TW201738658A - Negative-type photosensitive resin composition - Google Patents

Abstract

The present invention provides a negative-type photosensitive resin composition, comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an additive and a solvent, wherein the additive includes a silane coupling agent having an amino functional group; and at least one of a novolac epoxy resin and a phenol novolac oxetane resin. The photosensitive resin composition according to the present invention has excellent adhesion property, chemical resistance and storage stability, and can be cured at a low temperature.

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition. More particularly, the present invention relates to a negative photosensitive resin composition capable of curing at a low temperature and having excellent adhesive properties and chemical resistance, a photocurable pattern formed using the negative photosensitive resin composition, and including The image display device of the photocured pattern.

In the field of displays, a photosensitive resin composition is used to form various photo-cured patterns, such as photoresists, insulating films, protective films, black matrices, column spacers (column). Spacer). Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocured pattern. In order to improve the process yield and improve the physical properties of the object to be applied to the process, a photosensitive resin composition having high sensitivity is required.

Patterning using the photosensitive resin composition is performed by photolithography, which causes a polarity change and a crosslinking reaction of the polymer by photoreaction. In particular, characteristics such as a change in solubility of a solvent such as an alkaline aqueous solution after exposure are utilized.

The pattern formation using the photosensitive resin composition is classified into a positive type and a negative type depending on the solubility of development in the exposed region. In the positive photoresist, the exposed regions are dissolved by the developing solution. In the negative photoresist, the exposed regions are insoluble in the developing solution, but the unexposed regions are dissolved to form a pattern. The positive and negative types differ from each other in terms of the adhesive resin, the crosslinking agent, and the like.

In recent years, the use of touch screens equipped with touch panels has exploded. Recently, flexible touch screens have received a lot of attention. Therefore, various types of materials for substrates for touch screens must have flexible properties. Thus the materials available are limited to flexible polymeric materials and the manufacturing process is also required to be performed under milder conditions.

Therefore, regarding the curing conditions of the photosensitive resin composition, low-temperature curing is required instead of conventional high-temperature curing, and excellent adhesion to the substrate even under mild conditions and better chemical resistance for chemical treatment in subsequent processes are required. And other characteristics.

Korean Patent No. 10-1302508 discloses a negative photosensitive resin composition comprising a copolymer polymerized using a cyclohexenyl acrylate-based monomer, thereby exhibiting excellent heat resistance and light resistance. Sensitivity is improved, but it does not exhibit the required durability under low temperature curing conditions.

An object of the present invention is to provide a negative photosensitive resin composition which can be cured at a low temperature and which has excellent adhesive properties and chemical resistance.

Another object of the present invention is to provide a photocured pattern formed using a negative photosensitive resin composition.

It is still another object of the present invention to provide an image display apparatus including a photo-curing pattern.

According to an aspect of the present invention, there is provided a negative photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an additive, and a solvent, wherein the additive includes an amine functional group The base decane coupling agent, and at least one of a novolac epoxy resin and a phenol novolac oxetane resin.

In one embodiment of the invention, the decane coupling agent having an amine functional group may comprise a compound of the following formula I:

Wherein R ₁ to R ₄ are each independently an alkyl group having 1 to 6 carbon atoms; and n is an integer of 0 to 3.

In one embodiment of the present invention, the novolac epoxy resin may include at least one selected from the group consisting of poly[(o-cresolyl epoxypropyl ether)-co-formaldehyde] (poly[( O-cresyl glycidyl ether)-co-formaldehyde]), poly[(phenyl glycidyl ether)-co-formaldehyde], epoxy propyl end cap Poly(bisphenol A-co-epichlorohydrin)glycidyl end-capped, formaldehyde and (chloroform) (formaldehyde, polymer with (chloromethyl)oxirane and 4,4-(1-methylethylidene)bis (phenol) ).

According to another aspect of the present invention, there is provided a photocured pattern formed using a negative photosensitive resin composition.

According to still another aspect of the present invention, an image display apparatus including a photo-curing pattern is provided.

The negative photosensitive resin composition according to the present invention can be cured at a low temperature, has excellent adhesive properties when a coating film is formed on a metal substrate, and has excellent chemical resistance and storage stability to chemical treatment after development.

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

One embodiment of the present invention relates to a negative photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an additive, and a solvent, wherein the additive includes a decane coupling agent having an amine functional group And at least one of a novolak epoxy resin and a phenol novolac oxetane resin.

