KR101670245B1 - Photosensitive resin comopsition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition which comprises an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and a solvent (D) The present invention relates to a photosensitive resin composition which can form a photo-curable pattern having improved mechanical properties by including a compound represented by the general formula (1), and is excellent in developability and a photo-curable pattern formed by using the same.

Description

[0001] PHOTOSENSITIVE RESIN COMOPSITION [0002]

The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition which can form a pattern having excellent mechanical strength and is excellent in developability.

In the display field, the photosensitive resin composition is used for forming various photocuring patterns such as a photoresist, an insulating film, a protective film, a color filter, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve the process yield and improve the physical properties of the application object in this process, a photosensitive resin having a high sensitivity A composition is required.

On the other hand, a common display device has used a silica bead or a plastic bead having a certain diameter in order to maintain a predetermined distance between the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device. Currently, a spacer used in most display devices is formed by photolithography.

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

2. Description of the Related Art In recent years, as the demand for touch panels has increased due to the popularization of smart phones and tablet PCs, elastic recovery rate, which is a basic characteristic of a spacer for maintaining a space between a color filter substrate and an array substrate, It is required to have a hard characteristic so as not to deform the pixel. However, although the conventional photosensitive resin composition for forming a spacer has a sufficient elastic recovery rate, hard properties without pixel deformation due to external pressure can not be achieved satisfactorily.

In this regard, Japanese Laid-Open Patent Publication No. 1999-133600 discloses a photosensitive resin composition for forming a spacer containing a copolymer resin having a carboxyl group and a glycidyl ether group as a binder resin. The composition disclosed in Japanese Laid-Open Patent Publication No. 1999-133600 has a certain degree of heat stability and strength, but still fails to satisfy satisfactory elastic recovery and strength.

Japanese Laid-Open Patent Application No. 1999-133600

It is an object of the present invention to provide a photosensitive resin composition capable of forming a photo-curable pattern having a small total displacement amount and excellent elastic recovery rate.

It is another object of the present invention to provide a photosensitive resin composition excellent in developability.

It is another object of the present invention to provide a photocurable pattern formed from the photosensitive resin composition.

1. A photosensitive resin composition comprising an alkali soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the polymerizable compound (B) Resin composition:

[Chemical Formula 1]

(Wherein l, m, n and o are each independently an integer of 1 to 3).

2. The photosensitive resin composition according to 1 above, wherein the compound represented by the formula (1) is a compound represented by the following formula (2) or (3)

(2)

(3)

.

.

3. The photosensitive resin composition according to 1 above, wherein the compound represented by Formula 1 is contained in an amount of 50 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

4. The photosensitive resin composition according to 1 above, wherein the compound represented by the formula (1) is contained in an amount of 30 to 100 parts by weight per 100 parts by weight of the total polymerizable compound (B).

5. A photocurable pattern formed from the photosensitive resin composition of any one of items 1 to 4 above.

6. The photocurable pattern according to 5 above, wherein the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern and a black column spacer.

7. An image display apparatus comprising the photocuring pattern of the above item 6.

The photosensitive resin composition of the present invention can form a photo-curable pattern having excellent mechanical properties.

Further, the photosensitive resin composition of the present invention exhibits excellent developability.

1 to 4 show the dissolution process of the coating film according to the developability evaluation test.

The present invention relates to a photosensitive resin composition comprising an alkali soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and a solvent (E) A photocurable resin composition capable of forming a photocurable pattern having improved physical properties and excellent in developing property, and a photocurable pattern formed by using the same.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and a solvent (E).

The alkali-soluble resin (A)

The alkali-soluble resin (A) to be used in the present invention is a component which imparts solubility to an alkali developing solution used in a development processing step for forming a pattern, and is polymerized including an ethylenically unsaturated monomer having a carboxyl group.

The type of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, preferably acrylic acid and methacrylic acid. These may be used alone or in combination of two or more.

