TW202034086A - Positive-type photosensitive composition and cured film using the same - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition and a cured film prepared therefrom. The composition comprises a photoactive compound of a polymer, and/or a photoactive compound of a monomer, containing a repeat unit having a specific structure. Thus, the exposed portion (i.e., the portion exposed to light) is increased by the interaction between the binder resin (i.e., siloxane copolymer) and the photoactive compound, which increases the solubility in a developer, whereby the sensitivity can be enhanced. In addition, it is possible to form a cured film capable of achieving a high edge angle of a pattern by way of employing the photoactive compound in a proper amount.

Description

Positive photosensitive composition and cured film using the same

The present invention relates to a positive photosensitive resin composition capable of forming a cured film excellent in sensitivity, resolution and film retention, and a cured film prepared therefrom to be used in liquid crystal displays, organic EL displays, etc.

In general, positive photosensitive resin compositions that require fewer processing steps are widely used in liquid crystal display devices, organic EL display devices, and the like.

However, the planarization film or display element using the conventional positive type photosensitive resin composition has lower sensitivity than the planarization film and display element using the negative type photosensitive resin composition. Therefore, the sensitivity of the former needs to be improved.

Meanwhile, the conventional positive photosensitive resin composition usually contains a soluble resin (such as silicone polymer and acrylic polymer) as a binder resin together with a photosensitizer (such as quinonediazide-based compounds, aromatic aldehydes, etc.). ) (See Japanese Laid-open Patent Publication No. 1996-234421).

However, when using such a positive photosensitive resin composition to form a cured film, the thickness loss rate of the cured film caused by the developer during the development step is large, and a sufficiently satisfactory film retention rate, sensitivity, and resolution are achieved. There are restrictions on degrees, etc.

At the same time, the cured film requires the size of the pattern to be small and the edge angle of the pattern to be large in order to obtain high resolution. Specifically, in order to obtain high resolution, it is important that the size of the hole in the mask applied when forming the cured film reaches the target level of critical dimension (CD). At the same time, in order to prevent electrical interference between the lower wiring and the upper wiring, the edge angle of the pattern should be close to 90°.

At the same time, in order to increase the edge angle of the pattern, a method of increasing the content of a photosensitizer such as a quinonediazide-based compound, etc., has been proposed, which is widely used in the field of photoresist compositions, or a method of The method of increasing the temperature during the baking process. However, although these methods can increase the edge angle of the pattern, they have the disadvantage of deteriorating sensitivity.

Technical Problem Therefore, an object of the present invention is to provide a positive photosensitive resin composition capable of forming a cured film excellent in the edge corners of a pattern without deteriorating such physical properties such as sensitivity, resolution, etc., and a composition made of it The prepared cured film to be used in liquid crystal displays, organic EL displays, etc. The solution to the problem

A₁ 和A₂ 各自獨立地是氫、羥基、酚基、C_1-4 烷基、C_6-15 芳基、或C_1-4 烷氧基， R₁ 是氫或

，並且n是3至15的整數。In order to achieve the above object, the present invention provides a positive photosensitive resin composition comprising (A) a silicone copolymer; and (B) a photoactive compound comprising a repeating unit represented by the following formula 1. Compound: [Formula 1]

A ₁ and A ₂ are each independently hydrogen, hydroxyl, phenolic, C _1-4 alkyl, C _6-15 aryl, or C _1-4 alkoxy, and R ₁ is hydrogen or

, And n is an integer from 3 to 15.

In order to achieve another object, the present invention provides a cured film prepared by using the positive photosensitive resin composition. The beneficial effects of the present invention

The positive photosensitive resin composition according to the present invention includes a photoactive compound containing a polymer having a repeating unit of a specific structure and/or a monomeric photoactive compound. Therefore, the interaction between the binder resin (ie, the silicone copolymer) and the photoactive compound increases the exposed portion (ie, the exposed portion), which increases the solubility in the developer, thereby Can enhance sensitivity. In addition, since the composition contains an appropriate amount of the photoactive compound, a cured film capable of realizing a large edge angle of a pattern can be formed.

Best Mode for Carrying Out the Invention The present invention provides a positive photosensitive resin composition comprising (A) a siloxane copolymer; and (B) a photoactive compound.

The composition may optionally further include (C) epoxy compound; (D) surfactant; (E) adhesion extender; and/or (F) solvent.

Hereinafter, each component of the positive photosensitive resin composition will be explained in detail.

As used herein, the term "(meth)acryl" refers to "acryl" and/or "methacryl", and the term "(meth)acrylate" refers to "acrylate" And/or "methacrylate".

The weight average molecular weight (g/mole, Da) of each component as described below was measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran) with reference to polystyrene standards. (A) Silicone copolymer

A photosensitive resin composition containing a silicone copolymer (silicone polymer; A) can be formed into a positive pattern by a method from exposure to development.

