TWI629559B - Positive-type photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

Disclosed herein is a photosensitive resin composition comprising: (1) a mixture of copolymer A-1 and copolymer A-2, wherein copolymer A-1 comprises (1-1) a carboxyl group-derived Structural units of unsaturated monomers, (1-2) structural units derived from unsaturated monomers containing at least one epoxy group, (1-3) structural units derived from unsaturated monomers containing phenyl groups, and (1-4) Structural units derived from unsaturated monomers and different from structural units (1-1) to (1-3), and copolymer A-2 contains (1-5) Structural units of saturated monomers, (1-6) structural units derived from phenolic hydroxyl-containing unsaturated monomers, and (1-7) derived from unsaturated monomers and different from structural units (1-5) and ( 1-6) a structural unit; and (2) a photoactive compound. The cured film prepared from the photosensitive resin composition has high sensitivity, excellent pattern developing ability and anti-smearing characteristics, and it can be effectively used as a dielectric layer in a liquid crystal display (LCD). Device.

Description

Positive type photosensitive resin composition and hardened film prepared therefrom

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom, and more particularly to a positive photosensitive resin composition which can be used as an interlayer dielectric layer material of a thin film transistor (TFT) array of a liquid crystal display (LCD) Materials, and hardened films made therefrom.

A thin film transistor (TFT) substrate used in a liquid crystal display (LCD) has an interlayer dielectric layer disposed between a TFT device and a transparent conductive layer forming a pixel electrode to protect the TFT array. The contact holes are formed inside the interlayer dielectric layer, thereby connecting the electrical lines formed from the drain electrodes of the TFT array to the transparent conductive layer. Therefore, the dielectric layer system needs to have good light transmittance, chemical stability, and excellent interlayer adhesion.

A positive or negative photosensitive resin composition is used as a material for this interlayer dielectric layer.

In the processes of exposure, hard baking after development, and absorption of short-wavelength light such as UV rays, conventional positive-type photosensitive compositions containing alkali-soluble resins and diazo 1,2-quinonediazide compounds are often used. Companion With various problems, such as coloring due to pyrolysis or undesired afterimages in the LCD due to generation of impurities.

In this regard, attempts have been made to improve the characteristics of the positive photosensitive resin composition (see Korean Patent Case Early Publication No. 10-2004-0078554, Korean Patent Case No. 10-0758867, and Japanese Patent Case Early Publication No. 2004- No. 286968). Although these conventional photosensitive resin compositions have achieved quite high light transmittance, their level of sensitivity has not been satisfactory.

Accordingly, an object of the present invention is to provide a positive-type photosensitive resin composition having high sensitivity, excellent pattern developing ability, and anti-smearing characteristics, and a cured film prepared from the photosensitive resin composition.

According to one aspect of the present invention, a photosensitive resin composition is provided, which comprises: (1) a mixture of copolymer A-1 and copolymer A-2, wherein copolymer A-1 comprises (1-1) Structural units derived from carboxyl-containing unsaturated monomers, (1-2) structural units derived from unsaturated monomers containing at least one epoxy group, (1-3) derived from phenyl-containing unsaturated monomers And (1-4) are derived from unsaturated monomers and are different from the structural units (1-1) to (1-3), and the copolymer A-2 series contains (1-5) derivation Structural units derived from carboxyl-containing unsaturated monomers, (1-6) structural units derived from phenolic hydroxyl-containing unsaturated monomers, and (1-7) derived from unsaturated monomers and different from structural units (1 -5) and the structural units of (1-6); and (2) a photoactive compound.

The photosensitive resin composition of the present invention has high sensitivity, excellent pattern developing ability and anti-smearing characteristics, so it can be used in A dielectric layer is prepared in a liquid crystal display (LCD) device.

The positive photosensitive resin composition system of the present invention comprises (1) a mixture of copolymer A-1 and copolymer A-2, wherein copolymer A-1 comprises (1-1) an unsaturated monomer derived from a carboxyl group Structural units, (1-2) structural units derived from unsaturated monomers containing at least one epoxy group, (1-3) structural units derived from unsaturated monomers containing phenyl groups, and (1- 4) A structural unit derived from an unsaturated monomer and different from the structural units (1-1) to (1-3), and the copolymer A-2 contains (1-5) an unsaturated monomer derived from a carboxyl group Structural units, (1-6) derived from unsaturated monomers containing phenolic hydroxyl groups, and (1-7) derived from unsaturated monomers and different from structural units (1-5) and (1-6 ) A structural unit; and (2) a photoactive compound. It may further comprise (3) an epoxy-based compound, (4) a solvent, and / or (5) an additive if necessary, including (5-1) a surfactant and / or (5-2) a silane coupling agent.

The components of the present invention will be described in detail later.