In one embodiment of the invention, the decane coupling agent having an amine functional group may comprise a compound of the following formula I:

Wherein R ₁ to R ₄ are each independently an alkyl group having 1 to 6 carbon atoms; and n is an integer of 0 to 3.

As used herein, an alkyl group having 1 to 6 carbon atoms means a linear or branched monovalent hydrocarbon having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, Isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, etc., but are not limited thereto.

In the above formula I, n may be 3.

In particular, in the above formula I, R ₁ may be an ethyl group, R ₃ may be an isobutyl group, R ₄ may be a methyl group, and n may be 3.

The decane coupling agent having an amino functional group is excellent in reactivity with an epoxy resin and an oxetane resin, and can improve the adhesion property in the development step.

The amount of the decane coupling agent having an amino functional group may be included in the range of 0.1% by weight to 5% by weight based on the total weight of the photosensitive resin composition. If the content of the decane coupling agent is less than 0.1% by weight, the adhesion property of the coating film to the developing solution may be lowered. If the content of the decane coupling agent exceeds 5% by weight, coating uniformity may be lowered.

In one embodiment of the present invention, when a novolak epoxy resin and a phenol novolac oxetane resin are used together with an alkali-soluble resin having an epoxy group or an oxetane group, the preparation can be remarkably improved. The pattern is chemically resistant to chemical liquids such as etchants or strippers.

This is because the novolac epoxy resin and the phenol novolac oxetane resin have an epoxy group or an oxetane group, and thus are in the pattern formation process. The ring opening is performed by heat treatment to promote the polymerization reactivity of the alkali-soluble resin and includes a novolak structure having excellent chemical resistance.

In one embodiment of the invention, it is preferred that the epoxy group in the novolac epoxy resin is included in the repeating unit of the oligomer (oligomer). In this case, the novolak epoxy resin has a large amount of epoxy groups, thereby maximizing the reaction promoting effect.

For the novolac epoxy resin, for example, poly[(o-cresyl epoxypropyl ether)-co-formaldehyde]; poly[(phenylepoxypropyl ether)-co-formaldehyde]; Base-terminated poly(bisphenol A-co-epichlorohydrin); a polymer of formaldehyde and (chloromethyl)oxirane and 4,4-(1-methylethylidene)bis(phenol). Among them, preferred are polymers of formaldehyde and (chloromethyl)oxirane and 4,4-(1-methylethylidene)bis(phenol); and having an epoxy group in the repeating unit. Poly[(o-cresolyl epoxypropyl ether)-co-formaldehyde]. They may be used singly or in combination of two or more.

In one embodiment of the invention, the novolac epoxy resin may comprise a compound of the following formula II:

Wherein n is an integer from 3 to 10.

The molecular weight of the novolak epoxy resin is not particularly limited, and the number average molecular weight may be, for example, 200 to 5,000, preferably 500 to 3,000. When the number average molecular weight is within the above range, an excellent chemical resistance improving effect can be obtained without impairing the composition. Storage stability of the object.

In one embodiment of the invention, the phenol novolac oxetane resin may comprise a compound of the following formula III:

In the formula, n is an integer from 3 to 10, for example, n is 3.

The molecular weight of the phenol novolac oxetane resin is not particularly limited, and for example, the number average molecular weight may be from 500 to 2,000, particularly from 700 to 1,500. When the number average molecular weight is within the above range, an excellent chemical resistance improving effect can be obtained without impairing the storage stability of the composition.

The content of at least one of the novolak epoxy resin and the phenol novolac oxetane resin is not particularly limited, and may be, for example, 0.5% by weight to 5% by weight, preferably 1 part by weight based on the total mass of the photosensitive resin composition. % to 3% by weight. If the content is less than 0.5% by weight, the chemical resistance improving effect may not be remarkable. Further, if the content exceeds 5% by weight, residual and skew of the pattern may occur.

In one embodiment of the present invention, the alkali-soluble resin is a component that provides solubility in an alkali developing solution used in development when forming a pattern, and the alkali-soluble resin may contain an epoxy group or an oxetane. base.

The alkali-soluble resin is not particularly limited as long as the alkali-soluble resin has an epoxy group or an oxetane group, and can be reacted with a novolak epoxy resin or a phenol novolac oxetane resin while being alkaline-developed. Dissolve Solubility is provided in the liquid.