The silicone polymer (A) is a soluble resin that achieves developability in the development step, and also functions as a substrate for film formation during coating and a structure and binder for forming the final pattern.

The siloxane polymer (A) contains a condensate of a silane compound and/or its hydrolyzate. In this case, the silane compound or its hydrolyzate may be a monofunctional to tetrafunctional silane compound. As a result, the silicone polymer may contain silicone structural units selected from the following Q, T, D, and M types: -Q-type siloxane structural unit: a siloxane structural unit containing a silicon atom and four adjacent oxygen atoms, which can be derived from, for example, a tetrafunctional silane compound or a hydrolysis product of a silane compound with four hydrolyzable groups .

-T-type siloxane structural unit: a siloxane structural unit containing a silicon atom and three adjacent oxygen atoms, which can be derived from, for example, a trifunctional silane compound or a hydrolysis product of a silane compound with three hydrolyzable groups .

-D-type siloxane structural unit: a siloxane structural unit containing a silicon atom and adjacent oxygen atoms (ie, a linear siloxane structural unit), which can be derived from, for example, a bifunctional silane compound or has two The hydrolyzed product of a silane compound with a hydrolyzed group.

-M-type siloxane structural unit: a siloxane structural unit containing a silicon atom and an adjacent oxygen atom, which can be derived from, for example, a monofunctional silane compound or a hydrolysis product of a silane compound with a hydrolyzable group.

Specifically, the siloxane polymer (A) may include a structural unit derived from a silane compound represented by the following formula 2: [Formula 2] (R ₂ ) _m Si(OR ₃ ) _4-m

In the above formula 2, m is an integer from 0 to 3; R _{2 is} each independently a C _1-12 alkyl group, a C _2-10 alkenyl group, a C _6-15 aryl group, a 3-membered to 12-membered heteroalkyl group, 4-membered to 10-membered heteroalkenyl, or 6-membered to 15-membered heteroaryl; and R _{3 is} each independently hydrogen, C _1-6 alkyl, C _2-6 acyl, or C _6-15 aryl, Wherein the heteroalkyl group, the heteroalkenyl group, and the heteroaryl group each independently have at least one heteroatom selected from the group consisting of O, N, and S.

The compound can be a tetrafunctional silane compound (where m is 0), a trifunctional silane compound (where m is 1), a bifunctional silane compound (where m is 2), or a monofunctional silane compound (where m is 3).

Specific examples of the silane compound may include, for example, as the tetrafunctional silane compound, tetraethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, Silane, and tetrapropoxy silane; as trifunctional silane compounds, methyl trimethoxy silane, methyl triethoxy silane, methyl triisopropoxy silane, methyl tributoxy silane, ethyl Trimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane Yl silane, phenyl triethoxy silane, d ³ -methyl trimethoxy silane, nonafluorobutyl ethyl trimethoxy silane, trifluoromethyl trimethoxy silane, n-propyl trimethoxy silane, n Propyl triethoxy silane, n-butyl triethoxy silane, n-hexyl trimethoxy silane, n-hexyl triethoxy silane, decyl trimethoxy silane, vinyl trimethoxy silane, vinyl triethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- Acrylic oxypropyl triethoxysilane, p-hydroxyphenyl trimethoxysilane, 1-(p-hydroxyphenyl) ethyl trimethoxysilane, 2-(p-hydroxyphenyl) ethyl trimethoxysilane , 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl) ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl triethoxy silane, [(3-ethyl-3-oxetanyl) )Methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, And 3-trimethoxysilylpropyl succinic acid; as a bifunctional silane compound, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyl Diethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane Silane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethyl Methyl silane, 3-chloropropyl dimethoxy methyl silane, 3-mercaptopropyl dimethoxy methyl silane, cyclohexyl dimethoxy methyl silane, diethoxy methyl vinyl silane, two Methoxymethylvinylsilane, and dimethoxydi-p-tolylsilane; and as a monofunctional silane compound, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethane Oxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) ) Dimethyl ethoxysilane.

Among the tetrafunctional silane compounds, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are preferred; among the trifunctional silane compounds, methyltrimethoxysilane and methyl are preferred. Triethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropyl Oxysilane, ethyl tributoxy silane, butyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane, 2-(3 ,4-epoxycyclohexyl) ethyl trimethoxysilane, and 2-(3,4-epoxycyclohexyl) ethyl triethoxy silane; among the bifunctional silane compounds, dimethyl is preferred Dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, and dimethyldiethoxy Silane.

The conditions for obtaining the hydrolyzate or condensate of the silane compound having the above formula 2 are not particularly limited.

