TW201624135A - Positive-type photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition and a cured film prepared therefrom. The photosensitive resin composition, which comprises (A) a siloxane polymer containing at least onestructural unit derived from a silane compound represented by formula (I), (B) an epoxy compound, and (C) a 1,2-quinonediazide compound, can maintain the advantages of the conventional compositions containing a siloxane polymer such as high transparency, while having improved chemical resistance; thus, it can provide a cured film or a planarized film having improved stability during a post-processing.

Description

Positive photosensitive resin composition and cured film prepared therefrom

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom. Specifically, it relates to a positive photosensitive resin composition which can form a cured film having high transparency and excellent chemical resistance and can be used for a liquid crystal display (LCD) or an organic light emitting diode (OLED). )in.

It has been reported that a method of increasing the aperture ratio of a display device can produce an LCD or OLED having a higher accuracy/resolution characteristic. According to this method, a transparent planarizing film is disposed as a protective film on a thin film transistor (TFT) substrate, which allows the data lines and the pixel electrodes to overlap, thereby increasing the aperture ratio compared to the conventional method. To prepare such a transparent planarization film, several processing steps are employed to impart a particular pattern. The positive photosensitive resin composition is widely used in this method because it requires less processing steps. Specifically, the positive photosensitive resin composition containing a siloxane polymer has high heat resistance, high transparency, and low dielectric constant. As everyone knows.

Korean Patent Laid-Open Publication No. 2006-59202 discloses a composition comprising a phenolic hydroxyl group-containing oxirane polymer in an amount of 20 mol% or less, in the ortho position relative to the phenolic hydroxyl group therein or A diazide compound containing no methyl group in the para position, and a compound containing an alcoholic hydroxyl group and/or a ring compound containing a carbonyl group are used as a solvent. Also disclosed is a cured film prepared from the composition that satisfies a particular chromaticity coordinate and has a light transmission of at least 95%.

Korean Laid-Open Patent Publication No. 2010-43259 discloses a decane-based photosensitive resin composition comprising a decane polymer, an acrylic resin, a diazide compound, and a solvent. This composition has excellent adhesion properties to the substrate by using a combined siloxane polymer and an acrylic resin.

However, when the cured film is immersed in a solvent, an acid, a base, and the like or in contact with a solvent, an acid, a base, and the like, planarization is prepared from a conventional positive photosensitive composition containing such a siloxane polymer. The film or display device using the same may have problems such as swelling or delamination of the film from the substrate.

Accordingly, it is an object of the present invention to obtain a photosensitive resin composition which can form a cured film having high transparency and excellent chemical resistance and can be used in an LCD or an OLED.

According to an aspect of the invention, there is provided a photosensitive resin composition comprising: (A) a siloxane polymer having at least one structural unit derived from a decane compound represented by the formula (I), (B) an epoxy compound and (C) 1,2--quinonediazide _{^{compound: (R 1) n Si (}} R 2) 4-n (I)

Wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aromatic having 7 to 12 carbon atoms An alkyl group or an alkylaryl group having 7 to 12 carbon atoms, and in the case of a plurality of R ¹ , which may be the same or different from each other; R ² is a hydrogen atom, a halogen atom, and has 1 to 12 An alkoxy group of a carbon atom, an amine group, a decyloxy group having 2 to 12 carbon atoms or an aryloxy group having 6 to 12 carbon atoms, and in the case of a plurality of R ² , they may be identical to each other Or different; and n is an integer from 0 to 3.

The photosensitive resin composition of the present invention can maintain the advantages of a conventional composition containing a siloxane polymer, such as high transparency, and at the same time, has improved chemical resistance; therefore, it can provide curing with improved stability during post-treatment. Membrane or planarization film.

According to an embodiment of the present invention, the photosensitive resin composition comprises (A) a decyl alkane polymer, (B) an epoxy compound, and (C) a 1,2-diazide hydrazine compound, and optionally (D) a solvent, (E) a surfactant, and/or (F) an additive.

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

In the present specification, "(meth)acryloyl" means "acryloyl" and/or "methacryl", and "(meth)acrylate" means "acrylate" and/or "Methacrylate".

(A) alkane polymer

The siloxane polymer (or polyoxyalkylene) of the present invention contains a condensate of a decane compound and/or a hydrolyzate thereof. The decane compound or a hydrolyzate thereof may be a decane compound having 1 to 4 functional groups.

Thus, the siloxane polymer may comprise a oxoxane structural unit selected from the group consisting of the following Q, T, D, and M types:

- Q-type oxane structural unit refers to a siloxane structural unit containing a ruthenium atom and four adjacent oxygen atoms; for example, it may be derived from a tetrafunctional decane compound or a decane compound having four hydrolyzable groups Hydrolyzed product.

- a T-type decane structural unit refers to a siloxane structural unit containing a ruthenium atom and three adjacent oxygen atoms; for example, it may be derived from a trifunctional decane compound or a decane compound having three hydrolyzable groups Hydrolyzed product.

- a D-type oxane structural unit refers to a siloxane structural unit containing a ruthenium atom and two adjacent oxygen atoms (ie, a linear oxirane structural unit); for example, it may be derived from a difunctional decane compound or have A hydrolyzate of a hydrolyzable group of a decane compound.

- a M-type decane structural unit refers to a siloxane structural unit containing a ruthenium atom and an adjacent oxygen atom; for example, it may be derived from a monofunctional decane A hydrolysis product of a compound or a decane compound having a hydrolyzable group.

The siloxane polymer contains at least one structural unit derived from a decane compound represented by the formula (I). For example, the siloxane polymer may be a condensate of a decane compound represented by the formula (I) and/or a hydrolyzate thereof: (R ¹ ) _n Si(R ² ) _4-n (I)

Wherein R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, R ² is a hydrolyzable group, and n is an integer of 0 to 3.