For the specific example, the alkali-soluble resin may include a first resin containing a repeating unit represented by the following Chemical Formula IV, and a second resin containing a repeating unit represented by the following Chemical Formula V:

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen group or a methyl group; and R ₅ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (4); Group:

R ₆ is a structure derived from a monomer selected from the group consisting of (meth)acrylic acid, 2-(methyl)propenyloxyethyl hexahydrophthalate (2-( Meth)acryloyloxyethylhexahydro phthalate), 2-(meth)acryloyloxyethyl phthalate and 2-(meth)acryloxyethyl succinate (2-( Meth)acryloyloxyethyl succinate); R ₇ is a structure derived from a monomer represented by the following formula (5):

R ₁₇ is a hydrogen group or a methyl group; and R ₈ is a substituent having a double bond at its end, which is derived from an epoxy compound selected from the group consisting of the following formulas (6) to (14) Obtained by the structural reaction of the (meth)acrylic monomer:

a is from 5 mol% to 30 mol%, b is from 10 mol% to 20 mol%, c is from 30 mol% to 60 mol%, and d is from 10 mol% to 30 mol%;

Wherein R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen group or a methyl group; R ₁₂ is a structure derived from a monomer selected from the group consisting of (meth)acrylic acid, hexahydrogen 2-(methyl)propenyloxyethyl phthalate, 2-(methyl) propylene methoxyethyl phthalate and 2-(methyl) propylene methoxyethyl succinate; R ₁₃ is a structure derived from a monomer group of the following formulas (15) to (17):

R ₁₄ is a structure derived from a monomer represented by the following formula (18):

R ₁₅ is an alkylene group having 1 to 6 carbon atoms, R ₁₆ is an alkyl group having 1 to 6 carbon atoms; e is 10 mol% to 30 mol%, and f is 30 mol% to 60 mol%, and g is 20 mol% to 50 mol%.

As used herein, an alkylene group having 1 to 6 carbon atoms means a linear or branched divalent hydrocarbon having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethyl group, and a stretching group. A propyl group, a butyl group, etc., but is not limited thereto.

In the present specification, the term "(meth)acrylic-" means "methacrylic acid-", "acrylic acid-" or both.

In the present specification, each repeating unit represented by Chemical Formula IV and Chemical Formula V should not be construed as being limited to the repeating unit shown, and the sub-repeat unit in parentheses may be freely arranged in the chain within a predetermined molar % range. Any location. In other words, although each parenthesis in the chemical formula IV and the chemical formula V is represented by one block for indicating the % of the mole, each of the sub-repeat units may be arranged in a block or individual manner without limitation as long as they are within the resin.

In the present specification, a repeating unit or compound represented by a chemical formula includes a repeating unit or an isomer of a compound, and when a repeating unit represented by each chemical formula or an isomer of a compound is present, a repeating unit represented by a corresponding formula Or compounds include their isomers.

The first resin can improve durability, such as patterning property and chemical resistance of the photosensitive resin composition, and in this aspect, the weight of the first resin is flat The average molecular weight is preferably from 10,000 to 30,000.

The second resin can improve low-temperature reactivity, storage stability, and chemical resistance of the photosensitive resin composition, and in this aspect, the second resin preferably has a weight average molecular weight of 5,000 to 20,000.

The mixing ratio of the first resin to the second resin may be from 10:90 to 50:50, particularly from 15:85 to 35:75. If the content of the second resin is lower than the content of the first resin, low-temperature curability may be lowered, and storage stability may be deteriorated. If the content of the second resin is 9 times higher than the content of the first resin, durability such as chemical resistance may be lowered.

In one embodiment of the present invention, in addition to the repeating units of Chemical Formula IV and Chemical Formula V, the first resin and the second resin may each independently further comprise repeating units formed of other monomers known in the art, or They may be formed only by repeating units of Chemical Formula IV and Chemical Formula V.

The monomer forming the repeating unit may be further added to Chemical Formula IV or Chemical Formula V without particular limitation, and examples thereof include a monocarboxylic acid; a dicarboxylic acid and an acid anhydride thereof; and a single polymer having a carboxyl group and a hydroxyl group at both ends Acrylate; aromatic vinyl compound; N-substituted maleimide compound; alkyl (meth)acrylate; alicyclic (meth) acrylate; aryl (meth) acrylate An unsaturated oxetane compound; an unsaturated oxirane compound; a (meth) acrylate substituted with a cycloalkane or a bicycloalkane ring having 4 to 16 carbon atoms; These may be used alone or in combination of two or more.

In one embodiment of the invention, the acid value of the alkali-soluble resin is preferably in the range of 20 to 200 (KOH mg/g). When the acid value is within the above range, Excellent developability and stability over time can be obtained.

