KR20220095307A - A photosensitive resin composition and a cured layer formed therefrom, and a display device comprising the cured layer - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and a display device comprising the cured film. More specifically, the present invention relates to a photosensitive resin composition, a cured film formed therefrom, and a display device comprising the cured film, wherein the photosensitive resin composition exhibits excellent deep curing properties, which is advantageous for pattern formation and development processes using photolithography by mixing and using specific photopolymerization initiators with different absorption wavelengths in a specific content ratio, is particularly suitable for organic light-emitting material display panels by having excellent resistance to wet chemicals such as organic solvents, acids, and alkalis, and thus able to insulate and protect metal electrodes of organic light emitting devices or touch panels.

Description

A photosensitive resin composition and a cured film formed therefrom, and a display device comprising the cured film

The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and a display device including the cured film, and more particularly, by mixing and using specific photopolymerization initiators having different absorption wavelengths in a specific content ratio, excellent deep-section curability It is advantageous for pattern formation and development process using photolithography, and has excellent resistance to wet chemicals such as organic solvents, acids, and alkalis, so it is particularly suitable for organic light emitting material display panels, and also for organic light emitting devices or touch panels. It relates to a photosensitive resin composition capable of performing a role of insulating and protecting a metal electrode, a cured film formed therefrom, and a display device including the cured film.

In display devices, LTPS (Low Temperature Poly-Silicon) and oxide thin film transistors are being actively studied as devices for high resolution of UD (Ultra Definition) or higher and high speed driving of 240 Hz or higher. In general, the oxide thin film transistor minimizes the above-mentioned problems by introducing a light blocking layer because the properties of the semiconductor are changed by light. Since subsequent processes such as PE-CVD are performed at high temperatures after forming the light-shielding layer, a metal light-shielding layer is mainly used as the light-shielding layer. However, the metal light-shielding layer has high reflectivity, so light is reflected between the source and drain electrodes and the light-shielding layer, and a parasitic voltage is generated between the source and drain electrodes and acts as an element that applies resistance to the operation of the device. There is a problem that the load on the line increases.

In particular, in organic light-emitting material displays and transparent displays, a light-shielding layer is sometimes introduced in order to eliminate the characteristic that the contrast ratio is significantly lowered due to reflection of upper and lower metal wires. In addition, it is mainly required that the organic film have resistance, high transmittance, high adhesion, high resolution, etc. to withstand the deposition process, photo process, and wet etching process performed in the post process. Further, larger screen, higher luminance, thinner, etc. are additionally required, and from the viewpoint of shortening process time and cost reduction, higher sensitivity and higher resolution of the negative radiation-sensitive resin composition are required. In order to solve this problem, the technology of a radiation-sensitive resin composition including an oxime ester-based photopolymerization initiator is being studied.

Common examples of the photopolymerization initiator used in the photosensitive composition include acetophenone derivatives, benzophenone derivatives, triazine derivatives, biimidazole derivatives, acylphosphine oxide derivatives, and oxime ester derivatives. It absorbs and exhibits almost no color, has high radical generation efficiency, and has excellent compatibility and stability with photosensitive composition materials. However, the initially developed oxime derivative compound has a low photoinitiation efficiency and, in particular, has a low sensitivity during a pattern exposure process, so that an exposure amount must be increased, thereby reducing production. In order to improve these disadvantages, various oxime ester derivative compounds have been proposed as photopolymerization initiators (eg, Korean Patent Application Laid-Open Nos. 10-2001-0082580 and 10-2007-0044753).

An object of the present invention is a photosensitive resin composition and a cured film formed therefrom, which exhibit excellent deep part curability, which is advantageous for pattern formation and development process using the photolithography method, and can improve chemical resistance, transmittance, adhesion, and pattern resolution, and It is to provide the display element containing this cured film.

The present invention to achieve the above object, [A] alkali-soluble resin; [B] a polymerizable compound having an ethylenically unsaturated bond; [C] a photopolymerization initiator comprising a compound of Formula 1 and Formula 2; and [D] a solvent; it provides a photosensitive resin composition comprising the compound of Formula 2 per 1 part by weight of the compound of Formula 1, in an amount of greater than 0.01 parts by weight and less than 30 parts by weight:

[Formula 1]

[Formula 2]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, alkoxy, arylalkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl;

R ₃ is alkyl, aryl, arylalkyl or cycloalkyl.