Examples of the non-hydrolyzable organic group represented by R ¹ may include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An arylalkyl group having 7 to 12 carbon atoms and an alkylaryl group having 7 to 12 carbon atoms. It can be linear, branched or circular. Further, in the case where a plurality of R ¹ are present in the same molecule, they may be the same or different from each other and may be substituted and/or unsubstituted. R ¹ may contain structural units having a hetero atom such as an ether, an ester, and a thioether. The non-hydrolyzable nature required for R ¹ means that the compound must remain stable under conditions in which the hydrolyzable R ² is hydrolyzed.

The hydrolyzable group represented by R ² generally means that the compound can be hydrolyzed to form a stanol group or form a condensate when the compound is heated in the absence of a catalyst at a temperature of from 25 ° C to 100 ° C in the presence of excess water. Any group. Examples of the hydrolyzable group may include a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amine group, a decyloxy group having 2 to 12 carbon atoms, and having 6 to 12 carbons The aryloxy group of the atom. In the case where a plurality of R ² are present in the same molecule, they may be the same or different from each other.

The decane compound represented by the formula (I) may be, for example, four a hydrocarbyl-substituted decane compound (i.e., n = 0), a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups (i.e., n = 1), two non-hydrolyzable groups, and two hydrolyzable groups a group substituted decane compound (i.e., n = 2) or a decane compound substituted with three non-hydrolyzable groups and one hydrolyzable group (i.e., n = 3).

A representative example of a decane compound may include a decane compound substituted with four hydrolyzable groups such as tetrachlorodecane, tetraaminodecane, tetraethoxydecane, tetramethoxydecane, tetraethoxydecane, and tetra. Butoxy decane, tetraphenoxy decane, tetraphenyl methoxy decane, and tetrapropoxy decane; a decane compound substituted with a non-hydrolyzable group and three hydrolyzable groups, such as methyltrichloromethane, A Trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tributoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triiso Propoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, d ³ - methyl trimethyl Oxydecane, nonafluorobutylethyltrimethoxydecane, trifluoromethyltrimethoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltriethoxydecane, N-hexyltrimethoxydecane, n-hexyltriethoxydecane, decyltrimethyl Base decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3 - propylene methoxy propyl trimethoxy decane, 3-propenyl methoxy propyl triethoxy decane, p-hydroxyphenyl trimethoxy decane, 1-(p-hydroxyphenyl) ethyl trimethoxy decane, 2-(p-hydroxyphenyl)ethyltrimethoxydecane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3 , 3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3- Glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy Baseline, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy] Propyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, and 3-trimethoxydecylpropyl Succinic acid; a decane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, such as dimethyldichlorodecane, dimethyldiaminodecane, dimethyldiethoxydecane, two Methyldimethoxydecanediphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldiphenoxydecane, dibutyldimethoxydecane, dimethyldiethoxy Decane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)methyldiethoxydecane, 3-(2-aminoethylamino) Propyl dimethoxymethyl decane, 3-aminopropyl diethoxymethyl decane, 3-chloropropyl dimethoxymethyl decane, 3-mercaptopropyl dimethoxymethyl decane, Cyclohexyldimethoxymethyl decane, diethoxymethylvinyl decane, dimethoxymethylvinyl decane, and dimethoxy bis-p-tolyl decane; and via three non-hydrolyzable groups and a hydrocarbyl group-substituted decane compound such as trimethylchlorodecane, hexamethyldiazepine, trimethyldecane, tributyldecane, trimethylmethoxydecane, tributyl Silane group, (3-glycidoxypropyl) dimethylmethoxysilane Silane and (3-glycidoxypropyl) silane-dimethylethoxy.

Preferred among the decane compounds substituted with four hydrolyzable groups are tetramethoxynonane, tetraethoxydecane and tetrabutoxydecane; Preferred among the decane compound in which the hydrolyzable group and the three hydrolyzable groups are substituted are methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltributoxydecane. , phenyltrimethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltributoxydecane, and butyltrimethoxydecane; Preferred among the non-hydrolyzable group and the two hydrolyzable group-substituted decane compounds are dimethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, and diphenyldiene. Phenoxydecane, dibutyl dimethoxydecane, and dimethyl ethoxy decane.

These decane compounds may be used singly or in combination of two or more thereof.

The conditions for preparing the hydrolyzate of the decane compound represented by the formula (I) or a condensate thereof are not particularly limited. For example, the hydrolyzate of the decane compound represented by the formula (I) or a condensate thereof can be prepared, if necessary, by diluting the decane compound of the formula (I) in, for example, ethanol, 2-propanol, acetone, butyl acetate. a solvent of an ester or the like; a water necessary for the reaction, and an acid (for example, hydrochloric acid, acetic acid, nitric acid, and the like) or a base (for example, ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide) as a catalyst The base ammonium and the like); and then the mixture thus obtained is stirred to complete the hydrolysis polymerization.

Preferably, the condensate (i.e., the decane polymer) obtained by subjecting the decane compound of the formula (I) to hydrolysis polymerization has a weight average molecular weight (Mw) in the range of 5,000 to 50,000. Within this range, the photosensitive resin composition may have desirable film formation characteristics, solubility, and dissolution rate in the developer.

The kind of the solvent and the acid or base catalyst used for the preparation and the amount thereof are not particularly limited. The hydrolysis polymerization can be carried out at a low temperature of 20 ° C or lower. However, the reaction can also be promoted by heating or reflux. The time required for the reaction may vary depending on the kind and concentration of the decane monomer, the reaction temperature, and the like. Conventionally, the reaction time required to obtain a condensate having a weight average molecular weight of 5,000 to 50,000 is in the range of 15 minutes to 30 days; however, the reaction time in the present invention is not limited thereto.