The weight average molecular weight of the condensate (ie, siloxane polymer) obtained by the hydrolysis polymerization of the silane compound having the above formula 2 may be 500 to 50,000 Da, 1,000 to 50,000 Da, 3,000 to 30,000 Da, or 5,000 to 20,000 Da. If the weight average molecular weight of the silicone polymer is within the above range, the polymer is more preferable in terms of film-forming properties, solubility, dissolution rate in the developer, and the like.

The siloxane polymer (A) may contain a structural unit (ie, a Q-type structural unit) derived from the silane compound represented by the above formula 2 (where m is 0). Specifically, the siloxane polymer may contain a structural unit derived from the silane compound represented by the above formula 2 (wherein m is 0) in an amount of 10 to 50 mol% or 15 to 40 mol% based on the molar number of Si atoms . If the amount of the Q-type structural unit is within the above range, the photosensitive resin composition can maintain its solubility in the alkaline aqueous solution at an appropriate level during pattern formation, thereby preventing the solubility of the composition from decreasing or the solubility increasing sharply. Any defects caused.

The siloxane polymer (A) may contain a structural unit (ie, a T-type structural unit) derived from the silane compound represented by the above formula 2 (where m is 1). For example, the siloxane polymer may include a structural unit derived from a silane compound having the above formula 2 (where m is 1) in an amount ratio of 40 to 99 mol% or 50 to 95 mol% based on the molar number of Si atoms . If the amount of T-shaped structural units is within the above range, it is more preferable to form a more accurate pattern outline.

In addition, in consideration of the hardness, sensitivity, and retention rate of the cured film, it is preferable that the siloxane polymer (A) contains a structural unit derived from a silane compound having an aryl group. For example, the silicone polymer may include a structural unit derived from a silane compound having an aryl group in an amount of 20 to 80 mol%, 30 to 70 mol%, or 30 to 50 mol% based on the molar number of Si atoms. If the amount of the structural unit derived from the silane compound having an aryl group is within the above range, the compatibility of the siloxane polymer (A) with the photoactive compound (B) is excellent, which can prevent excessive sensitivity Reduce while obtaining a cured film with more favorable transparency.

The structural unit derived from the silane compound having an aryl group may be, for example, a silane compound derived from the above formula 2 (wherein R ₂ is an aryl group), specifically having the above formula 2 (where m is 1 and R ₂ is an aryl group) The silane compound, more specifically the structural unit of the silane compound having the above formula 2 (where m is 1 and R ₂ is a phenyl group) (ie, a T-phenyl type siloxane structural unit).

As used herein, the term "molar% based on the molar number of Si atoms" refers to the molar number of Si atoms contained in a specific structural unit relative to the Si atoms contained in all structural units constituting the siloxane polymer. Percentage of total moles.

The molar amount of the siloxane unit in the siloxane polymer can be measured by a combination of Si-NMR, ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, elemental analysis, ash measurement, etc. For example, in order to measure the molar amount of siloxane units with phenyl groups, Si-NMR analysis was performed on the entire silicone polymer, and then the Si peak area of bound phenyl groups and the Si peak area of unbound phenyl groups were analyzed. Analysis. Then the molar amount can be calculated from the peak area ratio between the two.

Meanwhile, the silicone polymer of the present invention may be a mixture of two or more silicone polymers having different dissolution rates from each other to an aqueous solution of tetramethylammonium hydroxide (TMAH). If a mixture of two or more silicone polymers as described above is used as the silicone polymer, it is possible to improve both the sensitivity and chemical resistance of the resin composition.

The photosensitive resin composition of the present invention may include the silicone polymer (A) in an amount of 50 to 90% by weight or 65 to 90% by weight based on the solid content (excluding solvent) based on the total weight of the composition. If the content of the silicone polymer is within the above range, it is possible to maintain the developability of the composition at an appropriate level, thereby producing a cured film excellent in film retention and pattern resolution. (B) Photoactive compound

The positive photosensitive resin composition according to the present invention may contain (b-1) a compound containing a repeating unit represented by the following formula 1 as the photoactive compound (B). It may further contain (b-2) a quinonediazide-based monomer as needed. (b-1) Compounds containing repeating units represented by the following formula 1

The positive photosensitive resin composition according to the present invention may contain a polymer compound containing an o-quinonediazide group as shown below as the photoactive compound (B).

Specifically, the photoactive compound (B) may include a compound (b-1) containing a repeating unit represented by Formula 1 below. [Formula 1]

，並且n是3至15的整數。In the above formula 1, A ₁ and A ₂ are each independently hydrogen, a hydroxyl group, a phenol group, a C _1-4 alkyl group, a C _6-15 aryl group, or a C _1-4 alkoxy group, and R ₁ is hydrogen or

, And n is an integer from 3 to 15.

More specifically, the compound (b-1) containing the repeating unit represented by the above formula 1 may be 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid Acid, 1,2-naphthoquinonediazide-5-4-sulfonic acid, etc., and/or compounds in which the hydroxyl group is substituted with an amino group.

