KR20180092529A - Black photo sensitive resin composition for a forming pixel defined layer of oled and qled - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition for forming a pixel defined layer of an organic light emitting device comprising a colorant (A), binder resin (B), a photo-polymerizable compound (C), a photo-polymerization initiator (D), and a solvent, wherein the binder resin (B) includes a compound (B1) represented by chemical formula 1. In addition, provided are an organic light emitting device including a pixel defined layer manufactured by the black photosensitive resin composition, a quantum dot light emitting device, and a display device including the organic light emitting device or the quantum dot light emitting device. According to chemical formula 1, R1 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, wherein the alkyl group can be substituted with a hydroxyl group. R2 represents an aliphatic or aromatic hydrocarbon of C1-C20 including or excluding a simple bond or a heteroatom. According to the present invention, the black photosensitive resin composition is able to remarkably reduce emission of outgas, thereby preventing brightness and performance of a device from being degraded.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black photosensitive resin composition for forming a pixel defining layer of an organic light emitting device and a quantum dot light emitting device,

The present invention relates to an organic light emitting device and a black photosensitive resin composition for forming a pixel defining film of a quantum dot light emitting device, an organic light emitting device and a quantum dot light emitting device including a pixel defining film made of the black photosensitive resin composition, And a display device including the device.

Since the organic light emitting device, which is one of the flat panel display devices, is self-emitting type, it has excellent viewing angle and contrast compared to a liquid crystal display device and requires a back light It is lightweight and thin because it does not, is also advantageous in terms of power consumption. In addition, it is possible to drive DC low voltage, fast response speed, and all of the constituent elements are solid, which is strong against external impact, has a wide temperature range, and is also inexpensive in terms of manufacturing cost.

Particularly, since the manufacturing process of the organic light emitting diode is a repetition and encapsulation process of a deposition / etching process, unlike a liquid crystal display device or a PDP (Plasma Display Panel) It has the advantage of being very simple.

 The organic light emitting device must have good contrast and brightness. However, when the external light is bright, the contrast is poor. In the case of an organic light emitting device of a bottom emission type, since the cathode of the device is made of a metal having a high reflectance, the light entering the device from the outside is reflected on the cathode surface and mixed with the light emitted from the light emitting layer.

 In order to solve the above problems, most of the organic light emitting devices currently have a circular polarizer formed under the transparent substrate, thereby reducing the reflection of external incident light by the cathode. That is, when external light is incident by the circularly polarizing plate, half is cut off, and the other half is blocked when it is reflected on the cathode, thereby suppressing a decrease in contrast due to external light.

 However, since the organic light emitting device having the circular polarizer on the above-mentioned conventional transparent substrate greatly reduces the reflection of the external incident light by the cathode and also blocks the light emitted to the outside from the organic light emitting layer, the contrast is improved, There is a problem in that the cost is reduced.

 Therefore, in order to solve the above problems, it is possible to form a black pixel defining layer that absorbs external incident light and improves the contrast. The black pixel definition layer is precisely patterned through a photolithography process, and reliability is required such that a gas component that is lethal to device driving is not eluted during a high-pressure deposition process for manufacturing organic light emitting device pixels.

However, the photosensitive resin composition for a BM (Black Matrix) used in a conventional liquid crystal display (OLED) device has a problem that a gas component that is critical to the organic light emitting device is eluted during the high pressure deposition process for manufacturing organic light emitting device pixels, There is a problem in that the luminance is lowered and the organic light emitting element is made incapable of driving so that it is difficult to apply it to the organic light emitting element.

Korean Patent Publication No. 10-2015-0072581

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art,

And an object of the present invention is to provide an organic light emitting device and a black photosensitive resin composition for forming a pixel defining layer of a quantum dot light emitting device which can significantly reduce the outgassing amount during the manufacture of organic light emitting devices such as high pressure deposition processes or quantum dot light emitting device pixels.

It is another object of the present invention to provide an organic light emitting device including a pixel defining layer made of the black photosensitive resin composition, a quantum dot light emitting device, and a display device including the organic light emitting device or the quantum dot light emitting device.

In order to achieve the above object,

The present invention relates to a colorant composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D)

There is provided a black photosensitive resin composition for forming a pixel defining layer of an organic light emitting device and a quantum dot light emitting device, wherein the binder resin (B) comprises a compound (B1) represented by the following formula (1)

[Chemical Formula 1]

In the above formula

R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group may be substituted with a hydroxyl group;

R 2 represents a C 1 -C 20 aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom.