The decane polymer (A) may include a structural unit derived from a decane compound represented by the formula (I), wherein n is 0 (i.e., a Q-type structural unit). Preferably, the siloxane polymer (A) comprises, in an amount of from 10 mol% to 60 mol%, based on the total moles of Si atoms, of structural units derived from a decane compound represented by the formula (I), wherein n is 0. As used herein, the term "% by mole based on the total number of moles of Si atoms" means the total number of moles of Si atoms contained in all structural units constituting the siloxane polymer (A), specific The percentage of the molar number of Si atoms contained in the structural unit. When the amount is in a preferred range, the photosensitive resin composition can maintain its solubility in an alkaline aqueous solution during the pattern formation in an appropriate range, thereby preventing a decrease in solubility of the composition or a sharp increase in solubility. Any defects.

Further, the siloxane polymer (A) may include a structural unit derived from a decane compound represented by the formula (I), wherein n is 1 (i.e., a T-type structural unit). Preferably, the siloxane polymer (A) comprises from 30 mole % to 90 mole %, more preferably from 50 mole % to 80 mole %, based on the total moles of Si atoms. The structural unit of the decane compound represented by free formula (I), wherein n is 1. Within this preferred range, the photosensitive resin composition can form a cured film having a more precise pattern.

Specifically, from the viewpoint of hardness, sensitivity, and retention of the cured film, the siloxane polymer preferably includes a structural unit derived from a decane compound represented by the formula (I), wherein n is 1 and R ¹ is aryl Base, preferably phenyl (ie T-phenyl type structural unit). Preferably, the siloxane polymer (A) comprises from 30 mole % to 70 mole %, more preferably from 35 mole % to 60 mole %, based on the total moles of Si atoms. From the T-phenyl type structural unit of the compound. Within this preferred range, the decane polymer and the 1,2-diazepine naphthoquinone compound may have desirable compatibility, thereby improving the transparency of the cured film and preventing a decrease in sensitivity.

The decane polymer (A) may include a structural unit derived from a decane compound represented by the formula (I), wherein n is 2 (i.e., a D-type structural unit). Preferably, the siloxane polymer (A) comprises a derivative in an amount of from 0.1 mol% to 60 mol%, more preferably from 1 mol% to 50 mol%, based on the total moles of Si atoms. The structural unit of the decane compound represented by free formula (I), wherein n is 2.

Within this range, the cured film will maintain a suitable hardness and have a certain flexibility, thereby being resistant to cracking caused by external stress.

The photosensitive resin composition of the present invention may comprise a polymerization of oxoxane in an amount of from 50% by weight to 95% by weight, preferably from 65% by weight to 90% by weight, based on the total weight of the solid content of the solvent-free composition. (A). Within this preferred amount range, the resin composition can maintain its developability at a suitable level, thereby producing a cured film having improved film retention and pattern resolution.

(B) epoxy compound

In the photosensitive resin composition of the present invention, an epoxy compound and a decane polymer are used to increase the internal density of the siloxane adhesive. The chemical resistance of the cured film thus prepared is improved.

The epoxy compound may be, for example, a compound containing a structural unit represented by the formula (II):

Wherein R ³ is H or C ₁ -C ₂ alkyl, preferably H; R ⁴ is H, or a straight or branched C ₁ -C ₅ alkyl group, preferably a straight or branched C ₁ -C ₅ alkane And m is an integer from 1 to 10, preferably from 1 to 5.

The epoxy compound may be, for example, a high oligomer having a structural unit of the above formula (II).

Compounds having structural units of formula (II) can be synthesized by any of the conventional methods well known in the art.

An example of a commercially available compound having a structural unit of the formula (II) may include GHP03 (glycidyl methacrylate homopolymer, Miwon Commercial Co., Ltd.) having the formula ( Repeat unit of III):

The epoxy compound (B) may further include a structural unit derived from a monomer different from the structural unit of the formula (II).

A representative example of a structural unit derived from a monomer different from the structural unit of the formula (II) may comprise any structural unit derived from styrene; styrene having an alkyl substituent such as methyl styrene, Methylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylbenzene Ethylene and the like; styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, iodine styrene and the like; styrene having an alkoxy substituent such as methoxystyrene or ethoxylate Styrene, propoxy styrene and the like; p-hydroxy-α-methylstyrene, ethyl styrene styrene; ethylenically unsaturated compounds having an aromatic ring, such as divinylbenzene, vinyl phenol, O-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether; unsaturated carboxylic acid esters such as methyl (meth) acrylate, (meth) acrylate Ethyl ester, butyl (meth)acrylate, dimethyl (meth)acrylate Aminoethyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofuran (meth)acrylate Ester, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) Glyceryl acrylate, α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, α-hydroxypropyl methacrylate, α-hydroxy methacrylate butyl, (meth) acrylate 2-methyl Oxyethyl ester, 3-methoxybutyl (meth)acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy three Propylene glycol (meth) acrylate, poly(ethylene glycol) methyl ether (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxy (meth) acrylate Ethyl ethyl ester, phenoxy diethylene glycol (meth)acrylic acid Ester, p-nonylphenoxy polyethylene glycol (meth) acrylate, p-nonyl phenoxy polypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, (meth) acrylate 1 , 1,1,3,3,3-hexafluoroisopropyl ester, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, (A) Isobornyl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, cyclopentenyl (meth) acrylate Ethyl ethyl esters and analogs; tertiary amines having N-vinyl groups such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine and the like; unsaturated ethers such as vinyl Methyl ether, vinyl ethyl ether and the like; an unsaturated ether having an epoxy group such as allyl glycidyl ether, 2-methylallyl glycidyl ether and the like; an unsaturated quinone imine, Such as N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-ring Hexyl maleimide and the like. The structural unit derived from the above-exemplified compound may be contained in the epoxy compound (B) in the form of a single compound or a combination of two or more thereof.

