JP2007286620A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which excels in performances such as sensitivity, heat resistance and chemical resistance and particularly forms a film having excellent hydrophobic property, accordingly which is suitable for use as a composition for lift-off as well as for forming a bank by an ink jet system. <P>SOLUTION: The photosensitive resin composition comprises (a) an acrylic copolymer obtained by copolymerizing (i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a mixture of these; (ii) an epoxy group-containing unsaturated compound; and (iii) an olefinically unsaturated compound and then removing unreacted monomers; (b) a 1,2-quinonediazide compound; (c) a fluorine compound of a specific structure; and (d) a solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition.

Conventionally, in a liquid crystal display (LCD) manufacturing process, a color resist, an electrode, a wiring, and a semiconductor material are formed by a photo and etching process.
Recently, low-cost displays and materials therefor have been demanded due to the low price of displays, and all organic display (AOD) materials for realizing flexible displays are required.

  As a result, various researches such as pattern formation using imprinting, color resist using an ink-jet method, formation of a soluble organic semiconductor, and formation of a soluble conductive polymer electrode and wiring using lift-off have been promoted.

  For this purpose, the interface characteristics of the bank and the lift-off material in the ink jet are important. In other words, most of the color inks, soluble organic semiconductors, and soluble conductive polymers are hydrophilic. Therefore, in order to improve the wettability with a non-bank substrate, it is necessary to make the interface of the banks hydrophobic. Become. However, when a bank is formed using a conventional photosensitive resin composition, wettability occurs in a bank that is not a substrate due to a small polarity difference between the bank interface and color ink, soluble organic semiconductor, and soluble conductive polymer. As a result, there is a problem that a defect is caused.

  Therefore, there is a need for further research to increase the degree of hydrophobicity of banks and lift-off materials applied to the inkjet method during the LCD manufacturing process.

  In order to solve the problems of the prior art, the present invention is suitable for forming a bank in an ink jet system by making the film have excellent hydrophobic characteristics, and at the same time for lift-off use. An object of the present invention is to provide a photosensitive resin composition suitable for application, an LCD substrate comprising a cured product of the photosensitive resin composition, and a method for forming a pattern on the LCD substrate.

  Another object of the present invention is not only excellent in performance such as sensitivity, heat resistance, and chemical resistance, but also increases the degree of hydrophobicity of the bank and lift-off material applied to the ink jet system particularly during the LCD manufacturing process. It is another object of the present invention to provide an LCD substrate and a pattern forming method for the LCD substrate, which include a photosensitive resin composition capable of forming a cured product, a cured product of the photosensitive resin composition.

In order to achieve the object, the photosensitive resin composition of the present invention comprises:
a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof;
ii) an epoxy group-containing unsaturated compound; and iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound and then removing unreacted monomers;
b) 1,2-quinonediazide compound;
c) The following formulas (1) to (5)
CF ₃ (CF ₂ ) _n COOH (1)
CF ₃ (CF ₂ ) _n CH ₂ OH (2)
CF ₃ C (CF ₃ ) ₂ CF ₂ CF (CF ₃ ) CF ₂ COOH (3)
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CF (CF ₃ ) CF ₂ COOH (4)
C ₁₁ HF ₁₇ O ₂ (5)
(In the formula, n is an integer of 6 to 10.)
And at least one fluorine-based compound selected from the group consisting of: and d) a solvent.

Preferably, a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, 5-40% by weight;
ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; and iii) 10 to 70% by weight of an olefinically unsaturated compound.
And then 100 parts by weight of an acrylic copolymer obtained by removing unreacted monomers;
b) 5-50 parts by weight of a 1,2-quinonediazide compound;
c) 3 to 20 parts by weight of at least one fluorine-based compound selected from the group consisting of formulas (1) to (5); and d) a solvent containing 10 to 10 solids in the photosensitive resin composition. 50% by weight is included.

Moreover, this invention provides the LCD substrate characterized by including the hardening body of the said photosensitive resin composition.
Furthermore, the present invention provides a method for forming a pattern on an LCD substrate using the photosensitive resin composition.