In addition,

An organic light emitting device including the pixel defining layer made of the black photosensitive resin composition, and a quantum dot light emitting device.

In addition,

And a display device including the organic light emitting device or the quantum dot light emitting device.

The black light sensitive resin composition for forming a pixel defining layer of the organic light emitting device and the quantum dot light emitting device of the present invention remarkably reduces the amount of outgassing during the production of the organic light emitting device or the quantum dot light emitting device pixel such as a high pressure deposition process, And the effect of preventing degradation of the luminance and driving performance of the device.

Therefore, an organic light emitting device, a quantum dot light emitting device, and a display device including the organic light emitting device or the quantum dot light emitting device including the pixel defining layer made of the black photosensitive resin composition provide excellent quality in terms of brightness, driving property and durability .

The present invention relates to a colorant composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D)

There is provided a black photosensitive resin composition for forming a pixel defining layer of an organic light emitting device and a quantum dot light emitting device, wherein the binder resin (B) comprises a compound (B1) represented by the following formula (1)

[Chemical Formula 1]

In the above formula

R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group may be substituted with a hydroxyl group;

R 2 represents a C 1 -C 20 aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom.

Each component constituting the black photosensitive resin composition of the present invention will be described below. However, the present invention is not limited to these components.

The colorant (A)

The colorant (A) is used for black coloring and imparts the light shielding property of the pixel defining layer and the anti-reflection of external light.

The coloring agent may be any coloring agent known in the art such as organic pigments, dyes and black pigments, as far as it is shielding from visible light, but it is preferable to use black pigments.

Specific examples of the black pigment include, but are not limited to, aniline black, lactam black, perylene black, carbon black, chromium oxide, iron oxide and titanium black. These may be used singly or in combination of two or more. Examples of the carbon black include channel black, furnace black, thermal black and lamp black.

Carbon black coated with a resin on its surface may be used for electrical insulation if necessary. In addition, since the resin-coated carbon black has a lower conductivity than the carbon black not coated with the resin, excellent electrical insulation can be imparted at the time of forming the black matrix and the pixel defining film.

The colorant may comprise a black pigment and a blue pigment, wherein the black pigment may be a black organic pigment and / or a black inorganic pigment.

When a black pigment and a blue pigment are used, the transmittance of the visible light region and the ultraviolet ray region can be adjusted depending on the pigment ratio, which is preferable.

As the black organic pigments, black inorganic pigments and blue pigments, any known pigments can be used, and for example, a compound classified as a pigment in the color index (The Society of Dyers and Colourists) And may contain known dyes.

As the black organic pigment, at least one selected from aniline black, lactam black and perylene black may be used in combination, but is not limited thereto.

The black inorganic pigments include carbon black, chromium oxide, iron oxide and titanium black.

Specific examples of the blue pigment include CI Pigment Blue 15: 6, CI Pigment Blue 15: 4, CI Pigment Blue 60, CI Pigment Blue 16, and the like.

The ratio of the black organic pigment, the black inorganic pigment and the blue pigment may be 70 to 95 wt%, 1 to 15 wt%, and 1 to 20 wt%, respectively.

When the black organic pigment and the black inorganic pigment are used together, they may be preferable in that they have a low dielectric property and a high coloring power.

In addition, the colorant may further optionally include a color correcting agent. As the color correcting agent, condensation polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments or organic pigments such as azo pigments can be used.

The colorant may be contained in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, based on the total weight of the black photosensitive resin composition. If the content of the colorant is less than the above range, the light shielding property is not sufficient and the above-mentioned effect can not be ensured. On the other hand, if the content exceeds the above range, the quality of the pattern obtained after patterning may deteriorate. .

The binder resin (B)

The binder resin (B) is characterized by being a copolymer obtained by a copolymerization reaction, which comprises a compound (B1) represented by the following formula (1)

[Chemical Formula 1]

In the above formula

R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group may be substituted with a hydroxyl group;

R 2 represents a C 1 -C 20 aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom.

Examples of R 2 include a linear or branched alkylene group having 1 to 10 carbon atoms, a linear or branched alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 12 carbon atoms, A substituted or unsubstituted cycloalkenylene group, a substituted or unsubstituted phenylene group, and an arylene group.

The binder resin (B) is a copolymer obtained by copolymerization reaction of the compound (B1) and at least one of the following compounds (B2) and (B3).

