KR101623606B1 - Photosensitive resin composition and organic light-emitting apparatus using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an organic light emitting device including the same. The photosensitive resin composition containing the polymer according to the present invention can be applied to various photosensitizers, and particularly applicable to the production of a color filter pattern for a white organic light emitting device (WOLED) among organic light emitting devices.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition and an organic light emitting device including the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition and an organic light emitting device including the same. More specifically, the present invention relates to a color filter including a photosensitive resin composition and an organic light emitting device including the color filter.

In recent years, OLED (Organic Light Emitting Diodes) have been applied to liquid crystal displays (LCDs), which have the largest share in the display market, and liquid crystal displays (LCDs) using backlight units (BLU) of light emitting diodes There is an increasing interest in an organic light emitting device using the organic light emitting diode. In general, organic light emitting devices (OLEDs) can be manufactured not only as thin films but also because they can obtain improved color characteristics and are significantly faster in response speed than liquid crystal displays (LCDs) using liquid crystal driving. It has the advantage of being suitable.

In the small mobile market, AMOLED products are already commercially available and various methods and technologies are being tried for large TVs. Among them, the white organic light emitting diode (WOLED) is a technology that can be more easily applied to a large display product using an organic light emitting diode (OLED). In order to implement color for each pixel, a separate color filter layer .

The present inventors have made intensive studies on a polymer and an organic light-emitting device including the same which can reduce the out-gassing of the binder resin while preventing the remanability and the process characteristics from deteriorating.

The present invention includes a binder resin comprising benzyl methacrylate, a polymerizable compound comprising an ethylenically unsaturated bond, a photoinitiator, a blue pigment and a solvent, wherein the content of benzyl methacrylate in the binder resin is more than 0 % Or less of the total weight of the photosensitive resin composition.

The present invention also provides a photosensitive material comprising the photosensitive resin composition.

Also, the present invention provides an organic light emitting device comprising any one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board made of the photosensitive material.

One embodiment of the present invention has the advantage of reducing the out-gassing of the binder resin.

One embodiment of the present invention has the advantage that the re-solubility and process characteristics are not degraded.

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

The present invention includes a binder resin comprising benzyl methacrylate, a polymerizable compound containing an ethylenically unsaturated bond, a photoinitiator, a blue pigment and a solvent,

Wherein the content of benzyl methacrylate in the binder resin is more than 0 and not more than 13 mol%.

When the content of benzyl methacrylate in the binder resin is 0 mol%, the adhesion to the substrate during development may be weakened and the fine pattern may be detached. When the content of benzyl methacrylate is more than 13 mol%, outgassing ) Is released in a large amount.

The organic light emitting diode OLED may be easily deteriorated by a minute amount of organic matter or moisture and the lifetime may be shortened. For this reason, if the number of materials that emit out-gassing among the materials used to form the color filter is large, it may adversely affect the function of the organic light emitting device OLED.

In addition, studies are needed to reduce out-gassing from materials used in organic light emitting devices, especially white organic light emitting devices (WOLED).

The binder resin may have an acid value of 50 to 130 KOH mg / g and a weight average molecular weight of 1, 000 to 40,000, but is not limited thereto.

The binder resin may include a monomer containing an epoxy group and an ethylenic unsaturated bond; At least one monomer selected from the group consisting of unsaturated carboxylic acid esters, aromatic vinyl monomers, unsaturated ethers, N-vinyl tertiary amines, and unsaturated imides; Monomers containing an acid group; And an acid anhydride.

Examples of the monomer containing an epoxy group and an ethylenic unsaturated bond include allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene- At least one compound selected from the group consisting of 2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene and 1,2-epoxy-9- But is not limited thereto.

Specific examples of the unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl Acrylates such as butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl (meth) (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl Rate, me (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene (Meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3, (Meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl Acrylate, ethyl [alpha] -hydroxymethyl acrylate, propyl [alpha] -hydroxymethyl acrylate and butyl [alpha] -hydroxymethyl acrylate, It is not.

Specific examples of the aromatic vinyl monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, Styrene, but are not limited thereto.