The alkali-soluble resin (A) according to the present invention may be polymerized by further comprising at least one other monomer copolymerizable with the monomer. Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p- Aromatic vinyl compounds such as vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds; Unsaturated oxiranes such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and methyl glycidyl compound; A (meth) acrylate substituted with a cycloalkane having 4 to 16 carbon atoms, a dicycloalkane, or a tricycloalkane ring; And the like. These may be used alone or in combination of two or more.

The acid value of the alkali-soluble resin (A) is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, it becomes possible to manufacture a spacer having excellent stability with time and elastic recovery.

The weight average molecular weight of the alkali-soluble resin (A) in terms of polystyrene is 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin is within the above range, it is preferable to prevent film reduction during development and to improve the missability of the pattern portion.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is within the above range, the developability is preferable.

The content of the alkali-soluble resin (A) is not particularly limited, but may be 10 to 90 parts by weight, preferably 25 to 70 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition, based on the solid content. When it is contained within the above-mentioned range, it is possible to form a photo-curable pattern having a sufficient degree of solubility in a developer and excellent developability, and having a good elastic recovery rate and a small total displacement.

Polymerizable  The compound (B)

The polymerizable compound (B) used in the photosensitive resin composition of the present invention includes a compound represented by the following formula (1).

[Chemical Formula 1]

(Wherein l, m, n and o are each independently an integer of 1 to 3).

The photosensitive resin composition of the present invention includes the compound of Formula 1 to significantly increase the crosslinking density during the manufacturing process, thereby enhancing the mechanical properties such as the reduction of the total displacement amount of the curing pattern and the improvement of the elastic recovery rate.

Specific examples of the compound represented by the formula (1) include, but are not limited to, the following formulas (2) and (3).

(2)

(3)

.

.

The amount of the compound represented by the formula (1) is not particularly limited and may be, for example, 50 to 200 parts by weight, preferably 80 to 180 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). When the above range is satisfied, it is possible to form a cured pattern having a good elastic recovery rate and a small total displacement amount.

The content of the compound represented by the formula (1) may be, for example, 30 to 100 parts by weight, preferably 60 to 80 parts by weight, per 100 parts by weight of the total polymerizable compound (B). When the above range is satisfied, it is possible to form a cured pattern having a good elastic recovery rate and a small total displacement amount.

The polymerizable compound (B) may further include an additional monomer (b1) in addition to the compound represented by the general formula (1) to significantly improve the developability.

The additional monomers (b1) are monofunctional monomers, bifunctional monomers and other polyfunctional monomers, and the kind thereof is not particularly limited, but examples thereof include the following compounds.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

The content of the polymerizable compound (B) is not particularly limited. For example, the content of the polymerizable compound (B) is 10 to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin and the polymerizable compound based on the solid content in the photosensitive resin composition Is used in the range of 30 to 80 parts by weight. When the polymerizable compound (B) is contained in the above content range, it is possible to form a cured pattern having a good elastic recovery rate and a small total displacement amount, and to improve the developability of the composition.

Light curing Initiator (C)

The photopolymerization initiator (C) according to the present invention is not particularly limited as long as it can polymerize the polymerizable compound (B), and examples thereof include acetophenone-based compounds, benzophenone- At least one compound selected from the group consisting of a basic compound, a non-imidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound can be used, and an oxime ester-based compound is preferably used.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole .

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octadione, (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl- Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca), NCI-831 (Ciba Geigy), CGI- Adeca).

The photopolymerization initiator (C) may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

Examples of the photopolymerization initiator include 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.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.

Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator (C) is not particularly limited and may be, for example, 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition based on the solid content . When the above range is satisfied, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened. Thus, the productivity is improved, the resolution can be maintained, and the strength of the formed pixel portion and the smoothness on the surface of the pixel portion can be improved. good.

The solvent (D)

The solvent (D) can be used without limitation as long as it is commonly used in the art.