For the polymerizability of the composition, styrenic compounds are preferred in these examples. Specifically, for the chemical resistance, the epoxy group-free epoxy compound (B) is preferably obtained by not using a structural unit derived from a monomer having a carboxyl group in these compounds.

The structural unit derived from the monomer different from the structural unit of the formula (II) may be 0 to 70 mol%, preferably 10 mol%, based on the total number of moles of the structural unit constituting the epoxy compound (B). 60% of the amount used. Within this preferred amount range, the cured film can have a desired hardness.

The Mw of the epoxy compound (B) can be from 100 to 30,000, Good range from 1,000 to 15,000. If the Mw of the epoxy compound is at least 100, the cured film may have an increased hardness. Further, if the Mw of the epoxy compound is 30,000 or less, the cured film may have a uniform thickness, which is suitable for leveling any step difference. The weight average molecular weight was determined by gel permeation chromatography (GPC, eliminator: tetrahydrofuran) using a polystyrene standard.

In the photosensitive resin composition of the present invention, the weight ratio of the siloxane polymer (A) to the epoxy compound (B), that is, A:B, may be 99.5:0.5 to 50, based on the total weight of the solid content. : 50, preferably 98:2 to 60:40, more preferably 97:3 to 70:30. Within the above range, the photosensitive resin composition can have improved sensitivity.

(C) 1,2-diazide ruthenium compound

The photosensitive resin composition of the present invention includes a 1,2-diazide ruthenium compound (C).

The 1,2-diazide compound can be any compound used as a sensitizer in the field of photoresist. Representative examples include esters of phenolic compounds with 1,2-diazidobenzoquinone-4-sulfonic acid or 1,2-diazidobenzoquinone-5-sulfonic acid; phenolic compounds and 1,2-diazepine naphthalene An ester of 醌-4-sulfonic acid or 1,2-diazepinenaphthoquinone-5-sulfonic acid; a phenol compound whose hydroxyl group is substituted with an amine group and 1,2-diazidobenzoquinone-4-sulfonic acid or 1 , a sulfonamide of 2-diazidobenzoquinone-5-sulfonic acid; and a phenolic compound whose hydroxyl group is substituted with an amine group and 1,2-diazepinenaphthoquinone-4-sulfonic acid or 1,2-double Sulfaguanamine of a naphthoquinone-5-sulfonic acid. The above compounds may be used in the form of a single compound or in a combination of two or more compounds.

Examples of the phenol compound 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-three (p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-three (2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl Phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1 , 1'-spirobiguanidine-5,6,7,5',6',7'-hexanol and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan. The above compounds may be used in the form of a single compound or in a combination of two or more compounds.

More specific examples of the 1,2-diazide ruthenium compound include an ester of 2,3,4-trihydroxybenzophenone and 1,2-diazepinenaphthoquinone-4-sulfonic acid, 2,3,4- An ester of trihydroxybenzophenone with 1,2-diazepinenaphthoquinone-5-sulfonic acid, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl Ester of ethyl]phenyl]ethylidene]bisphenol with 1,2-diazepinenaphthoquinone-4-sulfonic acid and 4,4'-[1-[4-[1-[4-hydroxyphenyl] An ester of 1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-diazepinenaphthoquinone-5-sulfonic acid. The above compounds may be used in the form of a single compound or in a combination of two or more compounds.

The above 1,2-diazide ruthenium compound can improve the transparency of the positive photosensitive resin composition.

The 1,2-diazide hydrazone compound (C) may be in an amount ranging from 2 to 50 parts by weight, preferably from 5 to 20 parts by weight, based on 100 parts by weight of the solid content of the siloxane polymer (A). use. When the 1,2-diazide compound is used in the above amount range, the resin composition can easily form a pattern having no defects such as a rough surface of the cured film and dross at the bottom of the pattern after development.

(D) solvent

The photosensitive resin composition of the present invention can be produced as a liquid composition by mixing the above components in a solvent. The amount of the solvent in the photosensitive resin composition according to the present invention is not particularly limited; however, for example, the resin composition may contain a solvent such that the solid content thereof is 10 parts by weight based on the total weight of the resin composition. % to 70% by weight, preferably 15% to 60% by weight, more preferably 20% to 40% by weight. The solid content means all components excluding any solvent contained in the resin composition of the present invention.

The solvent is not particularly limited as long as it can dissolve each component of the composition and is chemically stable. Examples of the solvent may include an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, a propylene glycol alkyl ether propionate, Aromatic hydrocarbons, ketones and esters. Specific examples of the solvent include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol single 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 Alcohol 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 diethyl ether acetate, propylene glycol propyl ether acetate Ester, dipropylene glycol methyl ether acetate, propylene glycol butyl ether acetate, toluene, xylene, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- methyl Methyl butyrate, methyl 2-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxyl Methyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethyl Indoleamine, N-methylpyrrolidone and the like. Preferred among these exemplary solvents are ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and ketone. Specifically, 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, propylene glycol methyl ether acetate are preferred. , methyl 2-methoxypropionate, γ-butyrolactone, and 4-hydroxy-4-methyl-2-pentanone.

The above compounds may be used singly or in combination of two or more thereof.

(E) surfactant

The photosensitive resin composition of the present invention may further include a surfactant in order to improve coatability.

The surfactant is not limited to a specific species. Preferred are fluorine-based surfactants, quinone-based surfactants, nonionic surfactants, and the like.