Specific examples of the unsaturated ethers include, but are not limited to, vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether.

Specific examples of the N-vinyl tertiary amines may be selected from the group consisting of N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine, but are not limited thereto.

Specific examples of the unsaturated imide are selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide But is not limited to these.

The acid group-containing monomer may be at least one member selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5- But are not limited thereto.

Examples of the acid anhydride include maleic anhydride, methylmaleic anhydride, and tetrahydrophthalic anhydride, but are not limited thereto.

The present invention relates to: 1) benzyl methacrylate; At least one monomer selected from the group consisting of unsaturated carboxylic acid esters, aromatic vinyl monomers, unsaturated ethers, N-vinyl tertiary amines, and unsaturated imides; Monomers containing epoxy groups and ethylenically unsaturated bonds; And an initiator,

2) reacting the product of step 1) with a monomer containing an acid group, and

3) reacting the product of step 2) with an acid anhydride,

Wherein the content of the benzyl methacrylate is 5 to 20 mol% based on the product of the step 1).

The polymer of the present invention can be synthesized through the above three-step reaction. Step 2) of introducing an unsaturated bond into the basic acrylic binder resin in step 1), and step 3) of imparting an acid group to the acrylic binder resin into which the unsaturated bond is introduced .

In the above step 1), a monomer containing an epoxy group and an ethylenic unsaturated bond and a monomer copolymerizable therewith are contained as repeating units.

Examples of the monomer copolymerizable with the monomer containing an epoxy group and an ethylenically unsaturated bond in the step 1) include unsaturated carboxylic acid esters; Aromatic vinyl monomers; Unsaturated ethers; N-vinyl tertiary amines; And unsaturated imides, but the present invention is not limited thereto.

The content of benzyl methacrylate is 5 to 20 mol% based on the product of step 1). When the content of benzyl methacrylate is less than 5 mol%, adherence to the substrate during development may be weakened, When the content is more than the mol%, a large amount of out-gassing is released.

The content of the monomer containing an epoxy group and the ethylenic unsaturated bond is 30 to 90 mol% based on the product of the step 1), and the content of the monomer copolymerizable with the monomer containing an epoxy group and an ethylenically unsaturated bond is 5 - 60 mole%.

The initiator and polymerization conditions used in the above step 1) are not particularly limited as long as they are used for ordinary radical polymerization.

In the step 2), an unsaturated bond is introduced into the side chain of the basic acrylic binder resin in the step 1), and the epoxy group contained in the basic acrylic binder resin in the step 1) is reacted with the acid group of the acid group-containing monomer .

In the step 3), the acid group is added to the binder resin containing the unsaturated bond in the step 2), and the hydroxyl group formed through the reaction of the epoxy group in the step 2) with the acid group of the acid group-containing monomer is reacted with the acid anhydride Can be obtained.

Examples of the acid anhydride that can be used in the step 3) include maleic anhydride, methylmaleic anhydride, and tetrahydrophthalic anhydride, but are not limited thereto.

In the photosensitive resin composition according to the present invention, the binder resin may be composed only of the polymer according to the present invention, and may further include a binder resin known in the art in addition to the polymer.

In the photosensitive resin composition according to the present invention, the content of the binder resin may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present invention, the polymerizable compound containing an ethylenically unsaturated bond includes ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylol propane (Meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra A compound obtained by esterifying a polyhydric alcohol and an?,? - unsaturated carboxylic acid selected from the group consisting of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; A compound obtained by adding (meth) acrylic acid to a compound containing a glycidyl group selected from the group consisting of trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; a compound having a hydroxyl group or an ethylenically unsaturated bond selected from the group consisting of a phthalic acid diester of? -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of? -hydroxyethyl (meth) An ester compound with an acid, or an adduct with a polyisocyanate; And (meth) acrylic acid alkyl esters selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl However, the present invention is not limited thereto.