The compound (b-1) containing the repeating unit represented by Formula 1 above can be used alone or in combination with aromatic aldehyde-based soluble resins such as polyhydroxy aromatic compounds.

For example, polyhydroxy alkyl compounds such as glycerin, pentaerythritol, etc., or polyhydroxy aromatic compounds such as novolac resin, bisphenol A, gallic acid esters, quercetin, morin, polyhydroxy benzophenone, etc. can be combined with Esters combination of 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-4-sulfonic acid, etc. use. Preferably, the novolak resin and/or polyhydroxybenzophenone can be used in combination with the ester of 1,2-naphthoquinonediazide-5-sulfonic acid.

In this case, the substitution rate (ie, esterification rate) of novolak resin can be 10% to 70% or 25% to 60% (ie, esterification product of novolak resin/total novolak resin × 100). The substitution rate of polyhydroxybenzophenone can be 50% to 95% (ie, esterification product of polyhydroxybenzophenone/total polyhydroxybenzophenone × 100). Within the above range, the resolution and sensitivity of the composition can be further enhanced. If the replacement rate is low, the resolution deteriorates. If the replacement rate is too high, the sensitivity may deteriorate.

The compound (b-1) containing the repeating unit represented by the above formula 1 may be 1 to 100% by weight, 10 to 100% by weight, or 20 to 100% by weight based on the polymer content based on the total weight of the photoactive compound (B) The amount used. Within the above content range, it is easier to form a pattern, the surface of the coating film is not roughened when it is formed, and it is possible to suppress the appearance of a defective pattern shape such as scum in the bottom part of the pattern during development. (b-2) Monomers based on quinonediazide

The positive photosensitive resin composition according to the present invention may further include a quinonediazide monomer (b-2), specifically a 1,2-quinonediazide-based compound as the photoactive compound (B).

The 1,2-quinonediazide-based compound is not particularly limited as long as it is used as a photosensitizer in the field of photoresist and has a 1,2-quinonediazide-based structure.

Examples of 1,2-quinonediazide-based compounds include ester compounds of phenolic compounds with 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid ; Phenolic compounds and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid ester compounds; wherein the hydroxyl group is substituted by amino-substituted phenolic compounds and 1, The sulfonamide compound of 2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; the phenolic compound in which the hydroxyl group is substituted by the amino group is the same as 1,2-naphthoquinone Sulfonamide compounds of azido-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. The above compounds can be used alone or in combination of two or more kinds thereof.

Examples of phenolic compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2 ,3,3',4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl) )Methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2 ,3,4-Trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[ 4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyl Phenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirodiindene-5,6,7,5',6',7'-hexanol, 2,2,4 -Trimethyl-7,2',4'-trihydroxyflavan, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-dimethylphenyl]methane, etc.

More specific examples of the 1,2-quinonediazide-based compound (b-2) include esters of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid , 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonic acid ester, 4,4'-[1-[4-[1-[4-hydroxybenzene Ester of 1-methylethyl]phenyl]ethylene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid, 4,4'-[1-[4-[1 -[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. If the above-exemplified compound is used as the 1,2-quinonediazide-based compound, the transparency of the photosensitive resin composition can be further enhanced.

Based on 100 parts by weight of the silicone copolymer (A), the photoactive compound (B) may be used in an amount of 1 to 40 parts by weight, 2 to 20 parts by weight, or 4 to 15 parts by weight based on the solid content. If the amount of the photoactive compound (B) is within the above range, it is easier to form a pattern from the resin composition, and it is possible to prevent defects such as a rough surface when the coated film is formed and at the bottom of the pattern during development. Partially appearing patterns like scum. (C) Epoxy compound

The epoxy compound can increase the internal density of the resin composition in order to thereby improve the chemical resistance of the cured film formed therefrom.

The epoxy compound (C) may be a homo-oligomer or a hetero-oligomer of an unsaturated monomer containing at least one epoxy group.

Examples of unsaturated monomers containing at least one epoxy group may include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, ( 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-(meth)acrylate Epoxycyclopentyl ester, 3,4-epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N-(4-(2,3-glycidoxy)-3,5-dimethylbenzyl)propenamide, N-(4-(2,3-glycidoxy)-3, 5-Dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methyl allyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and P-vinyl benzyl glycidyl ether. Specifically, glycidyl methacrylate can be used.

The epoxy compound can be synthesized by any conventional method well known in the art. An example of a commercially available epoxy compound may be GHP03HP (glycidyl methacrylate homopolymer, Miwon Commercial Co., Ltd.).

The epoxy compound (C) may further contain the following structural unit.