(B2): unsaturated carboxyl group-containing monomer

(B3): a compound having an unsaturated bond copolymerizable with (B1) and (B2)

The proportion of the structural unit derived from (B1) to the total number of the structural units of the binder resin (B) is preferably 20 to 90 mol%, more preferably 40 to 70 mol%. When the content of (B1) is less than 20 mol%, the effect of decreasing the outgassing amount is insufficient. When the content of (B1) is more than 90 mol%, the solubility in the developer is lowered, .

It is more preferable that the proportion of the constituent unit derived from the above-mentioned (B1) is more than 50 mol% relative to the total mol number of the constituent units of the binder resin (B).

When the binder resin (B) contains the above-mentioned (B2), the ratio of the constituent unit derived from (B2) to the total molar number of the constituent unit of the binder resin (B) is preferably from 0 to 70 mol% Do. When the above-mentioned (B3) is contained, the ratio of the structural unit derived from (B3) to the total number of moles of the structural units of the binder resin (B) is preferably from more than 0 to 70 mol%.

The binder resin (B) has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium for solids including colorants, and functions as a binder resin.

Examples of the unsaturated carboxyl group-containing monomer (B2) include an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid. have.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be mono (2-methacryloyloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

The carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the compound (B3) having an unsaturated bond capable of copolymerization with (B1) and (B2) include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, Styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentane Dienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as cyproxy acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like. These monomers may be used alone or in combination of two or more.

The binder resin (B) is directly polymerized or purchased so as to have a weight average molecular weight of 5,000 to 50,000. The binder resin (B) having a molecular weight distribution in the above range has a high hardness and is excellent in not only the high residual film ratio but also the solubility of the non-exposed portion in the developer, and the resolution can be improved.

The binder resin (B) may be used in an amount of 5 to 80% by weight, preferably 5 to 50% by weight based on the total weight of the black photosensitive resin composition. Such a content is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, So that the dropout of the non-pixel portion is improved.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) is not particularly limited, but may be a copolymer of a carboxyl group-containing unsaturated monomer, a copolymer of a carboxyl group-containing unsaturated monomer and a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof Or more can be used.

As the carboxyl group-containing unsaturated monomer, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids can be used. Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include fumaric acid, mesaconic acid, itaconic acid and citraconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Examples of the unsaturated polycarboxylic acid include mono (meth) acrylates, monomethyl maleic acid, 5-norbornene-2-one (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals such as omega -carboxylic polycaprolactone mono (Meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate, and the like. These unsaturated carboxyl group-containing compounds may be used singly or in combination of two or more thereof, and acrylic acid and methacrylic acid among them may be preferably used because of their excellent copolymerization reactivity and solubility in a developing solution.

As the monomer capable of copolymerizing with the carboxyl group-containing unsaturated monomer, an aromatic vinyl compound, an unsaturated carboxylate compound, an unsaturated aminoalkyl carboxylate compound, a vinyl cyanide compound, and an unsaturated oxetanecarboxylate compound can be used. One kind may be used singly or two or more kinds may be used in combination.

Specifically, examples of the copolymerizable monomer include aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinylcyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, Unsaturated oxetanecarboxylate compounds, and the like.

The photopolymerizable compound may be used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight based on the total weight of the black photosensitive resin composition. This content range is a range selected considering the strength and smoothness of the finally obtained pixel defining layer, etc. If the content is less than the above range, the strength and smoothness are insufficient. On the other hand, A problem that patterning is not easy due to high strength occurs, and therefore, it is suitably used within the above range.

Light curing Initiator (D)

Examples of the photopolymerization initiator (D) include photopolymerization initiators generally used in photosensitive resin compositions such as acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, anthracene, anthraquinone, Based compounds, etc. These may be used alone or in combination of two or more.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- Oligomers of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2- methyl [4- (1-methylvinyl) phenyl] propan- .

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, and the like.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2 - (p-methoxyphenyl) -4,6-bis -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis (trichloromethyl) (Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone. have.

Examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE-01 and OXE-02 manufactured by Ciba.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 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, a phenyl group in the 4,4', 5,5 'position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom.