According to another aspect of the present invention, there is provided a cured film formed from the photosensitive resin composition.

According to another aspect of the present invention, a display device (eg, an organic light emitting material display (OLED) device) including the cured film is provided.

The photosensitive resin composition of the present invention exhibits excellent deep hardenability, which is advantageous for pattern formation and development process using photolithography, has excellent resistance to wet chemicals such as organic solvents, acids, and alkalis, and is flexible due to repeated bending due to structural characteristics It is not destroyed even when the non-exposed part is developed quickly, so it exhibits excellent pattern resolution (eg, 20 micrometers or less), transmittance and adhesion, and in particular, it can be suitably used as a photosensitive resin composition for an organic light emitting material display panel. In addition, the photosensitive resin composition of the present invention is selectively patterned at a desired position to exist above or below the metal to serve as an insulating film and to protect the metal electrode from organic solvents, acids, and alkali solutions used during the manufacturing process. Therefore, it can serve to insulate and protect the metal electrode of the organic light emitting device or the touch panel.

Hereinafter, the present invention will be described in more detail.

The photosensitive resin composition of this invention is [A] alkali-soluble resin; [B] a polymerizable compound having an ethylenically unsaturated bond; [C] a photopolymerization initiator comprising a compound of Formula 1 and Formula 2; and [D] solvent.

[A] Alkali-soluble resin

[A] alkali-soluble resin contained in the photosensitive resin composition of the present invention is, for example, an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain, a silicone-based resin, a cardo-based resin, and an imide-based resin 1 selected from More than one species can be used.

In one embodiment, the acrylic polymer may be a (co)polymer of monomers including an acrylic monomer. Examples of such acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, Tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylic Late, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid mono Alkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 3, 4-Foxycyclohexylmethyl (meth) acrylate, 3-methyloxetane-3-methyl (meth) acrylate, 3-ethyloxetane-3-methyl (meth) acrylate, (meth) acrylamide, N- methyl (meth)acrylamide etc. are mentioned, These may be used individually or in combination of 2 or more types, respectively. In addition, these acrylic monomers and monomers such as styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide A copolymer obtained by copolymerizing

In one embodiment, the acrylic polymer having an acrylic unsaturated bond in the side chain may be a copolymer obtained by addition-reacting an epoxy resin to an acrylic (co)polymer containing carboxylic acid. For example, acrylic monomers containing carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic acid monoalkyl ester, and alkyl (meth) such as methyl (meth) acrylate and hexyl (meth) acrylate ) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl ( meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, (meth)acrylamide, N-methyl (meth)acrylamide, etc. obtained by copolymerizing the acrylic copolymer containing carboxylic acid Cydyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate What is obtained by addition-reacting an epoxy monomer such as those at a temperature of 40 to 180°C can be used as the binder resin.

Another example of the acrylic polymer having an acrylic unsaturated bond in the side chain is a copolymer obtained by addition reaction of a carboxylic acid to an acrylic copolymer containing an epoxy group. For example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl Acrylic monomers containing an epoxy group, such as (meth)acrylate, and alkyl (meth)acrylates such as methyl (meth)acrylate and hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acryl Rate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- Ethoxyethyl (meth)acrylate, styrene, α-methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide , (meth)acrylamide, N-methyl (meth)acrylamide obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid monoalkyl ester to an acrylic copolymer containing an epoxy group What is obtained by addition-reacting an acrylic monomer containing carboxylic acid at a temperature of 40 to 180°C can be used as the binder resin.

In one embodiment, the weight average molecular weight (g/mol) of the alkali-soluble resin may be 1,000 or more, 2,000 or more, or 3,000 or more, and may be 300,000 or less, 200,000 or less, 100,000 or less, or 50,000 or less, but is not limited thereto. .

Further, in one embodiment, the dispersion degree of the alkali-soluble resin may be 1.0 to 10.0, but is not limited thereto.