The content of the alkali-soluble resin is not particularly limited, and may be, for example, 10% by weight to 90% by weight, preferably 25% by weight to 70% by weight based on 100% by weight of the total solid content of the photosensitive resin composition. When the content of the alkali-soluble resin is included in the above range, the photosensitive resin composition has sufficient solubility in the developing solution, thus exhibiting excellent developability, and can form a photocured pattern having excellent mechanical properties.

In one embodiment of the invention, the photopolymerizable monomer can increase the crosslink density and enhance the mechanical properties of the photocurable pattern during the manufacturing process.

The photopolymerizable monomer can be used without particular limitation as long as it is generally used in the art, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers. The type of the photopolymerizable monomer is not particularly limited, and examples thereof may include the following compounds.

Specific examples of the monofunctional monomer may include mercapto carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyl Ethyl acrylate, N-vinyl pyrrolidone, and the like. Specific examples of the difunctional monomer may include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of other polyfunctional monomers may include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane Tri(meth)acrylate), propoxylated trimethylol propyl Propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol five (a) Acrylate, ethoxylated dipentaerythritol hexa(meth) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate, dipentaerythritol hexa(meth) acrylate Ester and the like. Among them, difunctional or higher polyfunctional monomers are preferably used.

The content of the photopolymerizable monomer is not particularly limited, and may be, for example, 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the photosensitive resin composition. When the photopolymerizable monomer is contained in the above content range, excellent durability can be obtained, and the developability of the composition can be improved.

In one embodiment of the present invention, the photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable monomer. For example, an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, or a thiophene can be used. At least one compound selected from the group consisting of a thioxanthone-based compound and an oxime ester-based compound, and an oxime ester-based compound is preferably used.

Specific examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiobenzene) 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-on e) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-(2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan- 1-one), 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-( Dimethylamino)-1-(4-morpholinylphenyl)butan-1-one and the like.

Specific examples of the benzophenone-based compound may include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone (3,3',4,4'-tetra( Tert-butylperoxycarbonyl)benzophenone), 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloro) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

Specific examples of the biimidazole-based compound may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, wherein at 4, An imidazole or the like in which the phenyl group at the 4', 5, 5' position is substituted with one or more carboalkoxy groups.

Specific examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiophene. Tons of ketone and so on. Specific examples of the oxime ester compound may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione, 1-(4-phenylthio). Phenyl, 2-(o-benzamide), ethyl ketone, 1-(9-ethyl)-6-(2-methylbenzimidyl)oxazol-3-yl, 1-(o-ethylidene)肟) and the like, and commercially available products include CGI-124 (purchased from CIBA-GEIGY), CGI-224 (purchased from CIBA-GEIGY), Irgacure OXE-01 (purchased from BASF), Irgacure OXE-02 (purchased) From BASF), N-1919 (purchased from ADEKA), NCI-831 (purchased from ADEKA), and the like.

Further, in order to improve the sensitivity of the negative photosensitive resin composition according to the present invention, the photopolymerization initiator may further comprise a photoinitiating adjuvant. The photosensitive resin composition according to the present invention may contain a photoinitiating adjuvant to have higher sensitivity to improve productivity.

For the photoinitiating adjuvant, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be used.

Specific examples of the amine compound may include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amines such as methyl 4-dimethylaminobenzoate and 4-dimethylaminobenzene. Ethyl formate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, benzo Acid 2-methylaminoethyl ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone) And 4,4'-bis(diethylamino)benzophenone. An aromatic amine is preferred.

The carboxylic acid compound is preferably an aromatic isocyanic acid, and examples thereof may include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethyl Phenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylsulfide Naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group may include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-tri ( 3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate) Trimethylolpropane tris(3-mercaptopropionate)), neopentyltetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate) ), tetraethylene glycol bis (3-mercaptopropionate) or the like.

The content of the photopolymerization initiator is not particularly limited, and may be, for example, 0.1% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight based on the total mass of the photosensitive resin composition. When the amount of the photopolymerization initiator satisfies the above range, the photosensitive resin composition can have high sensitivity to shorten the exposure time, thereby improving productivity and maintaining high resolution.

In one embodiment of the present invention, the solvent is not particularly limited, and may be used without limitation as long as it is generally used in the art.