(1) Mixture of copolymers A-1 and A-2

The mixture of copolymers used in the present invention comprises: Copolymer A-1, which comprises (1-1) a structural unit derived from an unsaturated monomer containing a carboxyl group, and (1-2) derived from at least one Structural units of epoxy-based unsaturated monomers, (1-3) structural units derived from phenyl-containing unsaturated monomers, and (1-4) derived from unsaturated monomers and different from structural units (1 -1) to (1-3), and the copolymer A-2 contains (1-5) unsaturated monomer derived from a carboxyl group Structural units, (1-6) derived from unsaturated monomers containing phenolic hydroxyl groups, and (1-7) derived from unsaturated monomers and different from structural units (1-5) and (1- 6) The structural unit.

(1-1) Structural units derived from unsaturated monomers containing carboxyl groups

The unsaturated monomer containing a carboxyl group can be exemplified by an unsaturated carboxylic acid, such as an unsaturated polycarboxylic acid having at least one carboxyl group, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, and the like. Examples of such unsaturated monocarboxylic acids include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Among the above compounds, (meth) acrylic acid is preferred for good development and polymerizable ability. The amount of the structural unit (1-1) may be 1 to 40% by weight, preferably 2 to 35% by weight based on the total weight of the copolymer A-1. Within this range, exposure sensitivity can be improved, and development characteristics can be easily maintained.

(1-2) Structural units derived from unsaturated monomers containing at least one epoxy group

The structural unit (1-2) is derived from an unsaturated monomer containing at least one epoxy group. Specific examples of the unsaturated monomer containing at least one epoxy group include glycidyl (meth) acrylate, glycidyl ether of 4-hydroxybutyl acrylate, 3,4-epoxybutyl (meth) acrylate, ( 4,5-epoxyamyl methacrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 2,3- (meth) acrylic acid Epoxy cyclopentyl ester, 3,4-epoxy cyclohexyl (meth) acrylate, α-ethyl glycidy acrylate, α-n-propyl glycidyl acrylate (α-n -propyl glycidyl acrylate), α-n-butyl glycidyl acrylate, N- (4- (2,3-epoxypropoxy) -3,5-dimethyl Benzyl) acrylamide, N- (4- (2,3-epoxypropoxy) -3,5-dimethylphenylpropyl) acrylamide, allyl glycidyl ether, 2- Methylallyl glycidyl ether, and mixtures thereof. From the viewpoint of storage stability and solubility at room temperature, preferred are glycidyl (meth) acrylate, glycidyl ether of 4-hydroxybutyl acrylate, and mixtures thereof.

The structural unit (1-2) can be used in an amount of 5 to 45 wt%, preferably 10 to 40 wt%, based on the total weight of the copolymer A-1. Within this content range, the storage stability of the composition can be maintained, and a good retention rate after hardening can be obtained.

(1-3) Structural units derived from phenyl-containing unsaturated monomers

Specific examples of the phenyl-containing unsaturated monomer may be at least one compound selected from the group consisting of: phenyl (meth) acrylate, benzyl (meth) acrylate, 2-benzene (meth) acrylate Ethoxyethyl ester, phenoxy diethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate Tribromophenyl (meth) acrylate; styrene; styrene with alkyl substituents, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylbenzene Ethylene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; halogen-containing styrenes such as fluorostyrene, chlorostyrene, bromostyrene And iodostyrene; styrenes with alkoxy substituents, such as methoxystyrene, ethoxystyrene, and propoxystyrene; ethylfluorenylstyrene, vinyltoluene, divinylbenzene, ( (O-, m-, p-)-vinylbenzyl methyl ether, and (o-, m-, p-)-vinylbenzyl Glycidyl ether. Specifically, for good polymerizability, a styrene-based compound is preferred; for good retention, benzyl (meth) acrylate or phenyl (meth) acrylate is preferred.

The structural unit (1-3) can be used in an amount of 1 to 40 wt%, preferably 5 to 35%, based on the total weight of the copolymer A-1. Within this content range, improvements in developing ability and exposure sensitivity can be obtained.

(1-4) Structural units derived from unsaturated monomers and different from the structural units (1-1) to (1-3)

Specific examples of unsaturated monomers other than the structural units (1-1) to (1-3) include: N -substituted maleimides, such as N -methylmaleimide, N- Ethylmaleimide, N -propylmaleimide, N -isopropylmaleimide, N -butylmaleimide, N -isobutylmaleimide, N - third maleate (PEI), N - (PEI) cyclohexylmaleimide, N - benzylmaleimide (PEI), N - phenylmaleimide (PEI), N - chlorophenyl maleimide XI Imine, N -methylphenylmaleimide, N -bromophenylmaleimide, N -methoxyphenylmaleimide, N -carboxyphenylmaleimide, N -nitrophenylmaleimide and N -naphthylmaleimide; unsaturated carboxylic acid esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Butyl ester, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethyl (meth) acrylate Hexyl ester, tetrahydrofuran methyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Ester, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, α-hydroxymethyl methacrylate, α-hydroxymethyl Ethyl acrylate, α-hydroxy methacrylate, α-hydroxy methacrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxylate Diethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate Ester, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, (meth) acrylic acid Heptafluorodecyl, isobornyl (meth) acrylate, dicyclopentane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate Esters, and dicyclopentenyloxyethyl (meth) acrylate; tertiary amines with N -vinyl, such as N -vinylpyrrole, N -vinylcarbazole, and N -vinylmorpholine ; And unsaturated ethers, such as vinyl methyl ether and vinyl Ethyl ether. These compounds may be used alone or in combination of two or more.