  The photosensitive resin composition according to the present invention is not only excellent in performance such as sensitivity, heat resistance, and chemical resistance, but also forms a bank in an ink jet system by making the film particularly have excellent hydrophobic properties. It is suitable for use for lift-off and at the same time.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof; ii) an epoxy group-containing unsaturated compound; and iii) an olefinically unsaturated compound. An acrylic copolymer obtained by removing unreacted monomers after polymerization; b) 1,2-quinonediazide compound; c) selected from the group consisting of the above formulas (1) to (5) One or more fluorine-based compounds; and d) a solvent.

The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which no scum is generated during development.
The acrylic copolymer of a) has a single amount of i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) an olefinic unsaturated compound. After synthesis by radical reaction in the presence of a solvent and a polymerization initiator as a body, it can be obtained by removing unreacted monomers by precipitation, filtration, and vacuum drying processes.

  The a) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or a mixture thereof used in the present invention is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citraconic acid, Unsaturated dicarboxylic acids such as metaconic acid and itaconic acid; or anhydrides of these unsaturated dicarboxylic acids, etc. can be used alone or in combination of two or more. Particularly, acrylic acid, methacrylic acid, or maleic anhydride can be used. It is more preferable to use the copolymerization reactivity and the solubility of the developer in an alkaline aqueous solution.

  The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or a mixture thereof is preferably contained in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight, based on the total monomer. If the content is too small, it tends to be difficult to dissolve in the alkaline aqueous solution, and if it is too large, the solubility in the alkaline aqueous solution tends to be excessively increased.

  The epoxy group-containing unsaturated compound of a) ii) used in the present invention is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl, acrylic acid-β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4 -Epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid -3,4-epoxycyclohexylmethyl, 4-vinylcyclo Hexene oxide, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, or the like can be used, and the above compounds can be used alone or in admixture of two or more.

  In particular, the epoxy group-containing unsaturated compound is glycidyl methacrylate, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p- The use of vinylbenzyl glycidyl ether is more preferable in improving the copolymerization reactivity and the heat resistance of the resulting pattern.

  The epoxy group-containing unsaturated compound is preferably contained in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total total monomers. If the content is too small, the heat resistance of the resulting pattern tends to decrease, and if it is too large, the storage stability of the copolymer tends to decrease.

  The a) iii) olefinically unsaturated compounds used in the present invention are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2 -Methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Cyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1 , 3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, and the like, and the above compounds can be used alone or in admixture of two or more.

  In particular, it is more preferable to use styrene, dicyclopentanyl methacrylate, or p-methoxystyrene as the olefinic unsaturated compound in terms of copolymerization reactivity and solubility in an alkaline aqueous solution of a developer.

  The olefinically unsaturated compound is preferably contained in an amount of 10 to 70% by weight, more preferably 20 to 50% by weight, based on the total total monomers. When the content is too small, the storage safety of the acrylic copolymer tends to be lowered, and when it is too large, the acrylic copolymer tends to be difficult to dissolve in the alkaline aqueous solution of the developer.

As the solvent used for solution polymerization of the above monomer, methanol, tetrahydroxyfuran, toluene, dioxane or the like can be used.
As the polymerization initiator used for solution polymerization of the above monomer, a radical polymerization initiator can be used, specifically 2,2-azobisisobutyronitrile, 2,2-azobis. (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl-2,2′- Azobisisobutyrate or the like can be used.

  The acrylic copolymer of a) obtained by radically reacting the monomer as described above in the presence of a solvent and a polymerization initiator and removing the unreacted monomer by precipitation, filtration, and vacuum drying processes is as follows. The weight average molecular weight (Mw) in terms of polystyrene is preferably 5,000 to 30,000, more preferably 5,000 to 20,000. If the weight average molecular weight in terms of polystyrene is too small, the heat resistance and the remaining film ratio tend to decrease, and if it is too large, the sensitivity tends to decrease and pattern development tends to be inferior.

The 1,2-quinonediazide compound b) used in the present invention is used as a photosensitive compound.
As the 1,2-quinonediazide compound, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, or the like can be used.