Specific examples thereof may include any structural unit derived from: styrene; styrene with alkyl substituents, such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, two Ethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; styrene with halogen, such as fluorostyrene, chlorostyrene, Bromostyrene and iodostyrene; styrenes with alkoxy substituents, such as methoxystyrene, ethoxystyrene, and propoxystyrene; p-hydroxy-α-methylstyrene, acetoxy Styrene; ethylenically unsaturated compounds with aromatic rings, such as divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p-vinylbenzyl methyl ether; no Saturated carboxylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate , Tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth) Base) 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, α-hydroxymethyl acrylate Ester, ethyl α-hydroxymethacrylate, propyl α-hydroxymethacrylate, butyl α-hydroxymethacrylate, 2-methoxyethyl (meth)acrylate, 3-methyl (meth)acrylate Oxybutyl ester, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) ) Methyl ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (methyl) Acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, (meth)acrylic acid 1,1,1,3,3,3-hexafluoroisopropyl, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate and dicyclopentyl (meth)acrylate Alkenyloxyethyl; tertiary amines with N-vinyl groups, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, Allyl glycidyl ether and 2-methylallyl glycidyl ether; unsaturated amides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide and N-cyclohexylmaleimide. The structural unit derived from the above-exemplified compound may be included in the epoxy compound alone or in a combination of two or more thereof.

Specifically, from the viewpoint of the polymerizability of the composition, styrene compounds are preferable in these examples. In particular, it is more preferable in terms of chemical resistance that the epoxy compound does not contain a carboxyl group by not using a structural unit derived from a carboxyl group-containing monomer among these compounds.

The weight average molecular weight of the epoxy compound (C) can be 100 to 30,000 Da, 1,000 to 20,000, 1,000 to 15,000, or 6,000 to 10,000 Da. If the weight average molecular weight of the epoxy compound is at least 100 Da, the hardness of the cured film may be more favorable. If it is 30,000 Da or less, the cured film can have a uniform thickness, which is suitable for any step of planarizing it.

Based on 100 parts by weight of the silicone copolymer (A), the epoxy compound (C) may be used in an amount of 0 to 40 parts by weight or 5 to 20 parts by weight based on the solid content. Within the above content range, the sensitivity and chemical resistance of the photosensitive resin composition are more advantageous. If it is used in a smaller amount than the above range, the chemical resistance is significantly deteriorated. If it is used in excess, the sensitivity deteriorates significantly. (D) Surfactant

If necessary, the positive photosensitive resin composition of the present invention may further contain a surfactant (D) to enhance its coatability.

The type of surfactant (D) is not particularly limited. Examples thereof may include fluorine-based surfactants, silicon-based surfactants, nonionic surfactants, and the like.

Specific examples of the surfactant (D) may include fluorine-based and silicon-based surfactants, such as FZ-2122 supplied by Dow Corning Toray Co., Ltd., supplied by BM Chemical Company (BM BM-1000 and BM-1100 supplied by CHEMIE Co., Ltd., Megapack F-142 D, F-172, F supplied by Dai Nippon Ink Chemical Kogyo Co., Ltd. -173 and F-183, Florad FC-135, FC-170 C, FC-430 and FC-431 supplied by Sumitomo 3M Ltd., supplied by Asahi Glass Co., Ltd. ) Sufron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC- 106, Eftop EF301, EF303 and EF352 supplied by Shinakida Kasei Co., Ltd., SH-28 PA, SH-190 supplied by Toray Silicon Co., Ltd. , SH-193, SZ-6032, SF-8428, DC-57 and DC-190; non-ionic surfactants, such as polyoxyethylene alkyl ethers, including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene Oxyethylene oleyl ether, etc.; polyoxyethylene aryl ether, including polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc.; and polyoxyethylene dialkyl ester, including polyoxyethylene dilauric acid Ester, polyoxyethylene distearate, etc.; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), copolymer based on (meth)acrylate Polyflow No. 57 and 95 (manufactured by Kyoei Yuji Chemical Co., Ltd.), etc. They can be used alone or in combination of two or more kinds thereof.

Based on 100 parts by weight of the silicone copolymer (A), based on the solid content, the surfactant (D) may be used in an amount of 0.001 to 5 parts by weight, 0.05 to 3 parts by weight, or 0.2 to 2 parts by weight. Within the above content range, the coating and leveling characteristics of the composition can be good. (E) Adhesion supplement

The photosensitive resin composition of the present invention may further include an adhesion supplement (E) to enhance the adhesion to the substrate.

The adhesion extender (E) may have at least one reactive group selected from the group consisting of carboxyl group, (meth)acrylic group, isocyanate group, amino group, mercapto group, vinyl group and epoxy group .