Specific examples of the solvent may include ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol Dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether ; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate, ethyl stilbene acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl Alkyl ether acetate; alkanediol alkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetic acid Ester and methoxypentyl acetate; propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ether such as propylene glycol Ethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; propylene glycol Ethyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; butanediol monoalkyl ether such as methoxybutyl Alcohol, ethoxybutanol, propoxybutanol and butoxybutanol; butanediol monoalkyl ether acetate such as methoxybutyl acetate, ethoxybutyl acetate, propoxy Butyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionate such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate and butoxybutyl propionate; dipropylene glycol II Alkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, Acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol; esters such as methyl acetate, acetic acid Ethyl ester, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, Ethyl hydroxyacetate, butyl glycolate, 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, B Oxyl Methyl acetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, propoxyacetic acid Butyl ester, methyl butoxyacetate, ethyl butoxide, 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 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propyl propionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Propyl propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and 3-butoxy Butyl propyl propionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone and the like.

The solvents exemplified herein may be used singly or in combination of two or more.

When considering the coating properties and drying properties, the solvent used herein may preferably be an alkylene glycol alkyl ether acetate, a ketone, a butanediol alkyl ether acetate, a butanediol monoalkyl ether, an ester. Classes such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, 3-ethoxypropionic acid can be used. Ethyl ester and methyl 3-methoxypropionate.

The amount of the solvent may be contained in the range of 40% by weight to 95% by weight, preferably 45% by weight to 85% by weight based on the total mass of the photosensitive resin composition. If the amount of the solvent satisfies the above range, when a coating device such as a spin coater, a slit coater, a slit coater (sometimes referred to as a die coater or a curtain coater) Coater)) When applied and inkjet, it provides an effect of improving coating properties.

The photosensitive resin composition according to an embodiment of the present invention may further include an additive such as a filler, other polymer compound, if necessary. A curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet (UV) absorber, a coagulation preventing agent, and a chain transfer agent are not limited thereto.

Specific examples of the filler may include glass, cerium oxide, and aluminum oxide, but are not limited thereto.

Specific examples of the other polymer compound may include a curable resin such as an epoxy resin and a maleimide resin, and a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluorocarbon. Acrylates, polyesters, and polyurethanes, but are not limited thereto.

A curing agent is used to enhance the depth curing properties and mechanical strength. Specific examples of the curing agent may include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound, but are not limited thereto.

As the leveling agent, a commercially available surfactant may be used, and examples thereof may include an anthrone type, a fluorine type, an ester type, a cationic type, an anionic type, a nonionic type, and an amphoteric type of surfactant. The active agents may be used singly or in combination of two or more.

As the adhesion promoter, a decane-based compound can be used, and specific examples thereof include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-( 2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyl 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3-glycidoxypropylmethyldimethoxysilane) 3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercapto Propyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, and the like. The adhesion promoters exemplified above may be used singly or in combination of two or more.

Specific examples of the antioxidant may include 4,4'-butylene bis[6-tert-butyl-3-methylphenol], 2,2'-thiobis(4-methyl-6-t-butyl group). Phenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

Specific examples of the coagulation preventing agent may include sodium polyacrylate and the like.

Specific examples of the chain transfer agent may include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

One embodiment of the present invention relates to a photocured pattern formed using the above negative photosensitive resin composition. The photocurable pattern can be used as an array planarization film pattern, a protective film pattern, an insulating film pattern, or the like, and can be used as a photoresist pattern, a black matrix pattern, a pillar spacer pattern, a black column spacer pattern, or the like, but Not limited to this. In particular, the photocurable pattern is very suitable for an insulating film pattern.

The photo-curing pattern according to an embodiment of the present invention can be prepared by coating the above-mentioned photosensitive resin composition on a substrate, then exposing it to light and developing it.

First, the photosensitive resin composition of the present invention is coated on a substrate, and then heated and dried to remove volatile components such as a solvent to obtain a smooth Coating film.

The coating method may include, for example, a spin coating method, a casting method, a roll coating method, a slit spin coating method, a slit coating method, or the like.

After coating, the film is heated and dried (prebaked) or dried under reduced pressure and then heated to remove volatile components such as solvents. Here, the heating temperature is from 70 ° C to 150 ° C, which is a relatively low temperature. The thickness of the coating film after heating and drying is usually from about 1 μm to 8 μm.

The coating film thus obtained is irradiated with ultraviolet rays through a photomask for forming a desired pattern. At this time, in order to uniformly illuminate the entire exposed area and precisely align the reticle with the substrate, a device such as a reticle aligner or a stepper is preferably used. When irradiated with ultraviolet rays, the region irradiated with ultraviolet rays is cured.

As the ultraviolet light, g-ray (wavelength: 436 nm), h-ray, i-ray (wavelength: 365 nm), or the like can be used. The radiation dose of ultraviolet rays can be appropriately selected as needed.