The quinonediazide compound as described above can be produced by reacting a naphthoquinonediazidesulfonic acid halogen compound and a phenol compound under a weak base.
Examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2′-tetrahydroxybenzophenone, 4,4′-tetrahydroxybenzophenone, 2,3,4, 3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy3 ′ -Methoxybenzophenone, 2,3,4,2'-pentahydroxybenzophenone, 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4 '-Hexahydroxybenzophenone, 2,4,6,5'-Hexahydroxybenzophenone, 3,4,5 , 3′-hexahydroxybenzophenone, 3,4,5,4′-hexahydroxybenzophenone, 3,4,5,5′-hexahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxy) Phenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2, 3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4 -Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, or bis (2,5-dimethyl-4-hydroxyphenyl) -2 -Hydroxyphenylmethane etc. can be used and the said compound can be used individually or in mixture of 2 or more types.

  When the quinonediazide compound is synthesized with the phenol compound and the naphthoquinonediazidesulfonic acid halogen compound as described above, the degree of esterification is preferably 50 to 90%. When the degree of esterification is too small, the remaining film ratio may be deteriorated, and when it is too large, the storage stability tends to be lowered.

  The 1,2-quinonediazide compound is preferably contained in an amount of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the acrylic copolymer of a). If the content is too small, the difference in solubility between the exposed portion and the non-exposed portion tends to be small, and pattern formation tends to be difficult. If the amount is too large, unreacted 1 when irradiated with light in a short time. , 2-quinonediazide compound may remain in a large amount, and the solubility of the developer in an alkaline aqueous solution may become excessively low, making development difficult.

  One or more fluorine-based compounds selected from the group consisting of the above formulas (1) to (5) of c) used in the present invention are a hydrophobic pattern of a bank and lift-off material pattern obtained from the photosensitive resin composition. Acts to improve properties.

  The fluorine compounds represented by the above formulas (1) to (5) can be used alone or in combination of two or more. The content is preferably 3 to 20 parts by weight, more preferably 3 to 15 parts by weight per 100 parts by weight of the acrylic copolymer of a). If the content is too small, the hydrophobic characteristics of the pattern may be deteriorated. If the content is too large, the sensitivity may be lowered and the solubility of the developer in an alkaline aqueous solution may be excessively lowered to generate scum. The solvent d) used in the present invention serves to form a uniform pattern profile without generating flatness and coating stain of the bank and lift-off material.

  Examples of the solvent include alcohols such as methanol, ethanol, benzyl alcohol and hexyl alcohol; ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; ethylene glycol methyl ether propionate and ethylene glycol ethyl ether. Ethylene glycol alkyl ether propionates such as propionate; ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. The Tylene glycol alkyl ethers; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol Propylene glycol alkyl ether propionates such as propyl ether propionate; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; dipropylene glycol dimethyl Dipropylene glycol alkyl ethers such as ether and dipropylene glycol diethyl ether; butylene glycol monomethyl ethers such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; dibutylene glycol alkyl such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether Ethers; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , Ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyric hydroxyacetate , Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate , Methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, methyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, butoxy Methyl acetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, -Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propo Esters such as butyl cypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. may be used alone or in combination of two or more. it can.

  The solvent is preferably included so that the total photosensitive resin composition has a solid content of 10 to 50% by weight, more preferably 15 to 40% by weight. If the total solid content of the total composition is too small, the coating thickness may be reduced and the coating flatness may be reduced.If the solid content is too large, the coating thickness may be increased. May give.

  If necessary, the photosensitive resin composition of the present invention comprising the above components may additionally contain e) an epoxy resin, f) an adhesive, g) an acrylic compound, or h) a surfactant.

The epoxy resin e) functions to improve the heat resistance and sensitivity of the pattern obtained from the photosensitive resin composition.
The epoxy resin is a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic epoxy resin, or a). A resin obtained by (co) polymerizing glycidyl methacrylate different from an acrylic copolymer can be used, and in particular, a bisphenol A type epoxy resin, a cresol novolak type epoxy resin, or a glycidyl ester type epoxy resin is used. preferable.

  The epoxy resin is preferably included in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the acrylic copolymer of the above a), and when the content is within the above range, the epoxy resin is based on the acrylic copolymer. There is an advantage that compatibility and sufficient coating performance can be obtained.

The adhesive f) improves the adhesion to the substrate, and is preferably contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer a).
As the adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group can be used. Specifically, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane and the like can be used.

Further, the acrylic compound of g) functions to improve the transmittance, heat resistance, sensitivity, etc. of the pattern obtained from the photosensitive resin composition.
Preferably, the acrylic compound is a compound represented by the following formula (6).