The structural unit (1-4) can be used in an amount of 15 to 70 wt%, preferably 20 to 65% based on the total weight of the copolymer A-1. Within this content range, a pattern having a good shape after development can be obtained.

(1-5) Structural units derived from unsaturated monomers containing carboxyl groups

The structural unit derived from the carboxyl group-containing unsaturated monomer is the same as the structural unit (1-1), but the amount of the structural unit (1-5) is based on the total weight of the copolymer A-2.

(1-6) Structural units derived from phenolic hydroxyl-containing unsaturated monomers

The structural unit derived from a phenolic hydroxyl-containing unsaturated monomer can be represented by the following formula (I):

Among them, R ¹ is hydrogen, C _1-6 alkyl, halogen or cyano; R ² is C _1-6 alkyl, a is an integer of 0 to 4, and when a is an integer of 2 or more, plural R ² are the same or different from each other; b is an integer from 1 to 5, and the sum of a and b is an integer from 1 to 5; and Y is a single bond or a C _1-6 alkyl group, wherein the alkyl group and The alkylene is optionally substituted with at least one halogen, nitro, C _1-6 alkoxy or C _6-12 aryl.

Specific examples of the phenolic hydroxyl-containing unsaturated monomer include, but are not limited to, p-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl methyl (meth) acrylate, α-chloroacrylic acid p-hydroxyphenyl methyl ester, (meth) acrylic acid m-hydroxyphenyl methyl ester, (meth) acrylic acid 2- (p-hydroxyphenyl) ethyl ester, α-trifluoromethacrylic acid 2- (p- Hydroxyphenyl) ethyl ester, 2- (p-hydroxyphenyl) ethyl α-chloroacrylate, 2- (p-hydroxyphenyl) ethyl α-bromoacrylate, 2- (p-hydroxyphenyl) α-cyanoacrylate Ethyl ester, 2- (m-hydroxyphenyl) ethyl (meth) acrylate, 2- (3,5-dihydroxyphenyl) ethyl (meth) acrylate, 2- (3,5) (meth) acrylate -Dimethyl-4-hydroxyphenyl) ethyl ester, (meth) acrylic acid 1- (p-hydroxyphenyl) -1-methylethyl ester, (meth) acrylic acid 1- (m-hydroxyphenyl) -1 -Methyl ethyl ester, 1- (3,5-dihydroxyphenyl) -1-methyl ethyl (meth) acrylate, and mixtures thereof.

The structural unit (1-5) can be used in an amount of 5 to 70 wt%, preferably 20 to 65%, based on the total weight of the copolymer A-2. Within this content range, patterns with good developed shape and high sensitivity can be obtained.

(1-7) Structural units derived from unsaturated monomers and different from the structural units (1-5) and (1-6)

Specific examples of unsaturated monomers different from the structural units (1-5) and (1-6) include, but are not limited to, ethylenically unsaturated monomers containing an aromatic ring, N -substituted maleimine Monomers, and other ethylenically unsaturated monomers.

Specific examples of the aromatic ring-containing ethylenically unsaturated monomer include at least one compound selected from the group consisting of: phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2 -Phenoxyethyl ester, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (methyl) Acrylate, tribromophenyl (meth) acrylate; styrene; styrene with alkyl substituents, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethyl Basic styrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene; halogen-containing styrenes such as fluorostyrene, chlorostyrene, bromine Styrene and iodostyrene; styrenes with alkoxy substituents, such as methoxystyrene, ethoxystyrene and propoxystyrene; ethenylstyrene, vinyltoluene, divinylbenzene (Ortho, meta, para) -vinylbenzyl methyl ether and (ortho, meta, para) -vinylbenzyl glycidyl ether. Among the above compounds, for good polymerizability, a styrene-based compound is preferred; for good retention, a benzyl (meth) acrylate or phenyl (meth) acrylate is preferred.