The coating film cured by UV irradiation is contacted with the developing solution to dissolve the unexposed areas for development, thereby obtaining a desired pattern.

The developing method may be any liquid addition method, dipping method, spray method, or the like. Further, the substrate can be inclined at an arbitrary angle during development.

The developing solution is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound may be an inorganic basic compound or an organic basic compound. Specific examples of the inorganic basic compound may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, Sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Specific examples of the organic basic compound may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine. , monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic basic compounds and organic basic compounds may be used singly or in combination of two or more. The amount of the basic compound may be included in the range of 0.01% by weight to 10% by weight, preferably 0.03% by weight to 5% by weight based on 100% by weight of the developing solution.

As the surfactant, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used. Specific examples of the nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl ether and other polyoxyethylene derivatives, oxyethylene-oxypropylene block copolymer (oxyethylene) -oxypropylene block copolymers), sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene olefins Alkylamine and the like. Specific examples of the anionic surfactant may include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkylarylsulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant may include an amine and a quarternary ammonium salt such as stearylamine hydrochloride and lauryltrimethylammonium chloride. These surfactants may be used singly or in combination of two or more. Based on 100% by weight The amount of the surfactant, the surfactant, is preferably from 0.01% by weight to 10% by weight, more preferably from 0.05% by weight to 8% by weight, still more preferably from 0.1% by weight to 5% by weight.

After development, the pattern is washed with water and then post-baked at a relatively low temperature of 70 ° C to 100 ° C for 10 minutes to 60 minutes.

One embodiment of the present invention is directed to an image display device including the above-described photo-curing pattern. The image display device may include a liquid crystal display device, an OLED, a flexible display, or the like, but is not limited thereto, and it may include all image display devices known to be applicable to the art.

Hereinafter, the present invention will be described in more detail with reference to the following examples, comparative examples, and experimental examples. It is obvious to those skilled in the art that the present invention is not limited to the scope of the invention, and the examples, comparative examples and experimental examples are merely illustrative of the invention.

Preparation Example 1: Preparation of alkali-soluble resin (first resin (A-1))

In a 1 L flask equipped with a reflux condenser, a dropping liquid (hereinafter referred to as a dropping funnel), and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to generate a nitrogen atmosphere, and then 200 g of propylene glycol monomethyl ether acetate was introduced. The ester is added to it. After raising the temperature to 100 ° C, 25.2 g (0.35 mol) of acrylic acid, 4.7 g (0.05 mol) of norbornene, 70.9 g (0.60 mol) of vinyl toluene and 150 g of propylene glycol monomethyl ether acetate were added. mixture. Then, a solution prepared by dissolving 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) in 150 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel over 2 hours. The flask was placed and further stirred at 100 ° C for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air and into the flask. 28.4 g of [0.20 mol (57 mol% based on the acrylic acid used in the reaction)] of glycyl methacrylate was added, and the reaction was continued at 110 ° C for 6 hours, thereby obtaining a solid. A copolymer resin (A-1) having an acid value of 70 mg KOH/g. The polystyrene measured by GPC had a weight average molecular weight of 14,500 and a molecular weight distribution (Mw/Mn) of 2.3.

Preparation Example 2: Preparation of alkali-soluble resin (second resin (A-2))

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to generate a nitrogen atmosphere, and then 150 g of diethylene glycol methyl ethyl ether (diethylene glycol methyl ethyl ether) Ether) was added thereto and heated to 70 ° C with stirring. Subsequently, 132.2 g (0.60 mol) of a mixture of the following chemical formula a and chemical formula b (mole ratio: 50:50), 55.3 g (0.30 mol) of (3-ethyl-3-oxetanyl) Methyl methacrylate and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution.

The prepared solution was added dropwise to the flask using a dropping funnel, and 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 200 g of diethyl In diol methyl ethyl ether. The dissolved solution was added dropwise to the flask using a separate dropping funnel over 4 hours. Complete the addition of polymerization After the hair solution, the mixture was maintained at 70 ° C for 4 hours and then cooled to room temperature. Thereby, a solution having a copolymer resin (A-2) having a solid content of 41.8% by weight and an acid value of 62 mg KOH/g (solid content) was obtained. The obtained resin had a weight average molecular weight (Mw) of 7,700 and a molecular weight distribution of 1.82.

Examples 1 to 9 and Comparative Examples 1 to 5: Preparation of photosensitive resin composition

Each component was mixed according to the components and compositions shown in Table 1 below, and stirred for 3 hours to prepare a photosensitive resin composition (unit: % by weight).