（式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、または炭素数１〜５のアルカノイル基であり、
１＜ａ＜６であり、ａ＋ｂ＝６である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkanoyl group having 1 to 5 carbon atoms,
1 <a <6 and a + b = 6. )

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, n-pentyl and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, t-butoxy, n-pentoxy and the like. Examples of the alkanoyl group include methanoyl, ethanoyl, propanoyl, isopropanoyl, n-butanoyl, t-butanoyl, n-pentanoyl and the like.

  The acrylic compound is preferably contained in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). When the content is within the above range, the pattern transmittance, heat resistance, sensitivity and the like are further improved.

Further, the surfactant h) functions to improve the coating property and developability of the photosensitive composition.
The surfactant is polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173 (trade name: Dainippon Ink & Chemicals, Inc.), FC430, FC431 (trade name: Sumitomo 3M Limited), Alternatively, KP341 (trade name: Shin-Etsu Chemical Co., Ltd.) or the like can be used.

  The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a), and when the content is within the above range, the photosensitive composition is applied. It is even better in improving the property and developability.

  The solid content concentration of the photosensitive resin composition of the present invention comprising the above components is preferably 10 to 50% by weight, and the composition having the solid content in the above range is 0.1 to 0.2 μm Millipore. It is good to use after filtering with a filter.

The present invention also provides an LCD substrate comprising a cured product of the photosensitive resin composition and a method for forming a pattern on the LCD substrate using the photosensitive resin composition.
The LCD substrate pattern forming method of the present invention is characterized in that the photosensitive resin composition is used in a method for forming a pattern of an LCD substrate by forming a photosensitive resin composition as a bank and a lift-off material.

Specifically, a method for forming an LCD substrate pattern using the photosensitive resin composition is as follows.
First, the photosensitive resin composition of the present invention is applied to the substrate surface by a spray method, a roll coater method, a spin coating method, or the like, and the solvent is removed by pre-baking to form a coating film. At this time, the pre-bake is preferably performed at a temperature of 80 to 110 ° C. for 1 to 15 minutes.

  Thereafter, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary portions. Form a pattern.

  The developer is preferably an alkaline aqueous solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as ethylamine and n-propylamine; diethylamine and n-propyl. Secondary amines such as amines; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; or tetramethylammonium hydroxide, tetraethylammonium hydroxy An aqueous solution of a quaternary ammonium salt such as dodo can be used. At this time, the developer is used by dissolving an alkaline compound in a concentration of 0.1 to 10% by weight, and a water-soluble organic solvent such as methanol and ethanol and a surfactant can be added in appropriate amounts. .

Moreover, after developing with the above developing solution, it can wash | clean with ultrapure water for 30 to 90 second, an unnecessary part is removed, and it can dry and can obtain a pattern.
The photosensitive resin composition of the present invention as described above is not only excellent in performance such as sensitivity, heat resistance, chemical resistance, etc., but also particularly in the ink jet system by making the film have excellent hydrophobic properties. This is advantageous in that it is suitable for forming a bank and at the same time suitable for application for lift-off.

Hereinafter, preferred examples will be presented for the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
(Acrylic copolymer production)
In a flask equipped with a condenser and a stirrer, 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 900 parts by weight of tetrahydroxyfuran, 25 parts by weight of methacrylic acid, 25 parts by weight of glycidyl methacrylate, styrene 25 parts by weight and 25 parts by weight of methyl methacrylate were added, and after nitrogen substitution, the mixture was gently stirred. The reaction solution was heated to 60 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 20 hours.

  In order to remove the unreacted monomer of the polymer solution containing the acrylic copolymer, 100 parts by weight of the polymer solution was precipitated with respect to 1,000 parts by weight of n-hexane as a poor solvent. Thereafter, in order to remove the solvent in which unreacted substances are dissolved by a filtering process using a mesh, vacuum drying is performed at 30 ° C. or lower to completely remove the solvent containing the remaining unreacted monomers. Thus, an acrylic copolymer having a weight average molecular weight of 10,000 was produced. At this time, the weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC.

(Production of 1,2-quinonediazide compound)
4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] 2 mol To give 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester. Manufactured.