Examples of N -substituted maleimide imide monomers include, but are not limited to, N -methylmaleimide, N -ethylmaleimide, N -propylmaleimide, N -isopropylmaleimide, N -butylmaleimide, N -isobutylmaleimide, N -tertiarybutylmaleimide, N -cyclohexylmaleimide (PEI), N - benzylmaleimide (PEI), N - phenylmaleimide (PEI), N - chlorophenyl maleimide (PEI), N - acyl methylphenyl maleic imide, N - bromo Phenylmaleimide, N -methoxyphenylmaleimide, N -carboxyphenylmaleimide, N -nitrophenylmaleimide, N -naphthylmaleimide Hydrazone, and mixtures thereof. In the above compounds, for improvement of retention, based preferred N - phenylmaleimide (PEI), N - cyclohexyl maleimide (PEI), or mixtures thereof, more preferably Department of N - phenylmaleimide (PEI).

Specific examples of other ethylenically unsaturated monomers include unsaturated carboxylic acid esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and dimethacrylate Methylaminoethyl, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth) acrylic acid Tetrahydrofuran methyl ester, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Glyceryl (meth) acrylate, α-hydroxymethyl methacrylate, α-hydroxymethyl acrylate, α-hydroxymethacrylate, α-hydroxymethacrylate, 2 (meth) acrylic acid 2 -Methoxyethyl, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy Tripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3 , 3-hexafluoroisopropyl ester, (meth) propyl Octafluoropentyl enoate, heptafluorodecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentane (meth) acrylate, dicyclopentene (meth) acrylate, ( Dicyclopentyloxyethyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate; tertiary amines with N -vinyl, such as N -vinylpyrrole, N -ethylene Carbazole and N -vinylmorpholine; and unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether. These compounds may be used alone or in combination of two or more.

The structural unit (1-7) can be used in an amount of 15 to 70 wt%, preferably 20 to 65% based on the total weight of the copolymer A-2. Within this amount, an improvement in the developing ability of the pattern can be obtained.

In this specification, "(meth) acrylfluorenyl" means "acrylfluorenyl" and / or "methacrylfluorenyl", and "(meth) acrylate" means "acrylate" and / or "Methacrylate".

In addition, the weight average molecular weight (Mw) of each copolymer, that is, each of the copolymers A-1 and A-2 may be in the range of 500 to 50,000, preferably 1,000 to 50,000, and more preferably 3,000 to 30,000. Within the scope of the disclosure, the adhesion, physical properties, and chemical resistance of the substrate can be as desired. The weight average molecular weight is a weight average molecular weight using polystyrene as a reference, which is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran).

Copolymers A-1 and A-2 can each be prepared by any conventional method known in the art to which the invention belongs.

The weight ratio of the copolymer A-1 to the copolymer A-2 may be 10 to 90:90 to 10.

Copolymers A-1 and A-2 can be used without the photosensitive resin composition Including the total amount of the solvent as a basis (ie, based on the solid content), an amount of 50 to 95% by weight, preferably 60 to 85% by weight, is used. Within the scope of the above disclosure, a pattern having a good developed shape can be obtained, and characteristics such as retention and chemical resistance can be improved.

(2) Photoactive compounds

The photosensitive resin composition of the present invention may include a diazoquinone-based photoactive compound, and as a photosensitizer, it is sensitive to g-rays, h-rays, and i-rays. The diazoquinone compound is a diazo1,2-quinone compound, which generates a carboxylic acid when exposed to radiation. For example, a condensation product of a phenol or alcohol compound (hereinafter referred to as a "scaffold") and a diazo 1,2-naphthoquinonesulfonium halide can be used as the diazo 1,2-quinone compound.

In the present invention, the stent may be, for example, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, or (polyhydroxyphenyl) alkane.

Specific examples of the scaffold include, but are not limited to, for example, trihydroxybenzophenones, such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; tetrahydroxydione Benzophenones, such as 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxydione Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone; five Hydroxybenzophenone, such as 2,3,4,2 ', 6'-pentahydroxybenzophenone; hexahydroxybenzophenone, such as 2,4,6,3', 4 ', 5'-hexa Hydroxybenzophenone and 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone; (polyhydroxyphenyl) alkanes, such as bis (2,4-dihydroxyphenyl) methane, Bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxybenzene) Methyl), methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenyl Propane, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylene) bisphenol, bis (2,5-dimethyl 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobisindene-5,6,7,5', 6 ', 7'-hexanol and 2,2,4-trimethyl-7,2 ', 4'-trihydroxypropane; and other scaffolds, such as 2-methyl-2- (2,4-dihydroxyphenyl) 4- (4-hydroxyphenyl) -7-hydroxybenzopiperan, 2- [bis {(5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] benzene, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3 -{1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene and 4,6-bis {1- (4- Hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

In addition, it is also possible to use a diazo1,2-naphthoquinonesulfonamide having a sulfonamide chain instead of the ester chain in the stent exemplified above. For example, 2,3,4-trihydroxybenzophenone-diazo 1,2-naphthoquinone-4-sulfonamide and the like can be preferably used.