The content of the polymerizable compound containing an ethylenically unsaturated bond may be 2 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photoinitiator may be an acetophenone compound; Nonimidazole-based compounds; Triazine compounds; And a oxime-based compound.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- - (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 2-methyl-2- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl- Amino-1- (4-morpholinophenyl) -butan-1-one, or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one. But is not limited thereto.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4,4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole, or 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole There is. But is not limited thereto.

Examples of the triazine compound include 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3 -Hexafluoropropyl] -3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionate, ethyl 2- {4- [ (Trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 2- epoxyethyl-2- {4- [ 6-yl] phenylthio} acetate, benzyl-2- {4- (4-fluorophenyl) (2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 3- { (Trichloromethyl) -s-triazine-6-yl] phenylthio} propionamide, 2,4-bis (trichloro (Trichloromethyl) -6- (1-p-methoxystyryl-s-triazine) Dimethylaminophenyl) -1,3, -butadienyl-s-triazine, or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine. But is not limited thereto.

Examples of the oxime-based compounds include CGI-242 and CGI-124 of Shiba, Japan, but the present invention is not limited thereto.

The content of the photoinitiator may be 0.1 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

As the pigment, a blue pigment may be used solely as a pigment for use in a blue light-sensitive composition, or a blue pigment and a violet pigment may be used in combination.

Pig.Blue # 1 (CI42595: 2), Pig.Blue # 2 (CI44045: 2), Pig.Blue # 9 (CI42025: 1), Pig.Blue # Pig.Blue # 14 (CI42700: 1), Pig.Blue # 19 (CI42750: 1), Pig.Blue # 56 (CI42800: ), Pig.Blue # 62 (CI44084); Cu phthalocyanine-based Pig.Blue # 15 (C.I.74160), Pig.Blue # 15: 1 (C.I.74160); Pig.Blue # 15: 6 (C.I.74160), Pig.Blue # 16 (C.I.74100), a metal phthalocyanine-based; Indanthrone system Pig.Blue # 60 (C.I.69800), Pig.Blue # 64 (C.I.69825); Pig.Blue # 66 (C.I.73000), Pig.Blue # 63 (C.I.73015: x) and the like may be used, but the present invention is not limited thereto.

(CI 45170: 2), Pig.Violet # 2 (CI45175: 1), Pig.Violet # 3 (CI42535: 2) and Pig.Violet # 27 (CI42535: 3), Pig.Violet # 39 (CI42555: 2); Anthraquinone system Pig.Violet # 5: 1 (C.I.58055: 1); Naphthol-based Pig.Violet # 25 (C.I.12321), Pig.Violet # 50 (C.I.12322); Quinacridone system Pig.Violet # 19 (C.I.73900); Pig.Violet # 23 (C.I.51319), Pig.Violet # 37 (C.I.51345); Perylene-based Pig.Violet # 29 (C.I.71129); Benzimidazolone-based Pig.Violet # 32 (C.I.12517), and the like, but the present invention is not limited thereto.

The content of the pigment may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

When the blue pigment and the violet pigment are used in combination, the ratio of the blue pigment to the violet pigment may be 50:50 to 90:10 based on the total weight of the pigment. If the content of the blue pigment exceeds 90 wt% in the whole pigment, the color reproduction rate increases but the luminance may decrease, and the efficiency of the white organic light emitting device (WOLED) panel may decrease. When the content of the blue pigment in the whole pigment is less than 50% by weight, the brightness is increased but the color reproduction rate is decreased, so that it may be difficult to realize the high color reproduction rate organic light emitting device.

On the transmittance spectrum, the range of the peak of the photosensitive composition for blue is 380 to 550 nm.

The solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 Cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2-ethylhexanoate, 2-trichloroethane, 1,1,2-trichloroethane, hexane, heptane, Methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl It may be at least one selected from the group consisting of citrate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether. But is not limited thereto.

The content of the solvent may be 45 to 95% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The light-sensitive resin composition may further include at least one additive selected from the group consisting of a photo-crosslinking agent, a curing accelerator, a dispersant, a surfactant, an adhesion promoter, an antioxidant, a thermal polymerization inhibitor and an ultraviolet absorber.