Specific examples of the surfactant include a fluorine- or quinone type surfactant such as FZ-2122 (manufactured by Dow Corning Toray Silicon Co., Ltd.), BM-1000, BM-1100 ( Made by BM CHEMIE Co., Ltd., Megapack F-142 D, Megapack F-172, Megapack F-173, and Megapack F-183 (Dai Nippon Ink) Chemical Kogyo Co., Ltd.), Florad FC-135, Florad FC-170 C, 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 And Sufron SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF301, Eftop 303, and 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.); non-ion Type of surfactant, such as polyoxyethylene alkyl ether, comprising polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc., polyoxyethylene aryl ether, comprising polyoxyethylene octylphenyl ether , polyoxyethylene nonylphenyl ether, and the like, and polyoxyethylene dialkyl ester, including polyoxyethylene dilaurate, polyoxyethylene distearate, etc.; and organic decane polymer KP341 (by Shinhman (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylate copolymer Polyflow No. 57 and No. 95 (Kyoeisha Yuji Chemical Co., Ltd.) Ltd.)) and so on. It may be used singly or in combination of two or more thereof.

The surfactant (E) may be used in an amount of from 0.001 part by weight to 5 parts by weight, preferably from 0.05 part by weight to 1 part by weight, based on 100 parts by weight of the solid content of the siloxane polymer (A). When the amount of the surfactant is 0.05 parts by weight or more, the composition may have improved coatability without cracks on the surface of the coating film formed of the composition. When the amount of surfactant When it is 1 part by weight or less, the composition may have an improved thermal stability at a high temperature and a price advantage.

(F) adhesion promoter

The photosensitive resin composition of the present invention may further include an adhesion promoter to improve the adhesion of the coating to the substrate.

The adhesion promoter may have at least one reactive group selected from the group consisting of a carboxyl group, a (meth) propylene group, an isocyanate group, an amine group, a decyl group, a vinyl group, and an epoxy group.

Adhesives are not limited to a particular species. Preferred is trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethyl Oxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, N-phenylaminopropyltrimethoxydecane, and β-(3,4 -Epoxycyclohexyl)ethyltrimethoxydecane. Preferably, in order to obtain the desired film retention and the adhesion of the coating to the substrate, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane or N- may be used. Phenylaminopropyltrimethoxydecane.

The adhesion promoter (F) may be used in an amount of from 0.001 part by weight to 5 parts by weight, preferably from 0.01 part by weight to 2 parts by weight, based on 100 parts by weight (in terms of solid content) of the siloxane polymer (A). Within the preferred range, the composition may have improved adhesion to the substrate without impairing the resolution of the coated film.

In addition to the above components, the photosensitive resin composition of the present invention must Other additives may be included as needed, as long as the physical properties of the composition are not adversely affected.

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

Specifically, the photosensitive resin composition of the present invention uses an epoxy compound and a siloxane polymer to increase the internal density of the siloxane adhesive. Accordingly, the present invention can provide a positive type resin composition which can form a cured film having improved chemical resistance (solvent, acid, alkali, etc.) during post-treatment.

Further, the present invention provides a cured film prepared from a photosensitive resin composition.

The cured film can be prepared by, for example, applying a photosensitive resin composition onto a substrate and subjecting it to a curing treatment by a conventional method well known in the art.

The coating process can be carried out by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, and the like, for example, at a desired thickness of 2 μm to 25 μm.

In order to cure the photosensitive resin composition, for example, the composition coated on the substrate may be subjected to prebaking at a temperature of, for example, 60 ° C to 130 ° C to remove any solvent; in the case of a photomask having a desired pattern The lower exposure to light; and development using a developer such as a tetramethylammonium hydroxide (TMAH) solution to form a pattern on the coated film. The exposure can be carried out at a wavelength in the range of 200 nm to 500 nm and an exposure of 10 mJ/cm 2 to 200 mJ/cm 2 (at a wavelength of 365 nm). As a light source for exposure, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal can be used. A halide lamp, an argon laser, or the like; and if necessary, X-rays, electron beams, or the like can also be used.

Next, if necessary, the patterned coating film is post-baked at a temperature of, for example, 150 ° C to 300 ° C for 10 minutes to 5 hours to prepare a film to be cured.

The cured film thus obtained has excellent physical properties in terms of heat resistance, transparency, dielectric constant, solvent resistance, acid resistance, and base resistance.

When the composition is subjected to heat treatment or immersion in a solvent, an acid, a base or the like or in contact with a solvent, an acid, a base or the like, the cured film has excellent light transmittance without surface swelling or roughness. Therefore, the cured film can be effectively used as a planarization film for a TFT substrate of an LCD or an OLED; a spacer of an OLED; an interlayer dielectric of a semiconductor device; an inner core or a cladding material of the optical waveguide, and the like.

Further, the present invention provides an electronic component 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 set forth to illustrate the invention, and the scope of the invention is not limited thereto.

In the following preparation examples, the weight average molecular weight was determined by gel permeation chromatography (GPC) using a polystyrene standard.

Preparation Example 1: siloxane polymer (a)

The reaction flask was charged with 0.07 g (0.0019 mol) of 0.1 equivalent hydrochloric acid and 40.57 g (2.25 mol) of deionized water, followed by stirring. Next, add 92.45 grams (0.383 moles) of phenyl triethoxylate to it. Baseline (Aldrich), 34.29 grams (0.192 moles) methyltriethoxydecane (Aldrich), 40.06 grams (0.192 moles) of tetraethoxydecane (Aldrich) and 12 Glucosamine monomethyl ether acetate (PGMEA, Aldrich) was then stirred at room temperature for one hour. The reaction flask was equipped with a condenser and a dean-stark trap, and the mixture was distilled at 105 ° C for 2 hours, and then at 100 ° C for 3 hours. Subsequently, 6 g of PGMEA was added to the reaction mixture, and then the mixture was cooled. The remaining acid in the reaction mixture is removed by an ion exchange column. The resulting mixture was charged into a reactor, followed by removing water and alcohol therefrom at 45 ° C under reduced pressure to obtain a decane polymer having a Mw of about 4,000, followed by adding PGMEA thereto to adjust the solid content to 40 weight. %.