A-1: resin obtained in Preparation Example 1

A-2: resin obtained in Preparation Example 2

B: Dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

C: oxime ester photopolymerization initiator OXE-01 (BASF)

D-1: 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine

D-2: 3-(ethoxydimethylsilyl)-N-(pent-3-yl)propan-1-amine (3-(ethoxydimethylsilyl)-N-(pentan-3-ylidene)propan- 1-amine)

D-3: 3-(methoxydimethylmethyl)-N-(pent-3-ylidene)propan-1-amine

D-4: 3-(ethoxydimethylmethyl)-N-(propan-2-ylidene)propan-1-amine

D-5: 3-(ethoxy(ethyl)(methyl)indenyl)-N-(propan-2-ylidene)propan-1-amine

D-6: 3-(butyl(ethoxy)(methyl)indenyl)-N-(propan-2-ylidene)propan-1-amine

D-7: 3-epoxypropylpropyltriethoxydecane

D-8: 3-isocyanate propyl triethoxy decane

E: poly[(o-cresolyl epoxypropyl ether)-co-formaldehyde]

F: Aron Oxetane PNOX-1009 (Toagosei)

G: oyster sauce additive SH-8400 (Dow Corning Toray)

H: MEDG (diethylene glycol methyl ethyl ether): PGMEA (propylene glycol methyl ether acetate) (4:6) mixture

Experimental Example 1: Evaluation of Adhesive Properties After Development

Each of the photosensitive resin compositions obtained in the examples and the comparative examples was spin-coated on a 4-inch tantalum wafer substrate, and then heated at 70 ° C for 120 seconds using a hot plate. After cooling the heated substrate to room temperature, an i-line stepper (DOF-0.15 μm, Nikon NSR-i11D) was used to form a 30 dot pattern at an interval of 2.5 mJ with an exposure dose (365 nm) of 25 mJ to 125 mJ. Exposure process. The substrate on which the exposure process was completed was immersed at 25 ° C and developed in an aqueous developing solution containing 2.38% of tetramethylammonium hydroxide for 60 seconds and then washed with water. At this time, the formed square dot pattern was observed with an optical microscope, and the results are shown in Table 2 below. The smaller the minimum pattern size that remains and is not lost, the better the adhesion property after development.

<Evaluation criteria>

◎: When the pattern is formed, the number of patterns remaining after the development of the coating film is 100%.

○: When the pattern is formed, the number of patterns remaining on the developed coating film is 95% to 99%.

△: When the pattern is formed, the number of patterns remaining on the developed coating film is 80% to 94%.

X: When the pattern is formed, the number of patterns remaining after the development of the coating film is less than 80%

Experimental Example 2: Evaluation of chemical resistance

After development, the substrate on which the adhesive properties were measured was post-baked at 80 ° C for 60 minutes. The thickness of the square dot pattern thus obtained was measured using a film thickness measuring device, immersed in an organic stripper solution, and treated at 60 ° C for 2 minutes, and the film thickness was measured again, and chemical resistance was evaluated according to the following criteria. The results are shown in Table 2 below.

<Evaluation criteria>

◎: The film thickness change before and after the stripper treatment is less than 1%

○: The film thickness change before and after the release agent treatment was 1% to 2%

△: film thickness change before and after the release agent treatment was 3% to 4%

X: The film thickness change rate before and after the release agent treatment is 5% to 6%

Experimental Example 3: Evaluation of surface damage

After the film thickness measurement of Experimental Example 2, the surface damage of the coating film was evaluated by electron microscope observation according to the following criteria, and the results are shown in Table 2 below.

<Evaluation criteria>

◎: No surface damage pattern was observed during SEM observation.

○: During the SEM observation, a surface damage pattern of 2% to 3% was observed in 100 patterns.

△: 10% to 30% of the surface damage pattern was observed in 100 patterns during SEM observation.

X: 50% to 80% of the surface damage pattern was observed in 100 patterns during SEM observation.

Experimental Example 4: Evaluation of storage stability

The respective photosensitive resin compositions obtained in the examples and the comparative examples were stored under storage conditions at 23 ° C for 60 days, and the change in viscosity was observed. Storage stability was evaluated according to the following criteria, and the results are shown in Table 2 below.