The photo-crosslinking sensitizer may be at least one selected from the group consisting of benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, Benzoate compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone or 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, isopropylthioxanthone or diisopropylthioxanthone, compound; Xanthone compounds such as xanthone or 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone or 2,6-dichloro-9,10-anthraquinone; (9-acridinylpentane), 1,3-bis (9-acridinyl) propane, and the like. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate or 2-n-butoxyethyl-4- (dimethylamino) benzoate; (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone or 2,6-bis Amino-synergists such as methyl-cyclopentanone; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- -Benzoyl-7-methoxy-coumarin or 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- Pyran o [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline, and the like can be used, but the present invention is not limited thereto.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercapto- Acetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate) or trimethylolpropane-tris (3-mercaptopropionate) But is not limited thereto.

The dispersant may be used either in a manner of internally adding to the pigment in the form of surface-treating the pigment in advance, or in a method of externally adding the pigment. As the dispersing agent, a polymer type, a nonionic, an anionic, or a cationic dispersing agent can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, But are not limited to, at least one member selected from the group consisting of an oxide adduct, a sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine.

The surfactant may be a silicone surfactant or a fluorinated surfactant. Specifically, the silicone surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK- , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-370, BYK-370, BYK-370, BYK-380 and BYK-390 may be used. Examples of the fluorine surfactant include DIC (Dai Nippon Ink & Chemicals) -177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F- , F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F- TF-1124SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441 Or TF-1442 may be used, but the present invention is not limited thereto.

The adhesion promoter may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane, Trimethoxysilane, and the like, but the present invention is not limited thereto.

The antioxidant may be 2,2-thiobis (4-methyl-6-t-butylphenol), or 2,6-g, t-butylphenol, -Butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, or alkoxybenzophenone. The thermal polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4- t-butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.

The thermal polymerization inhibitor may be at least one selected from the group consisting of p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine Aluminum salts, and phenothiazine, but are not limited thereto and may include those generally known in the art.

The ultraviolet absorber, plasticizer, filler, and the like may be all compounds that can be included in conventional photosensitive resin compositions.

The content of the additive may be independently 0.01 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

Meanwhile, the photosensitive resin composition according to the present invention is used for a roll coater, a curtain coater, a spin coater, a slot die coater, various printing, Or the like. It is also possible to apply it onto a support such as a film and then transfer it to another support or coat it on a first support, transfer it to a blanket or the like, and transfer it to a second support again.

Examples of the light source for curing the photosensitive resin composition according to the present invention include, but are not limited to, a mercury vapor arc, a carbon arc, and an Xe arc, which emits light having a wavelength of 250 to 450 nm.

The photosensitive resin composition containing the polymer according to the present invention has not only excellent sensitivity and developability, but also has a high taper angle and excellent adhesive strength. Accordingly, the photosensitive resin composition containing the polymer according to the present invention can be applied to various photosensitizers, and in particular, in the production of a color filter pattern for a white organic light emitting device (WOLED).

The present invention also provides a photosensitive material comprising the photosensitive resin composition.

The photosensitive resin composition according to the present invention can be used for forming a color filter of an organic light emitting device including an organic light emitting device, particularly a white organic light emitting device (WOLED), a photosensitive material for forming a black matrix of an organic light emitting device, Photosensitive material, and column spacer photosensitive material. It can also be used for photocurable paints, photocurable inks, photocurable adhesives, printing plates, photosensitive materials for printed wiring boards, other transparent photosensitive materials, and PDP manufacturing.

Also, the present invention provides an organic light emitting device comprising any one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board made of the photosensitive material.

The organic light emitting device is an organic light emitting diode (OLED) device. The organic light emitting device includes a panel and a backlight unit (BLU) including a color filter, a black matrix, an overcoat layer, a column spacer, a printed wiring board, and the like manufactured from the photosensitive material of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples illustrate the present invention and the scope of the present invention includes the scope of the following claims and substitutions and modifications thereof, which are not intended to limit the scope of the embodiments.