Preparation Example 2: a siloxane polymer (b)

The reaction flask was charged with 0.07 g (0.0019 mol) of 0.1 equivalent hydrochloric acid and 40.57 g (2.25 mol) of deionized water, followed by stirring. Next, 46.224 g (0.192 mol) of phenyltriethoxydecane (Aldrich), 68.4 g (0.383 mol) of methyltriethoxydecane (Aldrich), 40.06 g were added thereto. (0.192 mol) tetraethoxydecane (Aldrich) and 12 g of propylene glycol monomethyl ether acetate (PGMEA, Aldrich) were then stirred at room temperature for one hour. The reaction flask was equipped with a condenser and a Dean-Stark trap, and the mixture was distilled at 105 ° C for 2 hours, and then at 100 ° C for 3 hours. Subsequently, 6 g of PGMEA was added to the reaction mixture, and then the mixture was cooled. The remaining acid in the reaction mixture is removed by an ion exchange column. The resulting mixture is charged to the reactor, followed by The water and the alcohol were removed therefrom at 45 ° C under reduced pressure to obtain a decane polymer having a weight average molecular weight of about 4,000, and then PGMEA was added thereto to adjust its solid content to 30% by weight.

Preparation Example 3: Epoxy Compound (a)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight of a monomer mixture comprising glycidyl methacrylate (50 mol%) and styrene (50 mol%), 10 parts by weight of 2,2'-azobis(2-methylbutyronitrile) And 100 parts by weight of PGMEA was charged into the flask, and nitrogen was charged into the flask. The flask was heated to 80 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an epoxy compound having a weight average molecular weight of about 12,000, and then PGMEA was added thereto to adjust its solid content to 20% by weight.

Preparation Example 4: Epoxy Compound (b)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight of a monomer comprising glycidyl methacrylate (100 mol%), 10 parts by weight of 2,2'-azobis(2-methylbutyronitrile), and 100 parts by weight of PGMEA were placed in a flask. The flask was charged with nitrogen. The flask was heated to 80 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an epoxy compound having a weight average molecular weight of about 14,000, and then PGMEA was added thereto to adjust its solid content to 20% by weight.

Preparation Example 5: Acrylic Compound (a)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight including methacrylic acid (21 mol%), 3,4-epoxycyclohexylmethyl methacrylate (15 mol%), methyl methacrylate (21 mol%), and styrene ( a monomer mixture of 43 mol%), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), and 100 parts by weight of methyl 3-methoxypropionate were placed in a flask. The flask was charged with nitrogen. The flask was heated to 70 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 4,800, and then PGMEA was added thereto to adjust its solid content to 40% by weight.

Preparation Example 6: Acrylic Compound (b)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight of methacrylic acid (22.5 mol%), 3,4-epoxycyclohexylmethyl methacrylate (25 mol%), methyl methacrylate (9.5 mol%), and styrene (43 mol%) monomer mixture, 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were placed in a flask And the flask was charged with nitrogen. The flask was heated to 70 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 6,700, and then PGMEA was added thereto to adjust its solid content to 40% by weight.

Preparation Example 7: Acrylic Compound (c)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight containing methacrylic acid (24 moles) %), a monomer mixture of 3,4-epoxycyclohexylmethyl methacrylate (25 mol%) and styrene (51 mol%), 10 parts by weight of 2,2'-azobis (2) , 4-dimethylvaleronitrile) and 100 parts by weight of methyl 3-methoxypropionate were placed in a flask, and nitrogen was charged into the flask. The flask was heated to 70 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 6,800, and then PGMEA was added thereto to adjust its solid content to 40% by weight.

Preparation Example 8: Acrylic Compound (d)

A three-necked flask equipped with a condenser was placed on a hot plate stirrer with an automatic thermostat. 100 parts by weight of methacrylic acid (20 mol%), 3,4-epoxycyclohexylmethyl methacrylate (20 mol%), styrene (55 mol%), and 4-hydroxybutyl acrylate Monomer mixture of ester glycidyl ether (4HBAGE, 5 mol%), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 100 parts by weight of 3-methoxypropionic acid The methyl ester was charged into the flask, and the flask was charged with nitrogen. The flask was heated to 70 ° C while slowly stirring the mixture, and the temperature was maintained for 5 hours to obtain an acrylic compound having a weight average molecular weight of about 5,000, and then PGMEA was added thereto to adjust its solid content to 40% by weight.

Examples and Comparative Examples: Preparation of Photosensitive Resin Composition

The photosensitive resin compositions of the examples and the comparative examples were prepared by using the components obtained in the above preparation examples. In addition, the following compounds were used in the examples and comparative examples:

- 1,2-Diazide oxime compound: TPA-523, Meiyuan Commercial Co., Ltd.

- Adhesive: 3-glycidoxypropyltrimethoxydecane, GPTMS, Sigma-Aldrich

- Surfactant: bismuth leveling surfactant FZ-2122, Dow Corning Dongliyi Co., Ltd.

- Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Example 1

Uniform mixing of 14.45 g of the oxirane polymer (a) obtained in Example 1, 1.66 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazide ruthenium compound, and 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In a siloxane polymer, a T-type structural unit having a phenyl residue (T-phenyl type): a T-type structural unit having a methyl residue (T-methyl type): a Q-type structural unit The ear ratio is 50:25:25.