Specific examples of the solvent include ethylene glycol monoalkyl ethers 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 acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate; Dipropylene glycol dialkyl 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 glycerin; Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as? -butyrolactone. The solvents exemplified herein may be used alone or in combination of two or more.

The solvent may be selected from esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate And more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used.

The content of the solvent (D) may be in the range of 40 to 95 parts by weight, preferably 45 to 85 parts by weight, based on 100 parts by weight of the total of the photosensitive resin composition. When the above-mentioned range is satisfied, it is preferable because the coating property is improved when applied by a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater), an ink jet or the like.

Additive (E)

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like.

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

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

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

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

< Photocuring  Pattern and image display device>

An object of the present invention is to provide an image display device including the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.

The photocurable pattern made of the photosensitive resin composition has excellent adhesion to a base material. As a result, it can be used for various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and the like in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, However, it is not limited thereto, and is particularly suitable as a spacer pattern because of its excellent developability and mechanical properties.

The image display device having such a photo-curing pattern may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all image display devices known in the art that can be applied are exemplified.

The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).

First, a photosensitive resin composition is coated on a substrate and then heated and dried to remove a volatile component such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coat method or a slit coat method. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. If desired, the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, and a desired pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Synthetic example  1: Synthesis of alkali-soluble resin (A)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube. The atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, 47.2 g of vinyltoluene (0.40 mol) of methacrylic acid, 43.0 g (0.50 mol) of methacrylic acid, 40.0 g (0.40 mol) of methacrylic acid methyl ester, (0.20 mol) of propylene glycol and 136 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over a period of 2 hours from a dropping funnel, and a solution prepared by adding 3.6 g of azobisisobutyronitrile to the mixture was added dropwise to the flask at 100 占 폚 Stirring was continued for another 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate (0.20 mol (40 mol% based on the methacrylic acid used in the present reaction)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone The reaction was continued at 110 캜 for 6 hours to obtain a first resin A containing an unsaturated group having a solid acid value of 99 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 28,000 and the molecular weight distribution (Mw / Mn) was 2.2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC-8120GPC (manufactured by TOSOH CORPORATION), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL connected in series , The column temperature was 40 占 폚, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 占, and the detector RI was used. The concentration of the test sample was 0.6 mass% (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used.

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Example  And Comparative Example

Classification (parts by weight) Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 4 Alkali-soluble resin A 40 40 40 40 40 40 30 30 60 40 30 30 Polymerizable
compound B-1 60 - 40 - 45 - 35 30 - - - - B-2 - 60 - 40 - 45 - - - - - - B-3 - - 20 20 15 15 35 30 40 60 - 25 B-4 - - - - - - - - - - 50 25 Photopolymerization initiator C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 C-2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 C-3 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 menstruum D-1 20 20 20 20 20 20 20 20 20 20 20 20 D-2 45 45 45 45 45 45 45 45 45 45 45 45 D-3 30 30 30 30 30 30 30 30 30 30 30 30 additive E 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4

B-2:

B-3: 디펜타에리트리톨헥사아크릴레이트(KAYARAD DPHA ; 닛폰 화약 (주) 제조)
B-4:

TEP-G (아사히기재공업㈜)
광중합 개시제C
C-1: 2,2'-비스(o-클로로페닐)-4,5,4',5'-테트라페닐-1,2'-비이미다졸
(B-CIM: 호도가야 화학공업㈜ 제조)
C-2:

C-3:

용매 D:
D-1: 디에틸글리콜 메틸에틸 에테르
D-2: 프로필렌글리콜모노메틸에테르아세테이트
D-3: 3-메톡시-1-부탄올
첨가제(산화 방지제)E: 4,4'-부틸리덴 비스[6-tert-부틸-3-메틸페놀](BBM-S: 스미토모 정밀화학 제조)Alkali-soluble resin A: The alkali-soluble resin of Synthesis Example 1
Polymerizable compound B:
B-1:

B-2:

B-3: Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
B-4:

