KR102343709B1 - Composition for light shielding partition, light shielding partition using the same and display device including the light shielding partition - Google Patents

Abstract

(A) a cardo-based binder resin, (B) an acrylic photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light blocking agent, (E) a water repellent additive containing a fluorine atom (F) in the main chain, and (F) a solvent Provided are a light-shielding barrier rib composition comprising: a light-shielding barrier rib manufactured using the same, and a display device including the light-shielding barrier rib.

Description

Light-shielding barrier rib composition, light-shielding barrier rib and display device manufactured using the same

The present disclosure relates to a light-shielding barrier rib composition, a light-blocking barrier rib manufactured using the same, and a display device including the light-shielding barrier rib.

In order to realize high-resolution and high-brightness display elements, the panel structure is constantly being changed. Among these changes, there is a movement to improve devices by applying high-tech OLED and quantum dots to improve panel characteristics. In addition, to overcome the limitations of each technology and realize better characteristics, technology development to simultaneously apply OLED and quantum dots is being actively carried out.

In order to apply OLED and quantum dots at the same time, OLED should be used as a light source and color should be realized using quantum dots. bulkheads are needed Specifically, in order to prevent the quantum dot-containing ink from mixing with each other, the quantum dot-containing ink must be filled into the light-shielding barrier rib pattern. and the inside of the pattern constituting the barrier rib (the side wall of the barrier rib) should have hydrophilic (lyophilic) properties. That is, two properties should be implemented in one pattern. In the prior art, it was difficult to implement two properties (water repellency and hydrophilicity) that do not correspond to each other in one pattern. In addition, in the prior art, carbon black was used to increase the optical density of the light-shielding composition, but in this case, light was not irradiated to the lower end of the pattern during the exposure process, and the lower part of the film was not photocured. There was also the disadvantage of being severely induced and vulnerable to process margins. In the case of an inkjet barrier rib (light-shielding barrier) material, since the required film thickness is as high as 4 μm or more, after the exposure and development process, only the surface of the film is cured, the photocurability of the lower part is lowered, and the adhesive properties are also deteriorated. .

Therefore, research to develop a light-shielding barrier rib composition capable of solving the above problems and a light-shielding barrier rib using the same is continued.

One embodiment is to provide a barrier rib composition for blocking light that can prevent color mixing between inks during ink-jetting.

Another embodiment is to provide a light-shielding barrier rib manufactured using the light-shielding barrier rib composition.

Another embodiment is to provide a display device including the light blocking barrier rib.

In one embodiment, (A) a cardo-based binder resin, (B) an acrylic photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light blocking agent, (E) a water repellent additive comprising a fluorine atom (F) in the main chain, and ( F) Provided is a light-shielding barrier rib composition comprising a solvent.

The main chain of the water repellent additive may include a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

m and n are each independently an integer greater than or equal to 0, provided that 5 < m+n < 100.

The water repellent additive may include a (meth)acrylate group at the end.

The water repellent additive may have a weight average molecular weight of 5000 g/mol to 100000 g/mol.

The water repellent additive may be included in an amount of 0.1 wt% to 2 wt% based on the total amount of the light-shielding barrier rib composition.

The light blocking agent may include an inorganic black pigment or an organic black pigment.

The light blocking agent may include a mixture of three or more pigments selected from the group consisting of a red pigment, a blue pigment, a violet pigment, a green pigment, and an orange pigment.

The light blocking agent may include a mixture of a red pigment, a blue pigment, and a violet pigment, and the red pigment, the blue pigment and the violet pigment may be mixed in a weight ratio of 3 to 4: 2.5 to 3.5:1, respectively.

The barrier rib composition for light blocking may further include a diffusing agent.

The dispersing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

The light blocking barrier composition may further include malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, or a combination thereof.

Another embodiment provides a light-shielding barrier rib manufactured by using the light-shielding barrier rib composition.

The light blocking barrier rib may have a surface energy of 10 dyne/cm to 25 dyne/cm.

Another embodiment provides a display device including the light blocking barrier rib.

The display device may further include a light source and an overcoat layer, and quantum dots may be positioned between the light blocking barrier ribs.

The light source may be an organic light emitting diode (OLED).

The organic light emitting diode (OLED) may be a blue organic light emitting diode (OLED).

The specific details of other aspects of the invention are included in the detailed description below.

One embodiment may provide a light-shielding barrier rib composition capable of lowering the surface energy than the conventional light-shielding barrier rib composition, and the light-shielding barrier rib having a low surface energy manufactured by using the light-shielding barrier rib composition is a barrier between inks during inkjetting. It is possible to block color mixture in advance, and ultimately, it is possible to increase the luminous efficiency of the display device including the light-shielding barrier rib.

1 to 3 are schematic views each independently showing a display device according to an embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, , "heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" means a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, and "heteroarylene group" means a C3 to C20 hetero It means an arylene group, and "alkoxyylene group" means a C1 to C20 alkoxyylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof means substituted with a substituent.

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom among N, O, S and P is included in the formula.

In addition, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" is "acrylic acid" and "methacrylic acid" “It means that both are possible.

Unless otherwise defined herein, "combination" means mixing or copolymerization. Also, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymerization or random copolymerization.

Unless otherwise defined in the chemical formulas in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

As used herein, the cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 2-1 to 2-11 are included in the backbone of the resin.

Unless otherwise defined herein, "*" means the same or different atom (including a hydrogen atom) or a portion connected to a chemical formula.