The diazo 1,2-naphthoquinonesulfonium halide is preferably diazo 1,2-naphthoquinonesulfonyl chloride. Specific examples may include diazo1,2-naphthoquinone-4-sulfosulfonyl chloride and diazo1,2-naphthoquinone-5-sulfonyl chloride. Among the compounds disclosed above, diazo1,2-naphthoquinone-5-sulfonyl chloride is preferred.

The scaffold used in the condensation reaction and 1,2-naphthoquinone sulfonium diazonium can be used per 1 mol of the stent, and 1.0 to 6.0 mol of 1,2-naphthoquinone sulfonium halide is preferably used. It is used in an amount of 1.0 to 5.0 mol of diazo 1,2-naphthoquinone sulfonium halide. The condensation reaction of the present invention can be performed by any conventional method known in the technical field to which the invention belongs.

Considering the improvement of the sensitivity and retention of the photosensitive resin composition, the diazoquinone compound is preferably a compound having a structure of formula (II):

Among them, R is each independently hydrogen, a substituent of formula (IIa), or a substituent of formula (IIb), but at least one R is a substituent of formula (IIa) or a substituent of formula (IIb).

The amount of the photoactive compound may be 0.5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on the total weight (solid content) of the copolymer mixture as 100 parts by weight. Within the above range, good retention after development can be obtained, and characteristics such as sensitivity and development ability can be improved.

(3) epoxy compounds

The epoxy-based compound of the present invention may include a repeating unit of formula (III):

Wherein R ⁵ is hydrogen or C _1-4 alkyl; and R ⁶ is C _1-10 alkylene, phenylene, C _3-10 cycloalkyl, C _3-10 heterocycloalkyl, or C _2-10 heteroalkyl, wherein the R ⁶ is optionally substituted with at least one hydroxyl group.

As used herein, unless specifically stated otherwise, the term "heteroalkyl" refers to an alkylene compound having at least one heteroatom selected from O, S, and N.

Specific examples of R ⁵ in formula (III) include hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, and third butyl, and are preferably hydrogen or methyl.

Specific examples of R ⁶ include methylene, ethylene, propyl, butyl, pentyl, hexyl, heptyl, octyl, danyl, decyl, -C ₂ H ₄ -OC ₂ H _4- , -C ₄ H ₈ -OC ₄ H _8- , -C ₄ H ₈ -O-CH _2- , -C ₄ H ₈ -OC ₂ H _4- , -C ₂ H _4- O-CH _2- , -C ₂ H ₄ -COO-C ₂ H _4- , -C ₄ H ₈ -COO-C ₄ H _8- , -C ₄ H ₈ -COO-CH _2- , -C ₄ H ₈ -COO-C ₂ H _4- , -C ₂ H ₄ -COO-CH _2- , -C ₂ H ₄ -OCONH-C ₂ H _4- , -C ₂ H ₄ -CH (OH) -C ₂ H ₄ -etc., and preferably methylene or -C ₄ H ₈ -O-CH _2- .

In the present invention, the weight average molecular weight of the epoxy-based compound containing the repeating unit of the formula (III) may be in the range of 1,000 to 9,000, preferably 1,000 to 7,000, and more preferably 2,000 to 5,000. Within the above range, good adhesion and chemical resistance can be obtained. The weight average molecular weight is a weight average molecular weight using polystyrene as a reference, which is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran).

The epoxy-based compound may be any one known in the technical field to which the invention belongs. Prepared by conventional methods.

The epoxy-based compound may be used in an amount of 0.5 to 30 parts by weight, preferably 2 to 25 parts by weight, based on 100 parts by weight of the total weight of the copolymer mixture (as a solid content). Within the above range, good retention and chemical resistance can be obtained.

(4) Solvent

The photosensitive resin composition according to the present invention can be prepared by any conventional method known in the technical field to which the invention belongs, and is preferably prepared as a liquid composition by mixing the above components in a solvent. In the photosensitive resin composition of the present invention, the amount of the solvent is not specifically limited. However, considering the coating characteristics and stability of the photosensitive resin composition, the photosensitive resin composition of the present invention may include a solvent, and the content of the active agent is such that the solid content range of the composition is based on the total weight of the composition as a basis 5 to 70 wt%, preferably 10 to 50 wt%.

The solid content means the content of the components obtained after removing the solvent from the resin composition of the present invention.

Specific examples of the solvent include: ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether Ethers, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers, such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether Ethers; dipropylene glycol dialkyl ethers, such as dipropylene glycol dimethyl ether; propylene glycol monoalkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate and propylene glycol monobutyl ether acetate; cellosolves, such as ethylcellulose and butylcellulose; carbitols, such as butylcarbitol; lactates, such as lactic acid Methyl ester, ethyl lactate, n-propyl lactate and isopropyl lactate; aliphatic carboxylic acid esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid N-pentyl ester, isoamyl acetate, isopropyl propionate, n-butyl propionate and isopropyl propionate Butyl esters; esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methylpyruvate Esters and ethyl pyruvate; aromatic hydrocarbons, such as toluene and xylene; ketones, such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; amidoamines, such as N -dimethyl Methylformamide, N -methylacetamide, N, N -dimethylacetamide and N -methylpyrrolidone; lactones, such as γ-butyrolactone; and mixtures thereof.