Such a photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight based on the total weight of the black photosensitive resin composition. Such a content range takes into account the photopolymerization rate of the photopolymerizable compound and the physical properties of the resulting coating film. When the amount is less than the above range, the polymerization rate is low and the overall process time may become long. On the other hand, It may be deteriorated, and therefore, it is suitably used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination, the composition of the black photosensitive resin becomes more sensitive and productivity is improved, which is preferable. As the photopolymerization and opening adjuvant to be used, at least one compound selected from the group consisting of an amine compound and a carboxylic acid compound can be preferably used.

The photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

(F) Solvent

The solvent may be any solvent that can dissolve or disperse the above-mentioned composition and does not react with other components, and is not particularly limited. Preferably, an organic solvent having a boiling point of 100 to 200 in terms of coating property and dryness can be used.

Representative examples of usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene 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 dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; 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; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

The solvent may be contained in a balance such that the black photosensitive resin composition satisfies 100 wt%. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability).

(G) Additive

The black photosensitive resin composition of the present invention may further contain additives known in the art for various purposes. Examples of such an additive include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof for enhancing adhesion to a substrate. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyl Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used alone or in combination of two or more. Surfactants can be used to improve the coating properties. Examples include BM-1000, BM-1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., 190 / SZ-6032 (Doresilicon Co., Ltd.) can be used.

In addition,

An organic light emitting device including the pixel defining layer made of the black photosensitive resin composition, and a quantum dot light emitting device.

In addition,

And a display device including the organic light emitting device or the quantum dot light emitting device.

A typical patterning process for forming a pixel defining layer according to a photolithography method comprises the following steps:

a) applying a black photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking steps

The application may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 ° C, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner .

The post bake is performed to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 ° C for 10 to 120 minutes. Post-baking Pre-baking is carried out using an oven, hot plate or the like.

The pixel defining layer made of the black photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulating property and light shielding property, and is excellent in heat resistance and solvent resistance and can be used for an organic light emitting device, a quantum dot light emitting device, The reliability of a display device including an organic light emitting element or a quantum dot light emitting element can be improved.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Manufacturing example  1: Synthesis of Binder Resin A

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 177 (a) obtained by mixing 3,4-epoxy tricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9- , 23 parts of acrylic acid, 4 parts of t-butylperoxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (PGMEA) were added to prepare a stirrer. As a chain transfer agent, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Then 395 parts of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. The monomer and the chain transfer agent were then started to be added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG C after 1 hour, and maintained for 5 hours to obtain a resin having a solid acid value of 80 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 9,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Manufacturing example  2: Synthesis of Binder Resin B

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 20 of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate in a molar ratio of 50:50 , 30 parts of acrylic acid, 110 parts of cyclohexylmaleimide, 40 parts of 2-hydroxymethacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate and 40 parts of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared. As a chain transfer agent, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Then 395 parts of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. The monomer and the chain transfer agent were then started to be added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours each. After 1 hour, the temperature was elevated to 110 DEG C and maintained for 5 hours to obtain a resin having a solid acid value of 110 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 8,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Manufacturing example  3: Synthesis of binder resin C

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 20 of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate in a molar ratio of 50:50 , 30 parts of acrylic acid, 80 parts of cyclohexylmaleimide, 70 parts of 2-hydroxymethacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate and 40 parts of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared. As a chain transfer agent, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Then 395 parts of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. The monomer and the chain transfer agent were then started to be added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG C after 1 hour, and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 10,100 and the molecular weight distribution (Mw / Mn) was 2.2.

Manufacturing example  4: Synthesis of Binder Resin D

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 40 parts of propylene glycol monomethyl ether acetate and 140 parts of ropylene glycol monomethyl ether. The atmosphere in the flask was changed to nitrogen in air, , A solution prepared by adding 4 parts of azobisisobutyronitrile to a mixture containing 10 parts of benzylmaleimide, 60 parts of methyl methacrylate, 30 parts of methacrylic acid and 136 parts of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel The mixture was added dropwise to the flask over 2 hours, and stirring was further continued at 80 캜 for 4 hours. Subsequently, the inside of the flask was purged with nitrogen, air, 15 parts of glycidyl methacrylate, 0.5 part of trisdimethylaminomethylphenol and 0.1 part of hydroquinone were charged into the flask, and the reaction was continued at 110 DEG C for 6 hours. The solid acid value was 110 mg KOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000 and the molecular weight distribution (Mw / Mn) was 2.5.