TEP-G (Asahi Kasei Kogyo Co., Ltd.)
Photopolymerization initiator C
C-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-
(B-CIM: manufactured by Hodogaya Chemical Co., Ltd.)
C-2:

C-3:

Solvent D:
D-1: Diethylglycol methyl ethyl ether
D-2: Propylene glycol monomethyl ether acetate
D-3: 3-Methoxy-1-butanol
(Antioxidant) E: 4,4'-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S manufactured by Sumitomo Fine Chemical)

Test Methods

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were respectively spin-coated on the glass substrate and then pre-baked at 90 DEG C for 125 seconds using a hot plate. The prebaked substrate was cooled to room temperature and light was irradiated at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with an interval of 150 μm from the quartz glass photomask Respectively. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

The coating film was exposed to a water-based developer having circular openings (patterns) each having a diameter of 10 mu m and having an interval of 100 mu m and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after irradiation, And then subjected to post-baking at 230 캜 for 30 minutes in an oven. The obtained pattern height was 3 占 퐉. The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Table 2 below.

(1) Mechanical characteristics evaluation (total displacement and recovery rate)

The cured film obtained above was measured according to the following measurement conditions by using a dynamic ultra microhardness tester (HM-2000; Helmut Fischer GmbH + Co. KG) under the following measurement conditions: the total displacement amount (占 퐉) and the elastic displacement amount (%) Were calculated as follows, and the results are shown in Table 2 below.

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

The measurement conditions are as follows.

Test mode; Load-Unload test

Test force; 50.0 mN

Load speed; 4.41 mN / sec

Retention time; 5sec

Indenter; Square pyramid indenter (diameter 50 μm)

(2) Developability  evaluation

The cured film obtained above was observed for dissolution of the coating film for 60 seconds using a 0.06% KOH aqueous solution, and the results are shown in Table 2 below.

<Evaluation Criteria>

&Amp; cir &amp;: Dissolution completed within 30 seconds from the moment the coating film was deposited in the developer (see Fig. 1)

O: The coating film partially peeled off but dissolved in 30 seconds (see Fig. 2)

DELTA: Time required for 60 seconds to dissolve the coating film as a whole (refer to FIG. 3)

X: When the peeling or dissolution of the coating film itself in the state of being immersed in the developer is not completed even after a lapse of 60 seconds or more (see Fig. 4)

division Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 4 Total displacement (㎛) 0.68 0.73 0.81 0.88 0.77 0.80 0.86 0.84 1.52 1.21 0.91 1.09 Recovery Rate (%) 87.2 86.1 82.6 81.1 85.3 83.0 81.7 80.1 55.8 65.6 77.6 72.4 Developability ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ X △

Referring to Table 2, the photosensitive resin composition according to the present invention (Examples 1 to 8) is excellent in developing property, and when a pattern is formed using the photosensitive resin composition, the total amount of displacement of the pattern is very small and the recovery rate is high, Which is very suitable for

However, it was confirmed that the comparative examples not using the polymerizable compound of the present invention remarkably lowered developability and mechanical properties as compared with the examples. However, in the case of Comparative Example 1 in which no polymerizable compound was used at all, it was confirmed that the developability was equivalent to that in Examples.

Claims (7)

(A), a polymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the alkali-
The polymerizable compound (B) comprises a compound represented by the following formula (1) and a compound having at least one acrylic group in the molecule,
The compound represented by Formula 1 is contained in an amount of 60 to 80 parts by weight based on 100 parts by weight of the total polymerizable compound (B)
The photosensitive resin composition for forming a spacer, wherein the alkali-soluble resin (A) and the polymerizable compound (B) are contained in a weight ratio of 10:90 to 40:60,
[Chemical Formula 1]

(Wherein l, m, n and o are each independently an integer of 1 to 3).
The photosensitive resin composition for forming a spacer according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (2) or (3)
(2)

(3)

.
delete delete A spacer formed from the photosensitive resin composition of any one of claims 1 and 2.
delete An image display apparatus comprising the spacer of claim 5.

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