Among the above compounds, for good coating ability and high stability, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate and methyl 3-methoxypyruvate are preferred.

(5) Other ingredients

The photosensitive resin composition according to the present invention may further contain other components to improve its characteristics. For example, other ingredients may include (5-1) a surfactant and / or (5-2) a silane coupling agent.

(5-1) Surfactant

If necessary, in order to improve the coating ability and prevent the formation of defects, the photosensitive resin composition according to the present invention may further contain a surfactant. The surfactant is not limited to a specific category, and is preferably a fluorine-based surfactant, a silicon-based surfactant, a nonionic surfactant, and the like. Examples of the surfactant include fluorine-based or silicon-based surfactants, such as BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F-482, F-489 (manufactured by Dai Nippon Ink Chemical Kogyo Co., Ltd.), Florad FC-135, Florad FC- 170C, Florad FC-430, Florad FC-431 (manufactured by Sumitomo 3M Ltd.), Sufron S-112, Sufron S-113, Sufron S-131, Sufron S-141, Sufron S-145, Sufron S-382, Sufron SC-101, Sufron SC-102, Sufron SC-103, Sufron SC-104, Sufron SC-105, Sufron SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF301, Eftop 303, Eftop 352 ( (Manufactured by Shinakida Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicon Co., Ltd.) , DC3PA, DC7PA, SH11PA, SH21PA, SH8400, GE, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (manufactured by GE Toshiba Silicon Co., Ltd.), and BYK-333 (manufactured by BYK Co., Ltd.); non-ionic Surfactants, such as polyoxyethylene alkyl ethers, including polyoxyethylene lauryl ether, polyoxyethylene hard Ethers, polyoxyethylene oleyl ethers, etc., polyoxyethylene aryl ethers, including polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc., and polyoxyethylene dialkyl esters, including Polyoxyethylene dilaurate, polyoxyethylene distearate, etc .; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylate copolymer Polyflow No. 57, 95 (Kyoei Yuji Chemical Co., Ltd.) and the like. They can be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may include a surfactant in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on the total weight (solid content) of the copolymer mixture as 100 parts by weight. Within the above range, the composition can be easily applied.

(5-2) Silane coupling agent

The photosensitive resin composition according to the present invention may further include a silane coupling agent as an adhesive agent for improving the adhesion between the coating and the substrate. The silane coupling agent may have a reactive substituent selected from the group consisting of a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, an imidazolyl group, a mercapto group, an amino group, and the like. Examples of silane coupling agents include, but are not limited to, trimethoxysilylbenzoic acid, γ-methacrylfluorenyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane Γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N -phenyl-3-aminopropyltriethoxysilane, and mixtures thereof.

The silane coupling agent may be used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on the total weight (solid content) of the copolymer mixture as 100 parts by weight. Within the above range, the adhesion of the composition to the substrate can be improved.

Moreover, other additives such as a dissolution accelerator, a sensitizer, an antioxidant, a light stabilizer (UV absorber), and the like may be included without prejudice to the physical characteristics of the photosensitive resin composition.

Furthermore, the present invention provides a process for preparing the above-mentioned photosensitive resin composition. Hardened film.

The cured film can be prepared by any conventional method known in the technical field to which the invention belongs, for example, by coating a photosensitive resin composition on a substrate and subjecting it to a curing process. More specifically, the photosensitive resin composition coated on the substrate may be pre-baked at a temperature such as 60 ° C to 130 ° C to remove the solvent; exposed to light using a photomask having a desired pattern; and used A developer such as a tetramethylammonium hydroxide solution (TMAH) is developed to form a pattern on the coating film. Subsequently, if necessary, the obtained patterned coating film is baked at a temperature such as 150 ° C. to 300 ° C. for 10 minutes to 5 hours to prepare a desired cured film. Light exposure can be performed in a wavelength range of 200 to 450 nanometers (nm) and an exposure amount of 20 to 100 millijoules (mJ) / cm 2 (cm ² ).

When a cured film is produced from the positive-type photosensitive resin composition according to the present invention, the cured film system exhibits good pattern formation, retention, and chemical stability.

Due to its excellent characteristics, the cured film prepared according to the present invention can be effectively used as an interlayer dielectric layer in a liquid crystal display device. Accordingly, the present invention provides an electronic component including a cured film as a dielectric layer.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are described to illustrate the present invention, and the scope of the present invention is not limited thereto.

In the following examples, the weight average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene standards.