According to one embodiment, in terms of pattern property control and thin film properties such as heat and chemical resistance, the alkali-soluble resin content included in 100 parts by weight of the photosensitive resin composition of the present invention is 3 parts by weight or more, 5 parts by weight or more, It may be 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, and may be 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less, but is limited thereto not.

[B] Polymeric compound having an ethylenically unsaturated bond

[B] The polymerizable compound having an ethylenically unsaturated bond contained in the photosensitive resin composition of the present invention is crosslinked by photoreaction during pattern formation to form a pattern, and is crosslinked when heated at high temperature to impart chemical resistance and heat resistance do.

In one embodiment, the polymerizable compound having an ethylenically unsaturated bond may be a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group.

In one embodiment, as the polymerizable compound having an ethylenically unsaturated bond, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl Alkyl ester of (meth)acrylic acid such as (meth)acrylate, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate having 2 to 14 ethylene oxide groups, ethylene glycol di(meth)acrylate , Polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, trimethylolpropane di(meth)acrylate, bisphenol A Diglycidyl ether acrylic acid adduct, phthalic acid diester of dihydroxyethyl (meth) acrylate, toluene diisocyanate adduct of dihydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Polyhydric alcohols such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol tri (meth) acrylate and α,β-diunsaturated carboxylic acid, a compound obtained by esterification, and an acrylic acid adduct of a polyvalent glycidyl compound such as trimethylolpropane triglycidyl ether acrylic acid adduct, etc., each alone or two or more Can be used together.

According to one embodiment, the content of the polymerizable compound having an ethylenically unsaturated bond included in 100 parts by weight of the photosensitive resin composition of the present invention is 0.001 parts by weight or more, 0.01 parts by weight or more, 0.1 parts by weight or more, 1 parts by weight or more. Or it may be 5 parts by weight or more, and may be 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less, but is not limited thereto. If too much of the polymerizable compound having an ethylenically unsaturated bond is added to the photosensitive resin composition, the degree of crosslinking may be excessively high, which may cause disadvantages in that the ductility of the pattern is lowered, the flexibility of the film is lowered, and the bending properties may be deteriorated.

[C] Photoinitiator

[C] The photopolymerization initiator included in the photosensitive resin composition of the present invention includes the compounds of the following formulas 1 and 2, which have different absorption wavelengths to enhance deep part curability and provide excellent pattern formation:

[Formula 1]

[Formula 2]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, alkoxy, arylalkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl;

R ₃ is alkyl, aryl, arylalkyl or cycloalkyl.

More specifically, in the above, alkyl and alkoxy may have 1 to 30 carbon atoms, cycloalkyl may have 3 to 30 carbon atoms, and aryl may have 6 to 30 carbon atoms.

More specifically, in the above, alkyl and alkoxy may have 1 to 20 carbon atoms, cycloalkyl may have 3 to 20 carbon atoms, and aryl may have 6 to 20 carbon atoms.

In one embodiment, R ₁ and R ₂ are each independently hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n -Hexyl, i-hexyl, n-octyl, n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenane Tril, methoxyl, ethoxy, n-propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn -Butyl, hydroxy i-butyl, hydroxy n-pentyl, hydroxy i-pentyl, hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl , hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl.

In one embodiment, R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclo pentyl, cyclohexyl, or phenyl.

The compound of Formula 1 may include, but is not limited to, one or more representatively selected from the following group:

The photosensitive resin composition of the present invention includes the compound of Formula 2 per 1 part by weight of the compound of Formula 1, in an amount exceeding 0.01 parts by weight and less than 30 parts by weight. If the amount of the compound of Formula 2 included in the photosensitive resin composition of the present invention is 0.01 parts by weight or less based on 1 part by weight of the compound of Formula 1, the overall physical properties of the pattern, such as adhesion, acid resistance, and stripper resistance, are poor, and vice versa If it is 30 or more, it is difficult to implement a fine pattern of 50 micrometers or less, and the pattern is not formed cleanly.

