

Through Table 1, the positive photosensitive insulating film compositions prepared in Examples 1 to 16 according to the present invention were excellent in resolution, curing process margin, transmittance, heat discoloration resistance, and heat resistance. In addition, when compared with Examples 1 to 16, Comparative Examples 1 to 15 had poor transmittance and heat discoloration resistance, and had excellent heat resistance compared to Comparative Examples 5, 14, 15, and 16, In particular, since the sensitivity is excellent compared to Comparative Examples 1 to 17, the process tact can be shortened, and excellent optical properties and reliability of the panel can be secured with excellent transmittance and heat discoloration resistance, and the resolution and adhesion strength compared to Comparative Example 16 , it was able to secure excellent process margin due to good heat resistance. Through this, it was found that the photosensitive resin composition can be applied in various display processes.

Claims (13)

a) a 1,2-quinonediazide compound of Formula 2;
b) an acrylic copolymer;
c) a silane coupling agent; and
d) a solvent; a positive photosensitive resin composition comprising:
[Formula 2]

R ₃ in Formula 2 is each independently a hydrogen atom or a 1,2-quinonediazide-based sulfonic acid ester,
R ₄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
At least one of R ₃ is a 1,2-quinonediazide-based sulfonic acid ester.
According to claim 1,
a) 5 to 50 parts by weight of the 1,2-quinonediazide compound of 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; the positive photosensitive resin composition comprising a solid content of 10 to 50% by weight in the photosensitive resin composition.
delete delete According to claim 2, wherein the acrylic copolymer,
i) 5 to 40 parts by weight of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof,
ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound, and
iii) A positive photosensitive resin composition prepared by copolymerizing 10 to 70 parts by weight of an olefinically unsaturated compound.
The method of claim 5, wherein i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixtures thereof is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof. The positive photosensitive resin composition which is one or more types selected from the group which consists of anhydrides. 6. The method according to claim 5, wherein the epoxy group-containing unsaturated compound of ii) is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl Glycidyl acrylate, acrylic acid-β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4 -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl A positive photosensitive resin that is at least one selected from the group consisting of benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxy cyclohexyl methacrylate. composition.
6. The method of claim 5, wherein the olefinically unsaturated compound of iii) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, Isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1- Adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboronyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl Acrylate, isoboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene, 2-[methacryloyloxy]ethyl 6-hydroxyhexanate, 4-vinylphenol; 4-vinylcyclohexanol, 4-hydroxybenzyl methacrylate, [[4-hydroxymethyl] cyclohexyl] methyl methacrylate, 3-hydroxy-1-methacryloyloxyadamantane, 2-oxo The positive photosensitive resin composition which is one or more types selected from the group which consists of tetrahydrofuran-3-yl methacrylate and 4-hydroxycyclohexyl methacrylate.
The positive photosensitive resin composition according to claim 1, wherein the acrylic copolymer of b) has a polystyrene reduced weight average molecular weight (Mw) of 3,000 to 20,000.
According to claim 1, wherein the silane coupling agent of c) is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyl dime Toxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxy Silane, 3-triethoxysilly-N-(1,3 dimethyl-butylidene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-amino from the group consisting of propyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (3-isocyanatepropyl)triethoxysilane One or more types of positive photosensitive resin compositions are selected.
According to claim 1, wherein the solvent of d) is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 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, diphoropylene glycol diethyl ether , butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and 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 tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and The positive photosensitive resin composition which is one or more types selected from the group which consists of dipropylene glycol methylhexyl ether.

A display device comprising a cured product of the positive photosensitive resin composition of claim 1 .
The method of forming a pattern for a display device comprising the step of patterning an interlayer insulating film prepared by coating the positive photosensitive resin composition of claim 1 .