Example 2

Uniform mixing of 14.12 g of the oxirane polymer (a) obtained in Example 1, 2.22 g of the decane polymer (b) obtained in Preparation Example 2, and 1.66 g of the epoxy compound obtained in Preparation Example 3 (a) 0.83 g of 1,2-diazidoguanidine compound, 0.15 g of adhesion promoter, and 0.15 g of surfactant, and then dissolved in 11.43 g of solvent. The resulting solution was filtered through a 0.2 micron pore size membrane filter to obtain a solution having a solid content of 25% by weight. Resin composition. In the siloxane polymer, the T-phenyl type: T-methyl type: the molar ratio of the Q type structural unit is 47.4: 27.6:25.

Example 3

Uniformly mixing 13.29 g of the oxirane polymer (a) obtained in Example 1, 3.32 g of the decane polymer (b) obtained in Preparation Example 2, and 1.66 g of the epoxy compound obtained in Preparation Example 3 (a) 0.83 g of 1,2-diazidoguanidine compound, 0.15 g of adhesion promoter, and 0.15 g of surfactant, and then dissolved in 11.43 g of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, the T-phenyl type: T-methyl type: the molar ratio of the Q type structural unit is 46.1: 28.9:25.

Example 4

Uniformly mixing 16.11 g of the oxirane polymer (a) obtained in Example 1, 0.99 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 5

Uniform mixing of 14.45 grams of the oxime obtained in Example 1 Polymer (a), 2.22 g of the oxirane polymer (b) obtained in Example 2, 0.99 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazepine compound, 0.15 grams of adhesion promoter and 0.15 grams of surfactant, and then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, the T-phenyl type: T-methyl type: the molar ratio of the Q type structural unit is 47.4: 27.6:25.

Example 6

Uniformly mixing 13.62 g of the oxirane polymer (a) obtained in Example 1, 3.32 g of the decane polymer (b) obtained in Preparation Example 2, and 0.99 g of the epoxy compound obtained in Preparation Example 3 (a) 0.83 g of 1,2-diazidoguanidine compound, 0.15 g of adhesion promoter, and 0.15 g of surfactant, and then dissolved in 11.43 g of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, the T-phenyl type: T-methyl type: the molar ratio of the Q type structural unit is 46.1: 28.9:25.

Example 7

Uniformly mixing 16.11 g of the oxirane polymer (a) obtained in Example 1, 0.99 g of the epoxy compound (b) obtained in Preparation Example 4, 0.83 g of 1,2-diazide ruthenium compound, and 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 micron pore size membrane filter to obtain a solid content of 25% by weight. The resin composition in the form of a solution. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 8

Uniformly mixed 15.78 g of the oxirane polymer (a) obtained in Example 1, 1.66 g of the epoxy compound (b) obtained in Preparation Example 4, 0.83 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 9

Uniformly mixing 13.62 g of the oxirane polymer (a) obtained in Example 1, 3.32 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazide ruthenium compound, and 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 10

Uniform mixing of 14.12 g of the oxirane polymer (a) obtained in Example 1, 4.98 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 grams of 1,2-diazide compound, 0.15 grams of adhesion promoter, and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 11

Uniform mixing of 13.29 g of the oxirane polymer (a) obtained in Example 1, 6.64 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazide ruthenium compound, and 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 12

Uniformly mixed 11.63 g of the oxirane polymer obtained in Example 1 (a), 9.96 g of the epoxy compound (a) obtained in Preparation Example 3, 0.83 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Example 13

Uniformly mixed 9.798 g of the oxirane polymer (a) obtained in Example 1, 13.28 g of the epoxy compound (a) obtained in Preparation Example 3, 13.28 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Comparative example 1

Uniformly mixing 16.61 grams of the oxirane polymer (a) obtained in Example 1, 0.83 grams of 1,2-diazide oxime compound, 0.15 gram of adhesion promoter, and 0.15 gram of surfactant, and then dissolved in 11.43 gram of solvent in. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Comparative example 2

Uniformly mixed 15.78 g of the oxirane polymer (a) obtained in Example 1, 1.03 g of the acrylic compound (a) obtained in Preparation Example 5, 0.83 g of 1,2-diazepine compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In a siloxane polymer, T-phenyl Type: T-methyl type: The molar ratio of the Q type structural unit is 50:25:25.

Comparative example 3

Uniformly mixed 15.78 g of the oxirane polymer (a) obtained in Example 1, 1.01 g of the acrylic compound (b) obtained in Preparation Example 6, 0.83 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Comparative example 4

Uniformly mixed 15.78 g of the oxirane polymer (a) obtained in Example 1, 1 g of the acrylic compound (c) obtained in Preparation Example 7, 0.83 g of 1,2-diazide ruthenium compound, 0.15 g of adhesion promoting The agent and 0.15 grams of surfactant were then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Comparative Example 5

Uniformly mixed 15.78 g of the oxirane polymer (a) obtained in Example 1, 1.03 g of the acrylic compound (d) obtained in Preparation Example 8, 0.83 g of 1,2-diazide compound, 0.15 g of adhesion promoting Agent and 0.15 grams of surfactant was then dissolved in 11.43 grams of solvent. The resulting solution was filtered through a 0.2 μm pore size membrane filter to obtain a resin composition in the form of a solution having a solid content of 25% by weight. In the siloxane polymer, T-phenyl type: T-methyl type: Q-type structural unit has a molar ratio of 50:25:25.

Experimental Example 1: Evaluation of chemical resistance

Each of the photosensitive resin compositions obtained in the examples and the comparative examples was applied onto a glass substrate using a spin coater. The coated substrate was prebaked on a hot plate at 115 ° C for 90 seconds to form a film having a thickness of 3.1 μm. The film was then developed by spraying a developer aqueous solution (2.38 wt% tetramethylammonium hydroxide) at 23 ° C for 60 seconds. Subsequently, the developed film was exposed to light at a wavelength of 365 nm (i.e., bleaching method) at a wavelength of 200 mJ/cm 2 using a calibrator (model name: MA6) for a certain duration by using a calibrator (model name: MA6). For a time period, the calibrator emits light having a wavelength of from 200 nanometers to 450 nanometers. The film was then post-baked in a convection oven at 230 ° C for 30 minutes to obtain a cured film. The thickness (T1) of the cured film was measured by using a non-contact type height measuring device (SNU accuracy).