In one embodiment, the amount of the compound of Formula 2 included in the photosensitive resin composition of the present invention is based on 1 part by weight of the compound of Formula 1, for example, 0.02 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, 1 parts by weight or more, 2 parts by weight or more; 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, but is not limited thereto. Further, in another embodiment, the amount of the compound of Formula 2 included in the photosensitive resin composition of the present invention is based on 1 part by weight of the compound of Formula 1, for example, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less. or less, 26 parts by weight or less, 25 parts by weight or less, 24 parts by weight or less, 23 parts by weight or less, 22 parts by weight or less, 21 parts by weight or less, 20 parts by weight or less, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less It may be 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, or 2 parts by weight or less, but is not limited thereto.

According to one embodiment, in terms of making the deep part hardening smoothly, the photopolymerization initiator content included in 100 parts by weight of the photosensitive resin composition of the present invention is 0.01 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more. 1 part by weight or more. 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, or 2 parts by weight or more, and 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 It may be less than or equal to 5 parts by weight, less than or equal to 4 parts by weight, or less than or equal to 3 parts by weight, but is not limited thereto.

[D] solvent

The photosensitive resin composition of this invention contains a solvent.

According to one embodiment, as the solvent, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate , propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, Diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ- Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol Methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, etc. can be used individually or in mixture of two or more types.

In one embodiment, the solvent may be added in an amount such that the viscosity of the composition is in the range of 1 to 50 cps, for example, may be added in an amount of 10 to 95 parts by weight based on 100 parts by weight of the total composition, but is limited thereto it is not

any additional ingredients

The photosensitive resin composition of the present invention, in addition to the components [A] to [D], if necessary, may further include one or more components that can be added to the photosensitive resin composition.

In one embodiment, the photosensitive resin composition of the present invention may further include a silicone-based compound having an epoxy group or an amine group as an adhesion aid.

The silicone-based compound improves the adhesion between the ITO electrode and the photosensitive resin composition, and can be used to increase heat resistance after curing, and the amount used may be 0.0001 to 3 parts by weight based on 100 parts by weight of the composition, but is limited thereto not.

In one embodiment, as the silicone-based compound having an epoxy group or an amine group, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) ) Methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3 ,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclo hexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, etc. are mentioned, and these may be used individually or in mixture of 2 or more types.

In addition, the photosensitive resin composition of the present invention may further include one or more additives having compatibility such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent, and a dispersing agent, if necessary.

In addition, the photosensitive resin composition of the present invention is one selected from the group consisting of a thioxanthone-based compound, a ketone-based compound, a biimidazole-based compound, a triazine-based compound, an O-acyloxime-based compound, and a thiol-based compound, if necessary Or it may further contain 2 or more types of compounds.

In the photosensitive negative resist composition of the present invention, for example, an organic insulating film of an organic electroluminescent material or an overcoat of a touch panel can be formed by the following method.

A photosensitive negative resist composition is coated on a substrate, the solvent is removed to form a uniform coating film, and then the unexposed portion is developed by exposing the ultraviolet rays passing through the mask to an aqueous alkali solution. Thereafter, an organic insulating film and an overcoat can be obtained by heat treatment.

As the substrate, for example, glass, quartz, silicon, ITO, or the like can be used.

The coating method of the photosensitive negative resist composition solution is not particularly limited, and for example, spin coating, slot die coating, spraying, roll coating, etc. may be used.

The removal of the solvent is preferably carried out by heat treatment and reduced pressure through a vacuum device. Although these conditions of reduced pressure and heat treatment vary depending on the type and ratio of the organic solvent component used in the composition, it is preferable to heat-treat at a reduced pressure of 0.5 to 2.0 torr and at 80 to 120° C. for about 80 to 200 seconds.

The process of exposing the negative resist to ultraviolet light uses a GHI mixed wavelength and is carried out at an exposure dose of 10 to 300 mJ/cm 2 .

The process of curing the negative resist uses thermal crosslinking through heat treatment and the temperature is 180 to 230 ° C. for 15 to 120 minutes to finally form an organic insulating film of a flexible organic electroluminescent material or an overcoat of the touch panel. .

The thickness of the protective film formed as described above is preferably 0.1 to 6 μm, and when there are irregularities on the substrate forming the protective film for optical devices, the value should be understood as a value on the uppermost surface of the irregularities.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereby.