(Photosensitive resin composition production)
100 parts by weight of the prepared acrylic copolymer and the prepared 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2- 30 parts by weight of naphthoquinonediazide-5-sulfonic acid ester and the following formula (1-1)
CF ₃ (CF ₂ ) ₁₀ COOH (1-1)
10 parts by weight of a fluorine compound represented by the formula: Thereafter, the mixture was dissolved in propylene glycol monoethyl acetate so that the solid content of the mixture was 20% by weight, and then filtered through a 0.2 μm Millipore filter to produce a photosensitive resin composition.

Example 2
Instead of the fluorine-based compound represented by the formula (1-1) in Example 1, the following formula (2-1)
CF ₃ (CF ₂ ) ₈ CH ₂ OH (2-1)
A photosensitive resin composition was produced in the same manner as in Example 1 except that the fluorine compound represented by the formula (1) was used.

Example 3
Instead of the fluorine-based compound represented by the formula (1-1) in Example 1, the following formula (3)
CF ₃ C (CF ₃ ) ₂ CF ₂ CF (CF ₃ ) CF ₂ COOH (3)
A photosensitive resin composition was produced in the same manner as in Example 1 except that a fluorine-based compound represented by the formula (1) was used.
Example 4
Instead of the fluorine-based compound represented by the formula (1-1) in Example 1, the following formula (4)
(CF ₃ ) ₂ CF (CH ₂ ) ₃ CF (CH ₃ ) CF ₂ COOH (4)
A photosensitive resin composition was produced in the same manner as in Example 1 except that a fluorine-based compound represented by the formula (1) was used.

Example 5
Instead of the fluorine-based compound represented by the formula (1-1) in Example 1, the following formula (5)
C ₁₁ HF ₁₇ O ₂ (5)
A photosensitive resin composition was produced in the same manner as in Example 1 except that a fluorine-based compound represented by the formula (1) was used.
Example 6
A photosensitive resin composition was produced in the same manner as in Example 1 except that the fluorine-based compound represented by Formula (1-1) was used in 5 parts by weight in Example 1. .

Comparative Example 1
In Example 1, a photosensitive resin composition was produced in the same manner as in Example 1 except that the fluorine-based compound represented by Formula (1-1) was not used.

The physical properties were evaluated by the following methods using the photosensitive resin compositions produced in Examples 1 to 6 and Comparative Example 1, and the results are shown in Table 1.
B) Hydrophobic properties-after applying the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Example 1 on a glass substrate using a spin coater, prebaking on a hot plate at 90 ° C for 2 minutes, A film having a thickness of 1.0 μm was formed. After that, using the Kruss DNA-100 equipment, the contact angle is 90 degrees or more based on the average contact angle with respect to 40 points for 20 seconds at intervals of 0.5 seconds using the Sessile Drop Method. The case was indicated by ○, the case of 80 to 90 degrees was indicated by Δ, and the case of less than 80 degrees was indicated by ×. B) Sensitivity—After irradiating the film formed in a) with ultraviolet rays having an intensity of 20 mW / cm ² at 435 nm and a 10 μm line and space 1: 1 CD reference dose using a predetermined pattern mask, tetramethyl The resist film was developed with an aqueous solution of 0.38% by weight ammonium hydroxide at 23 ° C. for 2 minutes and then washed with ultrapure water for 1 minute to obtain a pattern film.

C) Resolution—The pattern film formed at the time of sensitivity measurement in the above b) was measured with the minimum size.
D) Heat resistance—The pattern film formed at the time of sensitivity measurement in b) was cured in a convection oven at 220 ° C. for 1 hour to form a final pattern film. At this time, the case where the 10 μm CD change rate before and after curing is 0 to 20% is indicated by ◯, the case where it is 20 to 40% is indicated by Δ, and the case where it exceeds 40% is indicated by ×.

  E) Chemical resistance—The pattern film obtained in d) above was dipped in NMP at 70 ° C. for 5 minutes and then rinsed with ultrapure water, and the 10 μm CD change rate before and after NMP treatment was measured. At this time, the case where the 10 μm CD change rate is 0 to 20% is indicated by ◯, the case where it is 20 to 40% is indicated by Δ, and the case where it exceeds 40% is indicated by ×.