<Evaluation criteria>

Viscosity change of 2cp or more: X

Viscosity change is less than 2cp: ○

As shown in Table 2, the photosensitive resin compositions according to Examples 1 to 9 of the present invention exhibited excellent post-development adhesive properties and chemical resistance even under low-temperature curing at 100 ° C or lower, and also exhibited excellent storage. Stability without surface damage. On the other hand, in the case of the photosensitive resin composition of the comparative example, it contains only one of a decane coupling agent, a novolac epoxy resin, and a phenol novolak oxetane resin, or contains an epoxy functional group. The base decane coupling agent or the isocyanate functional group serves as an additive, and the adhesion property, chemical resistance or storage stability after development is poor or surface damage may occur.

While the invention has been shown and described with respect to the specific embodiments of the present invention Various changes and modifications can be made without departing from the spirit and scope of the invention.

Therefore, the scope of the invention is defined by the scope of the appended claims and their equivalents.

Claims (13)

A negative photosensitive resin composition comprising: an alkali-soluble resin; a photopolymerizable monomer; a photopolymerization initiator; an additive; and a solvent; wherein the additive comprises a decane coupling agent having an amino functional group, and a novolac epoxy At least one of a resin and a phenol novolac oxetane resin. The negative photosensitive resin composition according to claim 1, wherein the decane coupling agent having an amino functional group comprises a compound of the following chemical formula I: Wherein R ₁ to R ₄ are each independently an alkyl group having 1 to 6 carbon atoms; and n is an integer of 0 to 3. The negative photosensitive resin composition as claimed in claim 2, wherein n is 3. The negative photosensitive resin composition according to claim 2, wherein R ₁ is an ethyl group, R ₃ is an isobutyl group, R ₄ is a methyl group, and n is 3. The negative photosensitive resin composition as claimed in claim 1, wherein the negative photosensitive resin composition The novolak epoxy resin comprises at least one selected from the group consisting of poly[(o-cresolyl epoxypropyl ether)-co-formaldehyde], poly[(phenylepoxypropyl ether)-co- -formaldehyde], epoxy propyl terminated poly(bisphenol A-co-epichlorohydrin), and formaldehyde with (chloromethyl)oxirane and 4,4-(1-methylethylidene) double a polymer of (phenol). The negative photosensitive resin composition according to claim 1, wherein the novolak epoxy resin comprises a compound of the following formula II: Wherein n is an integer from 3 to 10. The negative photosensitive resin composition according to claim 1, wherein the phenol novolac oxetane resin comprises a compound of the following formula III: Wherein n is an integer from 3 to 10. The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises a first resin containing a repeating unit represented by the following Chemical Formula IV, and a second resin containing a repeating unit represented by the following Chemical Formula V: Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen group or a methyl group; and R ₅ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (4); Group: R ₆ is a structure derived from a monomer selected from the group consisting of (meth)acrylic acid, 2-(methyl)propenyloxyethyl hexahydrophthalate, ortho-benzene 2-(methyl)propenyloxyethyl formate and 2-(methyl)propenyloxyethyl succinate; R ₇ is a structure derived from a monomer represented by the following formula (5): R ₁₇ is a hydrogen group or a methyl group; and R ₈ is a substituent having a double bond at its end, which is derived from an epoxy compound selected from the group consisting of the following formulas (6) to (14) Obtained by the structural reaction of the (meth)acrylic monomer: a is from 5 mol% to 30 mol%, b is from 10 mol% to 20 mol%, c is from 30 mol% to 60 mol%, and d is from 10 mol% to 30 mol%; R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or methyl; R ₁₂ is a structure derived from a monomer selected from the group consisting of (meth)acrylic acid, hexahydrophthalic acid 2-(Methyl)propenyloxyethyl ester, 2-(methyl)propenyloxyethyl phthalate and 2-(methyl)propenyloxyethyl succinate; R ₁₃ is derived freely The structure of the monomer of the group consisting of the following formulas (15) to (17): R ₁₄ is a structure derived from a monomer represented by the following formula (18): R ₁₅ is an alkylene group having 1 to 6 carbon atoms, and R ₁₆ is an alkyl group having 1 to 6 carbon atoms; e is 10 mol% to 30 mol%, and f is 30 mol% to 60 mol%, and g is 20 mol% to 50 mol%. The negative photosensitive resin composition according to claim 8, wherein a mixing ratio of the first resin to the second resin is from 10:90 to 50:50. The negative photosensitive resin composition according to claim 1, wherein the negative photosensitive resin composition is curable at a temperature of from 70 ° C to 100 ° C. A photocurable pattern formed using the negative photosensitive resin composition as described in any one of claims 1 to 10. The photocuring pattern according to claim 11, wherein the photocuring pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a tube string. Spacer pattern and black column spacer pattern. An image display device comprising the photocuring pattern as recited in claim 11.