[Example]

Synthesis Example: [A] Preparation of alkali-soluble resin

a) Preparation of A-1 resin

Methacrylic acid, methyl methacrylate and glycidyl methacrylate, and dicyclopentanyl acrylate were added in a molar ratio of 10:30:40:20, respectively, and then 30 parts by weight of the mixture, V-65 1 as a thermal initiator After putting parts by weight and 70 parts by weight of methyl 3-methoxy propionate in a reaction vessel, polymerization was carried out while stirring for 8 hours while maintaining 65° C. in a nitrogen atmosphere. The weight average molecular weight of the copolymer thus prepared was Mw=25,000.

b) Preparation of A-2 resin

231 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 150 mg of tetrabutylammonium chloride, and 74 g of propionic acid were heated at 120° C. and reacted for 12 hours. Propionic acid was analyzed by GC to complete the reaction, and a solid intermediate was obtained (yield: 92%). After dissolving 280 g of the obtained solid intermediate in 400 mL of propylene glycol methyl ether acetate (PGMEA), 101.4 g of 3,3′,4,4′-biethyltetracarboxylic acid dianhydride, tetrabutyl Ammonium chloride 500mg was added and reacted at 120°C. Finally, 35 g of phthalic anhydride was mixed, and the reaction was terminated at 90° C. to obtain a cardo-based polymer, A-2 resin. The weight average molecular weight was 3,800.

c) Preparation of A-3 resin

231 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 150 mg of tetrabutylammonium chloride, 100 mg of 2,6-di-t-butyl-4-methylphenol, and 72 g of acrylic acid were heated at 120° C. for 12 hours reacted while Acrylic acid was analyzed by GC to complete the reaction, and a solid intermediate was obtained (yield: 92%). After dissolving 280 g of the obtained solid intermediate in 400 mL of PGMEA, 101.4 g of 3,3',4,4'-biethyltetracarboxylic dianhydride and 500 mg of tetrabutylammonium chloride were added, followed by reaction at 120°C. Finally, 35 g of phthalic anhydride was mixed, and the reaction was terminated at 90° C. to obtain a cardo-based polymer, A-3 resin. The weight average molecular weight was 4,800.

Examples 1 to 15 and Comparative Examples 1 to 14: Preparation of photosensitive resin composition

[A] 40 parts by weight of the alkali-soluble resin (A-1, A-2 or A-3) prepared in Synthesis Example 1 as a binder polymer, [B] a photopolymerizable polyfunctional compound having an ethylenically unsaturated bond 10 parts by weight of a monomer (dipentaerythritol hexa(meth)acrylate), [C] 0.05 parts by weight of a photopolymerization initiator in an amount (parts by weight) shown in Table 1 below, and a surfactant (BYK-307) were mixed, and organic The solvent, 3-methoxy methyl propionate (MMP) and diethylene glycol methyl ethyl ether (MEDG) mixed solvent (mixing weight ratio 6:4) was added to adjust the total weight of the composition to 100 parts by weight, and then mixed using a shaker for 3 hours. did The mixed photosensitive solution was filtered using a filter having a size of 0.5 microns to prepare a photosensitive composition. The types of photoinitiators used in Examples and Comparative Examples are as follows.

[Compound 1]

(Wherein, R ₁ is hydrogen, R ₂ is a propyl (C ₃ H ₇ ) group, and R ₃ is a methyl (CH ₃ ) group)

[Compound 2]

[Compound 3]

[Compound 4]

The photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 14 were spin-coated on glass and pre-bake at about 100° C. for 2 minutes to form an even film having a thickness of about 3.0 μm. . After exposing the film using an isolated pattern photomask having a diameter of 3 to 50 μm, the pattern was developed for 60 seconds with an aqueous KOH alkali solution having a pH of 11.3 to 11.7, and washed with deionized water. After post-bake at 230°C for about 25 minutes, the state of the pattern was observed under a microscope to observe the remaining degree of the micropattern. cut) was checked, and the evaluation results are shown in Table 2 below.

1) Formable fine pattern level

As for the level of the formable fine pattern, the level of the mask size in which the pattern was formed was confirmed through an optical microscope after the photolithography process.