[Synthesis Example 1] Synthesis of binder resin according to an example of the present invention

(1) Step 1: Basic Acrylic Binder Resin Polymerization Step

10.3 g of each monomer, benzyl methacrylate, 23.8 g of N-phenylmaleimide and 14.0 g of styrene were mixed so that the molar ratio of benzyl methacrylate to N-phenylmaleimide and styrene was 1: 2: 2, 71.9 g of glycidyl methacrylate, 4 g of 1-dodecanethiol as a chain transfer agent, and 480 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were mixed for 30 minutes under a nitrogen atmosphere using a mechanical stirrer. The temperature of the reactor was raised to 60 DEG C under a nitrogen atmosphere, and when the temperature of the mixture reached 60 DEG C, 5 g of a V-65 solution as a thermal polymerization initiator was added and stirred for 15 hours. (Mw 6000, Av 0)

(2) Step 2: Introduction of unsaturated group

0.5 g of tetraethylammonium bromide and 0.1 g of 4-methoxyphenol as a thermal polymerization inhibitor were added and stirred for 3 hours in an air atmosphere. Then, 26.1 g of methacrylic acid And the temperature of the reactor was increased to 100 DEG C and the mixture was stirred for 24 hours. (Mw 8000, Av 5)

(3) Step 3: Granting an age

The temperature of the polymer solution prepared in Step 2 was lowered to 70 캜, 30.8 g of tetrahydrophthalic anhydride was added, and the mixture was further stirred at 80 캜 for 24 hours to synthesize a desired alkali-soluble binder resin. (Mw 10000, AV 80)

[Synthesis Example 2]

In the synthesis step 1 of Synthesis Example 1, 17.1 g of each monomer, benzyl methacrylate, 19.8 g of N-phenylmaleimide, N-phenylmaleimide, and the like were added so that the molar ratio of benzyl methacrylate to N-phenylmaleimide and styrene was 1: Except that 11.7 g of styrene and 71.9 g of glycidyl methacrylate were used to synthesize a binder resin (Mw 10000, AV 80)

[Synthesis Example 3]

In Synthesis Example 1 of Synthesis Example 1, 38.5 g of each monomer, benzyl methacrylate, 7.4 g of N-phenylmaleimide, N-phenylmaleimide and N-phenylmaleimide were added so that the molar ratio of benzyl methacrylate to N-phenylmaleimide and styrene was 6: Except that 4.4 g of styrene and 71.9 g of glycidyl methacrylate were used in the same manner as in Example 1. The binder resin was synthesized (Mw 10000, AV 80)

[Synthesis Example 4]

In the synthesis step 1 of Synthesis Example 1, methyl methacrylate was used in place of benzyl methacrylate to prepare methyl methacrylate, which is a monomer of each monomer, such that the molar ratio of methyl methacrylate to N-phenylmaleimide and styrene is 1: 2: A binder resin was synthesized (Mw 10000, AV 80) in the same manner as in Example 1 except that 6.8 g of the monomer, 23.8 g of N-phenylmaleimide, 14.0 g of styrene, and 71.9 g of glycidyl methacrylate were used.

[Example 1]

24.014 parts by weight of Pigment Blue 15: 6 as a pigment, 6.773 parts by weight of Pigment V23, 2.169 parts by weight of a binder resin prepared in Synthesis Example 1, 5.108 parts by weight of dipentaerythritol hexaacrylate as an ethylenically unsaturated polymerizable compound, 0.53 part by weight of I-907 (BASF), 1.36 parts by weight of I-369 (BASF), 0.09 part by weight of EMK (BASF), 2.009 parts by weight of an acrylic dispersant as an additive, 0.127 part by weight of oxypropyltrimethoxysilane, 0.06 part by weight of F-475 (DaiNippon Ink & Chemicals) as a surfactant, 56.146 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 27.654 parts by weight of acetic acid 3-methoxybutyl ester And the mixture was stirred for 5 hours to prepare a blue photosensitive composition of an organic light emitting device.

[Example 2]

A blue photosensitive composition of an organic light emitting device was prepared in the same manner as in Example 1, except that the binder resin of Synthesis Example 2 was used as the binder resin in Example 1 above.