[Example]

Preparation Example 1: Preparation of Copolymer A-1a

200 parts by weight of propylene glycol monomethyl ether acetate was placed in a flask equipped with a condenser tube and a stirrer as a solvent, stirred slowly, and the temperature was raised to 70 ° C. 13.5 parts by weight of methacrylic acid, 31.0 parts by weight of glycidyl (meth) acrylate, 13.6 parts by weight of styrene, 32.3 parts by weight of methyl (meth) acrylate, and 9.7 parts by weight of (meth) acrylic acid Isobornyl ester was added thereto, and this was made by adding 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator dropwise in a 5-hour interval. The obtained mixture was subjected to polymerization. Copolymer A-1a (solid content = 30 wt%) having a weight average molecular weight of 9,800 was obtained.

Preparation Example 2: Preparation of copolymer A-2a

200 parts by weight of propylene glycol monomethyl ether acetate was placed in a flask equipped with a condenser tube and a stirrer as a solvent, stirred slowly, and the temperature was raised to 70 ° C. 4.4 parts by weight of methacrylic acid, 52.2 parts by weight of p-hydroxyphenylmethyl (meth) acrylate, 35.2 parts by weight of methyl (meth) acrylate, and 8.1 parts by weight of isobornyl (meth) acrylate were added Among them, by adding dropwise 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator in a 5-hour interval, the mixture thus obtained was performed. Polymerization. Copolymer A-2a having a weight average molecular weight of 12,700 (solid content = 30 wt%) was obtained.

Preparation Example 3: Preparation of Copolymer A-1b

The procedure of Preparation Example 1 was repeated, but using 15.0 parts by weight of methacrylic acid, 31.0 parts by weight of glycidyl (meth) acrylate, 13.6 parts by weight of styrene, 30.6 parts by weight of methyl (meth) acrylate, and 9.7 Parts by weight Isobornyl (meth) acrylate to obtain a copolymer A-1b having a weight average molecular weight of 10,400 (solid content = 30 wt%).

Preparation Example 4: Preparation of copolymer A-2b

The procedure of Preparation Example 2 was repeated, but using 6.3 parts by weight of methacrylic acid, 52.4 parts by weight of p-hydroxyphenylmethyl (meth) acrylate, 33.1 parts by weight of methyl (meth) acrylate, and 8.2 parts by weight of ( Isobornyl (meth) acrylate to obtain copolymer A-2b (solid content = 30 wt%) having a weight average molecular weight of 11,800.

Preparation Example 5: Preparation of epoxy-based compound C-1

100 parts by weight of glycidyl (meth) acrylate and 195 parts by weight of methyl 3-methoxypropionate as a solvent were mixed in a flask equipped with a condenser and a stirrer. After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 60 ° C while slowly stirring the mixture. While maintaining the temperature, 3 parts by weight of azobisisobutyronitrile as a radical polymerization initiator was added dropwise over a period of 2 hours, so that the obtained mixture was subjected to polymerization. As a result, a compound C-1 containing a repeating unit of the formula (IV) and having a weight average molecular weight of 3,500 was obtained, and its solid content was 34.5%.

Example 1

340 parts by weight of methyl 3-methoxypropionate (MMP) as a solvent In (1) a mixture of (1) 70 parts by weight of copolymer A-1 obtained in Preparation Example 1 as a solid component and 30 parts by weight of copolymer A-2a obtained in Preparation Example 2 as a solid component, (2) 21.5 Part by weight of a diazoquinone-based photoactive compound (MIPHOTO TPA523, Miwon Commercial) as a solid component, (3) 0 parts by weight of an epoxy-based compound C-1, (4) 0.15 prepared in Preparation Example 5 as a solid component Parts by weight of solid surfactant (FZ-2122, Dow Corning Toray Silicon) and (5) 0.22 parts by weight of silane coupling agent (KBE-9007, Shin-Etsu) as solid ingredients are homogeneously mixed for 2 hours to obtain As a liquid photosensitive resin composition.

Examples 2 to 11 and Comparative Examples 1 to 8

To prepare the photosensitive resin composition, the procedure of Example 1 was repeated, but each solution was prepared using the ingredients and amounts (parts by weight) listed in Table 1 below.

In order to evaluate its sensitivity, pattern development ability, and turbidity after development, the cured films prepared using the resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were tested according to the following methods. The results are shown in Table 2 below.

Assessment of sensitivity

[Preparation of samples]

Each of the photosensitive resin compositions was coated on a glass substrate using a spin coater, and the coated substrate was post-baked at 100 ° C for 90 seconds to form a coating having a thickness of 4 micrometers (μm). Laminated. A pattern cover having a pattern consisting of square holes having a size ranging from 1 to 15 μm and a pitch of 1 μm was placed on top of the coating film thus obtained. With a distance between the cover and the substrate of 25 μm, the film was aligned with an aligner (model: MA6) under a UV light source with an intensity of 15 milliwatts (mW) / cm ² at a wavelength of 0 to 200 mJ based on 365 nm With an exposure rate of / cm ² for a period of time, the aligner emits light having a wavelength of 200 to 450 nm. Subsequently, the film was developed by spraying a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developer through a nozzle at 23 ° C.