2) Pattern Size

A photosensitive negative resist composition was formed on a glass substrate with a mask size of 20 x 20 μm, and the length of the bottom surface of the square hole was measured using a scanning electron microscope (SEM) device.

3) Adhesion

The organic insulating film and overcoat prepared on the glass substrate and the ITO substrate were left for 24 hours under high temperature (121° C.), high pressure (2 atm), and high humidity (100% humidity) conditions, and then adhesion was evaluated using the checkered tape method. The checkered tape method uses a cutter knife on the flattening film and the protective film to make 11 rows of 1 mm gaps to the depth of the top surface of the glass substrate, and then in the vertical direction, 11 rows of 1 mm gaps are made to the depth of the top surface of the glass substrate. After forming the checkerboard pattern of dogs, an adhesive tape (3M company, 310-M) was attached to the checkerboard pattern and then peeled off to perform an adhesion test, the number of peeled checkered patterns was measured, and the adhesiveness of the cured film was evaluated according to the following criteria .

○: The number of peeled checkerboard patterns 5 or less

△: 6 to 49 pieces of peeled checkerboard patterns

Χ: 50 or more of peeled checkerboard patterns

4) Remaining film rate

The film manufacturing method was carried out without a mask, and the ratio of the thickness change after heat curing to the thickness of the thin film before exposure was calculated.

If the thickness change ratio was 60% or more, it was judged as 'excellent', and if the thickness change ratio was 60% or less, it was judged as 'poor'.

5) Acid resistance

The specimen prepared on the glass substrate was immersed in a 7N aqueous aqua regia solution at 40° C. for 180 seconds, washed with ultrapure water for 60 seconds, and dried. At this time, by evaluating the thickness change rate and adhesive strength, the case where the thickness change rate is 0~3% based on the thickness after thermal curing is 'excellent', 3~5% is 'good', and if it exceeds 5%, it is 'bad'. and adhesion was determined using the above 3) adhesion evaluation method. The evaluation results are shown in Table 3 below.

6) Stripper resistance

The specimen prepared on the glass substrate was immersed in a stripper at 60° C. for 180 seconds, washed with ultrapure water for 60 seconds, and dried. At this time, by evaluating the thickness change rate and adhesive strength, the case where the thickness change rate is 0~3% based on the thickness after thermal curing is 'excellent', 3~5% is 'good', and if it exceeds 5%, it is 'bad'. and adhesion was determined using the above 3) adhesion evaluation method. The evaluation results are shown in Table 3 below.

From the results of Tables 2 and 3, it can be confirmed that the photosensitive negative resist composition of the present invention was superior to the photosensitive negative resist composition of Comparative Example in all items measured and evaluated.

Claims (7)

[A] alkali-soluble resin;
[B] a polymerizable compound having an ethylenically unsaturated bond;
[C] a photopolymerization initiator comprising a compound of Formula 1 and Formula 2; and
[D] includes a solvent;
A compound of formula 2 per 1 part by weight of compound of formula 1, comprising in an amount of greater than 0.01 parts by weight and less than 30 parts by weight,
Photosensitive resin composition:
[Formula 1]

[Formula 2]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, alkyl, aryl, alkoxy, arylalkyl, hydroxyalkyl, hydroxyalkoxyalkyl or cycloalkyl;
R ₃ is alkyl, aryl, arylalkyl or cycloalkyl. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is at least one selected from an acrylic resin, a silicone resin, a cardo-based resin, and an imide-based resin. The photosensitive resin composition according to claim 1, wherein the polymerizable compound having an ethylenically unsaturated bond is a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group. According to claim 1,
R ₁ and R ₂ are each independently hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl , n-octyl, n-decyl, i-decyl, n-dodecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, eth oxy, n-propyloxy, i-propyloxy, n-butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyn-butyl, hydroxyi -Butyl, hydroxyn-pentyl, hydroxyi-pentyl, hydroxyn-hexyl, hydroxyi-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl , hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl;
R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, cyclopentyl, cyclohexyl, or phenyl,
A photosensitive resin composition. The photosensitive resin composition of claim 1, wherein the compound of Formula 1 is at least one selected from the group consisting of:

The cured film formed from the photosensitive resin composition of any one of Claims 1-5. A display device comprising the cured film of claim 6 .