[Comparative Example 1]

A blue photosensitive composition of an organic light emitting device was prepared in the same manner as in Example 1 except that the binder resin of Synthesis Example 3 was used as the binder resin in Example 1.

[Comparative Example 2]

A blue photosensitive composition of an organic light emitting device was prepared in the same manner as in Example 1, except that the binder resin of Synthesis Example 4 was used as the binder resin in Example 1 above.

[Experimental Example]

1. Evaluation of composition of out-gassing

The blue photosensitive resin compositions of the above Examples and Comparative Examples were spin-coated on glass, pre-baked on a hot plate for 100 seconds and 80 seconds, exposed to the front without mast at 40 mJ / cm ² , And fired in a convection oven for 20 minutes. The substrate coated with the blue photosensitive resin composition was cut into a size of 1 cm x 5 cm and was subjected to a purge and trap method using a GC / mass spectrometer (out-gassing).

2. Re-solubility evaluation

The blue photosensitive resin compositions of the above Examples and Comparative Examples were spin-coated on glass, pre-baked on a hot plate at 100 degrees for 2 minutes, 5 minutes, and 10 minutes, cut into 1 cm x 5 cm size pieces and washed with propylene glycol monomethyl ether acetate (PGMEA) solvent to observe the dissolution characteristics of the coated and dried blue photosensitive composition.

3. Evaluation of process characteristics

The blue photosensitive resin compositions of the above Examples and Comparative Examples were spin-coated on glass and pre-baked on a hot plate at 100 ° C. for 80 seconds. Using a mask having a square pattern, mJ / cm ² and developed with potassium hydroxide (KOH) 0.04% alkali developer at 25 ° C for 70 seconds, and the degree of remained unremoved by the development process of a small square pattern Respectively.

Out-gassing content Reuse characteristics Process characteristics (pattern size) Example 1 2.2 μg / g Dissolve in 10 minutes > 10 μm Example 2 2.5 μg / g Dissolve in 10 minutes > 10 μm Comparative Example 1 3.4 μg / g Dissolve in 10 minutes > 10 μm Comparative Example 2 2.08 μg / g Dissolve in 10 minutes > 20 μm

As can be seen from the results of Table 1, when the content of benzyl methacrylate was reduced (Example 1 and Example 2) as in the present invention, the amount of the component of the outgassing gas was compared with that of Comparative Example 1 However, when the benzyl methacrylate having an effect on the adhesion of the substrate is completely removed (Comparative Example 2), the development process characteristic is poor and the fine pattern is dropped.

Claims (7)

A binder resin containing benzyl methacrylate, a polymerizable compound containing an ethylenically unsaturated bond, a photoinitiator, a blue pigment, a violet pigment and a solvent,
Wherein the content of benzyl methacrylate in the binder resin is 0 to 13 mol%
Wherein the ratio of the blue pigment to the violet pigment is 50:50 to 90:10 based on the total weight of the pigment,
And the peak range on the transmittance spectrum is 380 to 550 nm. [2] The method according to claim 1, wherein the binder resin comprises a monomer containing an epoxy group and an ethylenic unsaturated bond; At least one monomer selected from the group consisting of unsaturated carboxylic acid esters, aromatic vinyl monomers, unsaturated ethers, N-vinyl tertiary amines, and unsaturated imides; Monomers containing an acid group; And an acid anhydride. The photosensitive resin composition according to claim 1, wherein the binder resin has an acid value of 50 to 130 KOH mg / g and a weight average molecular weight of 1, 000 to 40,000. delete The photosensitive resin composition according to claim 1, further comprising at least one additive selected from the group consisting of a photo-crosslinking agent, a curing accelerator, a dispersant, a surfactant, an adhesion promoter, an antioxidant, a thermal polymerization inhibitor and an ultraviolet absorber By weight based on the total weight of the photosensitive resin composition. A photosensitive material comprising the photosensitive resin composition according to any one of claims 1 to 3 and 5. An organic light emitting device comprising any one selected from the group consisting of a color filter, a black matrix, an overcoat layer, a column spacer, and a printed wiring board made of the photosensitive material of claim 6.