The type of adhesion supplement (E) is not particularly limited. For example, it may be at least one selected from the group consisting of trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl triacetoxy Silane, vinyl trimethoxy silane, γ-isocyanatopropyl triethoxy silane, γ-glycidoxypropyl trimethoxy silane, γ-glycidoxy propyl triethoxy silane , N-Phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and mixtures thereof.

Preferably, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-isocyanate propyl group, which can improve the film retention rate and adhesion to the substrate Triethoxysilane, or N-phenylaminopropyl trimethoxysilane.

Based on 100 parts by weight of the silicone copolymer (A), based on the solid content, the adhesion extender (E) may be used in an amount of 0.001 to 5 parts by weight or 0.01 to 4 parts by weight. Within the above content range, the adhesion to the substrate can be further enhanced. (F) Solvent

The positive photosensitive resin composition of the present invention can be prepared in the form of a liquid composition in which the above components are mixed with the solvent (F). The solvent (F) may be, for example, an organic solvent.

The amount of solvent (F) in the photosensitive resin composition according to the present invention is not particularly limited. For example, a solvent may be used so that the solid content is 10 to 70% by weight or 15 to 60% by weight based on the total weight of the composition. The solid content refers to the components constituting the resin composition of the present invention, excluding the solvent. If the amount of the solvent is within the above range, coating of the composition can be easily performed while maintaining its fluidity at an appropriate level.

The solvent (F) of the present invention is not particularly limited as long as it can dissolve the above-mentioned components and is chemically stable. For example, the solvent may be alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, Aromatic hydrocarbons, ketones, esters, etc.

Specific examples of the solvent (F) include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, ethylene glycol monomethyl ether, ethyl acetate Glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether Acetate, dipropylene glycol methyl ether acetate, propylene glycol butyl ether acetate, toluene, xylene, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexane Ketone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutyrate, methyl 2-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 -Methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N- Dimethylacetamide, N-methylpyrrolidone, etc.

Preferred among the above are ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, ketone and the like. Particularly, preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol methyl ether acetate. , Methyl 2-methoxypropionate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, etc. The solvents exemplified above may be used alone or in a combination of two or more thereof.

In addition, the photosensitive resin composition of the present invention may further contain other additives as long as it does not adversely affect the physical properties of the photosensitive resin composition.

The photosensitive resin composition according to the present invention can be used as a positive photosensitive resin composition.

In particular, the positive photosensitive resin composition according to the present invention contains a photoactive compound of a polymer containing a repeating unit having a specific structure and/or a photoactive compound of a monomer. Therefore, the interaction between the binder resin (ie, the silicone copolymer) and the photoactive compound increases the exposed portion (ie, the exposed portion), which increases the solubility in the developer, thereby Can enhance sensitivity. In addition, a cured film capable of realizing a large edge angle of a pattern can be formed by using an appropriate amount of the photoactive compound.

The present invention provides a cured film formed of a photosensitive resin composition.

The cured film can be formed by a method known in the art, for example, a method in which a photosensitive resin composition is coated on a substrate and then cured. More specifically, in the curing step, the photosensitive resin composition coated on the substrate may be subjected to pre-baking at a temperature of, for example, 60°C to 130°C to remove the solvent; then, a photomask having a desired pattern is used. The mold is exposed to light; and a developer, such as tetramethylammonium hydroxide (TMAH) solution is used to subject it to development to form a pattern on the coating. Thereafter, if necessary, the patterned coating is subjected to post-baking at a temperature of 150°C to 300°C for 10 minutes to 5 hours to prepare a desired cured film. Exposure can be performed in a wavelength band of 200 to 500 nm based on a wavelength of 365 nm at an exposure rate of 10 to 200 mJ/cm ² . According to the method of the present invention, from the viewpoint of the method, it is possible to easily form a desired pattern.

The photosensitive resin composition can be applied to the substrate by a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc. in a desired thickness (for example, 2 to 25 µm) . In addition, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used as a light source for exposure (irradiation). If necessary, X-rays, electron rays, etc. can also be used. The photosensitive resin composition of the present invention can form a cured film, which is excellent in heat resistance, transparency, dielectric constant, solvent resistance, acid resistance, and alkali resistance. Therefore, when the cured film of the present invention thus formed is subjected to heat treatment or immersed in or brought into contact with a solvent, acid, or the like, the cured film has excellent light transmittance and no surface Roughness. Therefore, the cured film can be effectively used as a flattening film for thin film transistor (TFT) substrates of liquid crystal displays or organic EL displays; partitions of organic EL displays; interlayer dielectrics for semiconductor devices; core or cladding materials for optical waveguides, and many more. In addition, the present invention provides electronic components including a cured film as a protective film.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto. In the following preparation examples, the weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) with reference to polystyrene standards. Preparation of Silicon siloxane copolymer (A) is: EXAMPLES Example 1 Preparation of