表１から、本発明によって製造した実施例１〜６の感光性樹脂組成物は感度、解像度、耐熱性、および耐化学性が全て優れており、特に比較例１と比較して、顕著に向上した疎水特性を有することによってインクジェット方式でのバンクおよびリフトオフ用として適用可能であることが分かった。これに反し、前記フッ素系化合物を使用していない比較例１の場合には疎水特性が劣ってインクジェット方式でのバンクおよびリフトオフ用として適用しにくいことが分かった。

From Table 1, the photosensitive resin compositions of Examples 1 to 6 produced according to the present invention are all excellent in sensitivity, resolution, heat resistance, and chemical resistance, and particularly remarkably improved as compared with Comparative Example 1. It has been found that by having the hydrophobic characteristics, it can be applied for banking and lift-off in the ink jet system. On the other hand, it was found that the comparative example 1 in which the fluorine-based compound was not used was inferior in hydrophobic characteristics and was difficult to apply for banking and lift-off in the ink jet method.

Claims (12)

a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof;
ii) an epoxy group-containing unsaturated compound; and iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound and then removing unreacted monomers;
b) 1,2-quinonediazide compound;
c) The following formulas (1) to (5)
CF ₃ (CF ₂ ) _n COOH (1)
CF ₃ (CF ₂ ) _n CH ₂ OH (2)
CF ₃ C (CF ₃ ) ₂ CF ₂ CF (CF ₃ ) CF ₂ COOH (3)
(CF ₃ ) ₂ CF (CF ₂ ) ₃ CF (CF ₃ ) CF ₂ COOH (4)
C ₁₁ HF ₁₇ O ₂ (5)
(In the formula, n is an integer of 6 to 10.)
A photosensitive resin composition comprising: at least one fluorine-based compound selected from the group consisting of: and d) a solvent. a) i) 5-40% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof;
ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; and iii) 10 to 70% by weight of an olefinically unsaturated compound.
And then 100 parts by weight of an acrylic copolymer obtained by removing unreacted monomers;
b) 5-50 parts by weight of a 1,2-quinonediazide compound;
c) 3 to 20 parts by weight of at least one fluorine-based compound selected from the group consisting of formulas (1) to (5); and d) a solvent containing 10 to 10 solids in the photosensitive resin composition. The photosensitive resin composition of Claim 1 contained so that it may become 50 weight%.   A) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a mixture thereof is acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is one or more compounds selected from the group consisting of anhydrides.   The epoxy group-containing unsaturated compound of a) ii) is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid- β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic Acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4- Epoxy cyclohexyl methyl, 4-vinyl cyclohexylene oxide The photosensitivity according to any one of claims 1 to 3, which is at least one compound selected from the group consisting of o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Resin composition.   The olefinic unsaturated compound of a) iii) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, di- Cyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methyl Cyclohexyl acrylate, dicyclopentanyloxyethyl acrylate , Isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3 The photosensitive resin composition according to claim 1, which is at least one compound selected from the group consisting of butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene.   The photosensitive resin composition according to claim 1, wherein the acrylic copolymer of a) has a polystyrene-reduced weight average molecular weight (Mw) of 5,000 to 30,000.   The 1,2-quinonediazide compound of b) is selected from the group consisting of 1,2-quinonediazide-4-sulfonic acid ester, 1,2-quinonediazide-5-sulfonic acid ester, and 1,2-quinonediazide-6-sulfonic acid ester The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is one or more kinds of compounds.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the 1,2-quinonediazide compound of b) has an esterification degree of 50 to 90%.   The solvent of d) is methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether Propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, butylene glycol Monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropion Ethyl acetate Loxymethyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3 -Ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate Propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl toxipropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxy The photosensitive resin composition according to any one of claims 1 to 8, which is one or more compounds selected from the group consisting of propyl propionate and butyl 3-butoxypropionate.   The photosensitive resin composition additionally includes one or more additives selected from the group consisting of e) an epoxy resin, f) an adhesive, g) an acrylic compound, and h) a surfactant. The photosensitive resin composition as described in any one of 9.   An LCD substrate comprising a cured product of the photosensitive resin composition according to claim 1. The pattern formation method of the LCD substrate using the photosensitive resin composition as described in any one of Claims 1-10.