[Measurement of sensitivity]

For the hole pattern formed by patterning through a mask size of 10 μm, the exposure dose required to reach a critical dimension (CD, unit: μm) of 10 μm was measured.

2. Evaluation of pattern development ability (dose: 70mJ / cm ² , Cover size: 10μm)

In the process of preparing the cured film for the sensitivity measurement test, the exposure was performed at a radiation dose of 70 mJ / cm ² through a mask size of 10 μm. The critical dimension of the obtained pattern is measured, and then the value (%) of the pattern developing ability is calculated using the following equation. The lower the value of the pattern developing ability, the better the characteristics of the hardened layer.

Pattern developing ability (%) = [(size of cover-CD of hole pattern) / (size of cover)] × 100

3. Turbidity after development

The haze after development of the unexposed portion of the cured film obtained from each sample was evaluated (×: no haze; ○: haze was observed).

When the cured film shows no turbidity, the characteristics of the film are regarded as satisfactory.

As can be seen from the test results in Table 2 above, the photosensitive resin composition containing the binary adhesive prepared from Examples 1 to 11, that is, the copolymer mixture, is provided with high sensitivity and does not show turbidity after development ( Tail problem) A cured film with excellent pattern development ability.

In another aspect, the photosensitive resin composition prepared in Comparative Examples 1 to 8 using only one copolymer without using a binary adhesive is provided with a cured film having relatively poor sensitivity and pattern development ability. In particular, the cured films prepared using the photosensitive resin compositions of Comparative Examples 2 and 4 to 8 showed a certain degree of haze after development.

Claims (5)

A photosensitive resin composition comprising: (1) a mixture of copolymer A-1 and copolymer A-2, wherein the copolymer A-1 comprises (1-1) a carboxyl group-containing unsaturated monomer Structural units, (1-2) structural units derived from unsaturated monomers containing at least one epoxy group, (1-3) structural units derived from unsaturated monomers containing phenyl groups, and (1-4) A structural unit derived from an unsaturated monomer and different from the structural units (1-1) to (1-3), wherein the copolymer A-1 includes a basis based on the total weight of the copolymer A-1 The structural units (1-1), (1-2), (1-3), and (1-4) in the range of 1 to 40 wt%, 5 to 45 wt%, 1 to 40 wt%, and 15 to 70 wt%, respectively. ); And the copolymer A-2 comprises (1-5) a structural unit derived from an unsaturated monomer containing a carboxyl group, (1-6) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group, and ( 1-7) Structural units derived from unsaturated monomers and different from the structural units (1-5) and (1-6), wherein the copolymer A-2 comprises the total of the copolymer A-2 The weight is based on the structural unit (1-5) in the range of 1 to 40 wt%, 5 to 70 wt%, and 15 to 70 wt%, respectively. (1-6) and (1-7), and wherein the mixture of the copolymer A-1 and the copolymer A-2 includes the copolymer A-1 and the copolymer A-1 in a weight ratio of 10 to 90:90 to 10 The copolymer A-2; and (2) a diazoquinone-based photoactive compound, wherein the diazoquinone-based photoactive compound is 0.5 to 40 parts by weight based on the total weight of the mixture of the copolymer. content. The photosensitive resin composition according to item 1 of the patent application scope, wherein the phenyl-containing unsaturated monosystem styrene. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the structural unit (1-6) is represented by formula (I): Wherein R ¹ is hydrogen, C _1-6 alkyl, halogen or cyano; R ² is C _1-6 alkyl, a is an integer of 0 to 4, and when a is an integer of 2 or more, the A plurality of R ² are the same or different from each other; b is an integer from 1 to 5 and the sum of a and b is an integer from 1 to 5; and Y is a single bond or a C _1-6 alkylene group, wherein the alkyl group And alkylene is optionally substituted with at least one halogen, nitro, C _1-6 alkoxy or C _6-12 aryl. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the diazoquinone-based photoactive compound is a compound having a structure of formula (II): Among them, R is each independently hydrogen, a substituent of formula (IIa) or a substituent of formula (IIb), but at least one R is a substituent of formula (IIa) or a substituent of formula (IIb): The photosensitive resin composition according to item 1 of the scope of the patent application, which contains an epoxy-based compound, the compound containing a repeating unit of formula (III): Wherein R ⁵ is hydrogen or C _1-4 alkyl; and R ⁶ is C _1-10 alkylene, phenylene, C _3-10 cycloalkyl, C _3-10 heterocycloalkyl, or C _2-10 heteroalkyl, wherein the R ⁶ is optionally substituted with at least one hydroxyl group.