A reactor equipped with a reflux condenser was charged with 40% by weight of phenyltrimethoxysilane, 15% by weight of methyltrimethoxysilane, 20% by weight of tetraethoxysilane, and 20% by weight of distilled water, and 5 wt% of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and then the mixture was refluxed and vigorously stirred for 7 hours in the presence of 0.1 wt% of an oxalic acid catalyst. Then, the mixture was cooled and diluted with PGMEA so that the solid content was 40%. As a result, a silicone copolymer (A) having a weight average molecular weight of 5,000 to 10,000 Da is prepared. Preparation of the epoxy compound (C) is: Example 2 Preparation of

The three-neck flask was equipped with a cooling tube and placed on a stirrer equipped with a thermostat. Into the flask was charged 100 parts by weight of a monomer consisting of 100 mol% of glycidyl methacrylate, 10 parts by weight of 2,2'-azobis(2-methylbutyronitrile) and 100 parts by weight The PGMEA is then charged with nitrogen. Thereafter, the temperature of the solution was increased to 80°C while slowly stirring the solution, and the temperature was maintained for 5 hours. Next, the resultant was diluted with PGMEA so that the solid content was 20% by weight. As a result, an epoxy compound (C) having a weight average molecular weight of 6,000 to 10,000 Da is prepared. Examples and comparative examples: preparation of positive photosensitive resin composition

The photosensitive resin compositions of the following Examples and Comparative Examples were each prepared using the compound prepared in the above Preparation Example.

The components used in the following examples and comparative examples are as follows. [Table 1] Component Solid content (wt%) manufacturer Silicone copolymer (A) Preparation example 1 40 - Photoactive compound (B) b-1 B-1 Polymer PAC (MCAD1040) CAS number 142443-61-6 100 Shinryo Corp. (Shinryo Corp.) B-2 Polymer PAC (D4 PAC) CAS number 181229-58-3 100 Shinryo Corporation b-2 B-3 Monomer PAC (MIPHOTO TPA517) 100 Miwon Corporation Epoxy compound (C) Preparation example 2 20 - Surfactant (D) Silicone-based leveling surfactant, FZ-2122 100 Dow Corning Toray Corporation Solvent (F) F-1 Propylene glycol monomethyl ether acetate (PGMEA) - Chemtronics F-2 γ-butyrolactone - BASF Corporation (BASF) Example 1

100 parts by weight of the silicone copolymer (A) prepared in Preparation Example 1, 13.7 parts by weight of the polymer PAC (MCAD1040) (B-1) as the photoactive compound (B), and 12.4 parts by weight The epoxy compound (C) prepared in Preparation Example 2 and 0.1 parts by weight of FZ-2122 as the surfactant (D) were uniformly mixed. The mixture was dissolved in a mixed solvent of PGMEA and GBL (PGMEA:GBL=93:7) so that the solid content of the mixture was 17% by weight. The resultant was stirred for 2 hours, and filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a photosensitive resin composition solution having a solid content of 17% by weight. Examples 2 to 8 and Comparative Examples 1 to 3

The photosensitive resin composition solutions were each prepared in the same manner as in Example 1, except that the types and/or contents of the respective components were changed as shown in Table 2 below. [Table 2] Silicone copolymer (A) Photoactive compound (B) Epoxy compound (C) Surfactant (D) b-1 b-2 B-1 B-2 B-3 Example 1 100 13.7 - - 12.4 0.1 Example 2 100 11.4 - 2.3 12.4 0.1 Example 3 100 9.1 - 4.6 12.4 0.1 Example 4 100 6.8 - 6.8 12.4 0.1 Example 5 100 4.6 - 9.1 12.4 0.1 Example 6 100 - 11.4 2.3 12.4 0.1 Example 7 100 - 9.1 4.6 12.4 0.1 Example 8 100 - 6.8 6.8 12.4 0.1 Comparative example 1 100 - - 13.7 12.4 0.1 Comparative example 2 100 2.3 - 11.4 12.4 0.1 Comparative example 3 100 - 2.3 11.4 12.4 0.1 [ Evaluation example ] Evaluation example 1 : Evaluation of membrane retention rate

The compositions prepared in the Examples and Comparative Examples were each coated on a glass substrate by spin coating. The coated substrate was then pre-baked on a hot plate maintained at 105° C. for 90 seconds to form a dry film. A mask with a square hole pattern with a size of 2 µm to 25 µm is placed on the dry film. Then, using an aligner (model name: MA6) emitting light with a wavelength of 200 nm to 450 nm, the film is exposed for a certain period of time based on a wavelength of 365 nm at an exposure rate of 0 to 200 mJ/cm ² (ie, the bleaching step) ). The exposed film was developed with 2.38% by weight of tetramethylammonium hydroxide aqueous developer through a stirring nozzle at 23°C for 80 seconds. The thus-obtained exposed film was heated in a convection oven at 230° C. for 30 minutes to prepare a cured film having a thickness of 3 µm (ie, a hard baking step).