Example  1 to 7 and Comparative Example  1 to 2: Preparation of Black Photosensitive Resin Composition

After adding a solvent to the mixer, a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and an additive were added and uniformly mixed by stirring to prepare a black photosensitive resin composition. The composition was as shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 The colorant (A) Carbon black 8.00 8.00 8.00 8.00 8.00 A-1 A-2 8.00 8.00 The binder resin (B) Resin A (Preparation Example 1) 7.24 3.62 3.62 7.24 2.10 Resin B (Production Example 2) 7.24 3.62 7.24 Resin C (Production Example 3) 7.24 3.62 Resin D (Preparation Example 4) 7.24 5.14 The photopolymerizable compound (C) Dipentaerythritol hexaacrylate
(Kayarad DPHA: Nippon Kayaku Co., Ltd.)) 3.12 3.12 3.12 3.12 3.12 3.12 3.12 3.12 3.12 Photopolymerization initiator (D) (O-acetyloxime) (Irgacure OXE-02, manufactured by Ciba) was added to a solution of 1- [9- ethyl-6- (2-methylbenzoyl) 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 Solvent (E) Propylene glycol monomethyl ether acetate 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 additive Pigment dispersant (polyester type) 1.33 1.33 1.33 1.33 1.33 1.33 1.33 1.33 1.33

(Unit: wt%)

week)

A-1: Black organic pigment (aniline black) 71% by weight + Black inorganic pigment (carbon black) 12% by weight + Blue pigment (Pigment Blue 60) 17%

A-2: Black organic pigment (aniline black) 75% by weight + Black inorganic pigment (carbon black) 10% by weight + Blue pigment (Pigment Blue 60) 15%

Test Example  1: Outgas characteristics evaluation

(1) Preparation of colored substrate

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated on the glass substrate such that the final film thickness was 2.0 탆, prebaked at 80 to 120 캜 and dried for 1 to 2 minutes to remove the solvent Respectively. Then, exposure was performed at an exposure dose of 40 to 100 mJ / cm ² to form a 1 cm x 3 cm pattern, and an unexposed area was removed using an aqueous alkaline solution. Subsequently, the substrate was baked at 220 캜 for 20 minutes to prepare a colored substrate.

(2) Outgassing evaluation

The outgassing was carried out by pyrolyzing the colored substrate prepared above at 230 DEG C for 30 minutes and analyzing the collected compound by Py-GC / MS. The results of the analysis are shown in Table 2 below.

Item Example 1 Example 2 Example
3 Example 4 Example 5 Example
6 Example
7 Comparative Example 1 Comparative Example 2 Outgas volume 7,805,
702 7,867,
164 8,282,
034 7,850,
039 8,095,
337 9,500,
387 9,638,
720 15,365,
555 12,930,
859

As can be seen from the above Table 2, in the case of the example pattern made of the black photosensitive composition of the present invention, the outgas generation amount is remarkably reduced as compared with the comparative example pattern.

Claims (10)

(A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent,
Wherein the binder resin (B) comprises a compound (B1) represented by the following formula (1) and a black photosensitive resin composition for forming a pixel defining layer of a quantum dot light emitting device:
[Chemical Formula 1]

In the above formula
R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group may be substituted with a hydroxyl group;
R 2 represents a C 1 -C 20 aliphatic or aromatic hydrocarbon containing a simple bond or a hetero atom. The method according to claim 1,
(A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of a binder resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.01 to 10% by weight of a photopolymerization initiator %, And (F) residual amount of a solvent. The method according to claim 1,
Wherein the binder resin (B) has a constituent unit ratio of the compound (B1) represented by the general formula (1) is 20 to 90 mol% based on the total mol number of the constituent units of the binder resin (B). The method according to claim 1,
Wherein the binder resin (B) has a weight average molecular weight of 5,000 to 50,000. Claim 3
Wherein the proportion of the constituent units of the compound (B1) represented by the formula (1) is more than 50 mol% based on the total mol number of the constituent units of the binder resin (B). The method according to claim 1,
The photopolymerization initiator (D) is at least one selected from the group consisting of acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, anthracene, anthraquinone, Based on the weight of the black photosensitive resin composition. An organic light emitting device comprising a pixel defining layer made of the black photosensitive resin composition according to any one of claims 1 to 6. A quantum dot light emitting device comprising a pixel defining layer made of the black photosensitive resin composition according to any one of claims 1 to 6. A display device comprising the organic light emitting device according to claim 7. A display device comprising the quantum dot light-emitting element according to claim 8.