The reworked chemical (product name: EP-6) was introduced into a constant temperature bath and then maintained at 50 °C. The cured film was placed in a bath for 10 minutes and thermally cured on a hot plate for 10 minutes. Next, the thickness (T2) of the cured film was measured.

The chemical resistance value (%) of the cured film was calculated by using the following Equation 1: [Equation 1] Chemical resistance (%) = [(thickness after heat curing (T2) / (immersion in rework) Initial thickness (T1) before the product] × 100

When the above chemical resistance value is close to 100% (i.e., the cured film returns to its original state after swelling), the chemical resistance of the cured film is considered to be satisfactory.

Experimental Example 2: Evaluation of Resolution (Sensitivity)

Each of the compositions obtained in the examples and the comparative examples was coated on a glass substrate by using a spin coater, and the coated substrate was prebaked on a hot plate maintained at 110 ° C and dried for 90 seconds to form a thickness of 3.1 micron film. By using a calibrator (model name: MA6), the film is passed through a mask having a pattern consisting of square holes ranging in size from 2 micrometers to 25 micrometers, based on an exposure of 0 to 200 millijoules per square centimeter based on 365 nai. The wavelength of the meter is exposed to light for a certain period of time, and the calibrator emits light having a wavelength of from 200 nm to 450 nm. The film was developed by spraying an aqueous developer solution (2.38 wt% tetramethylammonium hydroxide) by a nozzle at 23 °C. The film was then heated in a convection oven at 230 ° C for 30 minutes to obtain a cured film.

The amount of exposure dose required to reach a critical dimension (CD, unit: micron) of 19 micrometers was measured for a hole pattern formed by a mask having a square hole pattern having a size of 20 μm. The lower the exposure dose, the better the resolution (sensitivity) of the cured film.

Experimental Example 3: Evaluation of developability (scumming during development)

Each of the compositions obtained in the examples and the comparative examples was coated on a ruthenium substrate by using a spin coater, and the coated substrate was prebaked on a hot plate maintained at 110 ° C and dried for 90 seconds to form a thickness of 3.1 micron film. By using Calibrator (model name: MA6), the film was exposed to light through a pattern mask at an exposure of 100 mJ/cm 2 based on a wavelength of 365 nm for a certain period of time, the calibrator emitting wavelength of 200 nm Light to 450 nm. The film was developed by spraying a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as a developer by a nozzle at 25 °C. The film was then heated in a convection oven at 200 ° C for 30 minutes to obtain a thermosetting film.

The developability of the thermosetting film was evaluated based on the shape of the developed pattern. Specifically, the shape of the developed pattern was evaluated according to the following criteria by observing a pattern formed in a contact hole having a line width of 20 μm in the thermosetting film using a scanning electron microscope.

◎: The rectangular shape was clear, and no bottom smearing was observed.

○: The rectangular shape is clear, but the surface is not smooth.

△: The rectangular shape is clear, but the surface is not smooth or leaves a residual film.

X: The rectangular shape is not clear, or a cured film is not produced.

Experimental Example 4: Evaluation of film retention

The same procedures as in Experimental Example 3 were repeated for each of the compositions obtained in the examples and the comparative examples, including prebaking, exposure by masking, development, and post-baking to prepare a thermosetting film. The film retention ratio was obtained from the final thickness of the thermosetting film relative to the thickness of the cured film immediately after the prebaking process as measured by a non-contact type thickness measuring device (SNU precision).

Experimental Example 5: Evaluating light transmittance

Each of the examples and comparative examples obtained by using a spin coater The composition is coated on a ruthenium substrate. The same procedure as in Experimental Example 3 was repeated, including prebaking, mask exposure, development, and post-baking to prepare a thermosetting film having a thickness of about 3 μm.

The transmittance of the thermosetting film in the wavelength in the range of 400 nm to 800 nm is measured using ultraviolet/visible spectrophotometry.

The results of the above experimental examples are shown in the table below.

As shown in Tables 1 and 2 above, the composition obtained in the examples of the present invention has equally good chemical resistance, sensitivity, developability, and light transmittance. In contrast, at least one of the above characteristics of the composition obtained in the comparative example did not meet the requirements.

Claims (5)

A photosensitive resin composition comprising: (A) a siloxane polymer containing at least one structural unit derived from a decane compound represented by the formula (I), (B) an epoxy compound, and (C) 1,2- A diazide oxime compound: (R ¹ ) _n Si(R ² ) _4-n (I) wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, An aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms or an alkylaryl group having 7 to 12 carbon atoms, and in the case of a plurality of R ¹ They may be the same or different from each other; R ² is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amine group, a decyloxy group having 2 to 12 carbon atoms or having 6 to 12 An aryloxy group of one carbon atom, and in the case of a plurality of R ² 's, may be the same or different from each other; and n is an integer from 0 to 3. The photosensitive resin composition according to claim 1, wherein the epoxy compound (B) does not contain a carboxyl group. The photosensitive resin composition according to claim 1 or 2, wherein the siloxane polymer (A) is more than the epoxy compound (B) based on the total weight of the solid content The weight ratio, that is, A:B is from 97:3 to 70:30. The photosensitive resin composition according to claim 3, wherein the siloxane polymer (A) comprises a structural unit derived from a decane compound represented by the formula (I), wherein n is 0. The photosensitive resin composition according to claim 4, wherein the azide polymer (A) comprises from 10 mol% to 60 mol%, based on the total number of moles of Si atoms. The structural unit of the decane compound represented by the formula (1), wherein n is 0.