A non-contact thickness measuring device (SNU Precision) was used to measure the film thickness after coating and the film thickness after curing (or hard baking). The film retention rate (%) is obtained as a percentage of the ratio of the film thickness after curing to the film thickness after coating (ie, (thickness after curing/thickness after coating)×100). Evaluation example 2 : Sensitivity evaluation - hole size

A cured film was obtained in the same manner as in Evaluation Example 1, except that the exposure rate at the time of exposure was 100 mJ/cm ² . For the hole pattern formed with the mask size of 10 µm in the above formula, the size of CD (critical dimension; unit: µm) was measured. If it is at least 10 µm, the sensitivity is good (○). If it is less than 10 µm, the sensitivity is poor (×). Evaluation example 3 : Evaluation of pattern edge - measurement of cone angle

A cured film was obtained in the same manner as in Evaluation Example 1. For the 4 µm holes in the pattern of the cured film, a cross-sectional view was taken with a scanning electron microscope (S-4300, manufacturer: Hitachi). A micro-optical microscope (STM6-LM, manufacturer: OLYMPUS) was used to measure the angle between the pattern edge and the substrate side at the interface between the pattern edge and the substrate. It was evaluated according to the following criteria. Evaluation criteria: ○ (70° or greater), × (less than 70°) [Table 3] Film retention rate (%) Evaluation of hole size Cone angle (°) Example 1 93.9 ○ 92.6 ○ Example 2 96.2 ○ 83.0 ○ Example 3 96.0 ○ 82.2 ○ Example 4 95.7 ○ 81.5 ○ Example 5 95.7 ○ 84.6 ○ Example 6 94.9 ○ 80.0 ○ Example 7 94.6 ○ 81.0 ○ Example 8 94.8 ○ 82.9 ○ Comparative example 1 95.1 ○ 62.9 × Comparative example 2 94.0 ○ 63.4 × Comparative example 3 93.9 ○ 68.5 ×

As shown in Table 3 and FIG. 1, all cured films prepared from the compositions of the examples (which fall within the scope of the present invention) are excellent in terms of film retention rate. It was found that all the hole patterns were 10 µm or larger, and thus the sensitivity was excellent. In addition, all cured films prepared from the compositions of the examples have a taper angle of at least 80°. In contrast, the cured films prepared from the compositions of Comparative Examples 1 to 3 had a poor taper angle of less than 70°, although they were comparable to the cured films prepared from the compositions of the Examples in terms of film retention and sensitivity.

no

[Fig. 1] shows each photograph of a cross section of a 4 µm-hole in a pattern formed on the surface of the cured film obtained from the compositions of Examples 1, 5 and Comparative Example 1 by a scanning electron microscope.

no

Claims (7)

A positive photosensitive resin composition comprising: (A) a siloxane copolymer; (B) a photoactive compound comprising a compound containing a repeating unit represented by the following formula 1: [Formula 1]

In the above formula 1, A ₁ and A ₂ are each independently hydrogen, a hydroxyl group, a phenol group, a C _1-4 alkyl group, a C _6-15 aryl group, or a C _1-4 alkoxy group, and R ₁ is hydrogen or

, And n is an integer from 3 to 15. The positive photosensitive resin composition according to the first item of the scope of patent application, wherein the silicone polymer (A) comprises a structural unit derived from a silane compound represented by the following formula 2: [Formula 2] (R ₂ ) _m Si(OR ₃ ) _4-m In the above formula 2, m is an integer from 0 to 3, and R _{2 is} each independently a C _1-12 alkyl group, a C _2-10 alkenyl group, a C _6-15 aryl group, 3-membered to 12-membered heteroalkyl, 4-membered to 10-membered heteroalkenyl, or 6-membered to 15-membered heteroaryl, and R _{3 is} each independently hydrogen, C _1-6 alkyl, C _2-6 acyl , Or a C _6-15 aryl group, wherein the heteroalkyl group, the heteroalkenyl group, and the heteroaryl group each independently have at least one heteroatom selected from the group consisting of O, N, and S. The positive photosensitive resin composition described in item 2 of the scope of patent application, wherein the siloxane polymer (A) contains a structural unit derived from the silane compound represented by the above formula 2 where m is 0. The positive photosensitive resin composition according to the first item of the patent application, wherein the photoactive compound (B) further includes a quinonediazide-based monomer. The positive photosensitive resin composition as described in the first item of the scope of patent application, which further contains an epoxy compound (C). The positive photosensitive resin composition as described in item 1 of the scope of patent application, which further comprises (D) a surfactant, (E) an adhesion supplement, or a combination thereof. A cured film is prepared from the positive photosensitive resin composition described in item 1 of the scope of patent application.

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