The barrier rib composition for light blocking according to an embodiment includes (A) a cardo-based binder resin, (B) an acrylic photopolymerizable monomer, (C) a photopolymerization initiator, (D) a light blocking agent, (E) a water repellent additive, and (F) a solvent And, since the water repellent additive contains a fluorine atom (F) in the main chain, not the side chain, the light-shielding barrier rib manufactured using the light-shielding barrier rib composition according to an embodiment has a higher surface energy compared to the conventional light-shielding barrier rib. Since it is significantly lower, it is possible to improve the luminous efficiency of a display device including the same.

Specifically, the light-shielding barrier rib manufactured using the light-shielding barrier rib composition according to an embodiment serves to confine ink including quantum dots between two or more barrier ribs. That is, the ink containing quantum dots is injected between the two or more light-blocking barrier ribs through an inkjet process. At this time, when the ejected inks are mixed (color mixing), the luminous efficiency of the display device including the light-shielding barrier rib is lowered. Problems can arise. This is because, when the color mixing occurs, the quantum efficiency of the quantum dots in the ink may decrease. Therefore, it is important to lower the surface energy of the light-shielding barrier rib to well trap the quantum dot-containing ink so that color mixing does not occur. In addition, in order to increase the resolution, the light-shielding barrier rib requires a taper angle close to 90˚ and must have light-shielding properties. material must be included.

Hereinafter, each component will be described in detail.

(E) water repellent additive

The barrier rib composition for light blocking according to an exemplary embodiment includes a water repellent additive, wherein the water repellent additive includes a fluorine atom (F) in a main chain rather than a side chain. Conventionally, an acrylic resin in which a fluorine atom (F) or a silicon atom (Si) is substituted in a side chain other than the main chain was used as a water repellent additive. However, the conventional light-shielding barrier rib composition including the water-repellent additive has a problem in that it is difficult to maintain sufficient liquid-repellent properties after curing because the surface of the film is washed away during exposure and development processes.

However, according to one embodiment, by using a resin in which a fluorine atom (F) is substituted in the main chain, not the side chain, as the water repellent additive, the above-described problem can be solved.

For example, the main chain of the water repellent additive may include a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

m and n are each independently an integer greater than or equal to 0, provided that 5 < m+n < 100.

For example, the water repellent additive may include a (meth)acrylate group at the end. Since the water repellent additive includes a (meth)acrylate group at the end, it reacts with the cardo-based binder resin and the photopolymerizable monomer during the exposure process, thereby further improving the washout phenomenon by the developer.

For example, the water repellent additive may have 2 to 6 ends, and according to this, the water repellent additive may include 2 to 6 (meth)acrylate groups at the ends.

The water repellent additive may have a weight average molecular weight of 5000 g/mol to 100000 g/mol. When the water repellent additive has a weight average molecular weight within the above range, the surface uniformity characteristics after coating may be improved and liquid repellency characteristics may also be improved.

For example, the water repellent additive is 0.01 wt% to 2 wt%, such as 0.01 wt% to 1.9 wt%, such as 0.01 wt% to 1.8 wt%, such as 0.01 wt% to 1.7 wt%, based on the total amount of the light-shielding barrier rib composition 0.02% to 2% by weight, such as 0.02% to 1.9% by weight, such as 0.02% to 1.8% by weight, such as 0.02% to 1.7% by weight. When the water-repellent additive is included in the above content range, it may be easier to adjust only the upper surface of the barrier rib to have liquid repellency by lowering only the surface energy value of the surface of the light-shielding barrier rib, not the inside of the light-shielding barrier rib.

(A) Cardo-based binder resin

The cardo-based binder resin may be represented by the following formula (2).

[Formula 2]

In Formula 2,

R ⁵¹ and R ⁵² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁵⁵ R ⁵⁶ , SiR ⁵⁷ R ⁵⁸ (wherein R ⁵⁵ to R ⁵⁸ are each independently a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group) or Any one of the linking groups represented by the following Chemical Formulas 2-1 to 2-11,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

(In Formula 2-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.)

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

Z ² is an acid dianhydride residue,

n1 and n2 are each independently an integer of 0 to 4.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 1,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, a pattern can be formed without a residue when manufacturing the light-shielding barrier rib, and there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may include a functional group represented by the following Chemical Formula 3 at at least one of both ends.

[Formula 3]

In Formula 3,

Z ³ may be represented by the following Chemical Formulas 3-1 to 3-7.

[Formula 3-1]

(In Formula 3-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

(In Formula 3-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group, or C2 to C20 allylamine group.)

[Formula 3-6]

[Formula 3-7]

The cardo-based binder resin may include, for example, a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, phenol anhydride compounds such as rylenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

The cardo-based binder resin may be included in an amount of 10 wt% to 30 wt%, for example, 15 wt% to 25 wt%, based on the total amount of the light-shielding barrier rib composition. When the cardo-based binder resin is included within the above range, the sensitivity, developability, resolution, and patternability of the manufactured light-shielding barrier rib may be improved.

(B) acrylic photopolymerizable monomer

The acrylic photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

Since the acrylic photopolymerizable monomer has the ethylenically unsaturated double bond, it is possible to form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate , pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane tri ( and meth)acrylate, tris(meth)acryloyloxyethyl phosphate, and novolac epoxy (meth)acrylate.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth)acrylic acid, Toagosei Chemical Industry Co., Ltd. Aronix M-101 ^® , Aronix M-111 ^® , Aronix M-114 ^® and the like; Nippon Chemical Co., Ltd. KAYARAD TC-110S ^® , KAYARAD TC-120S ^®, etc.; ^{V-158 ®} of Osaka Yuki Chemical Industry Co., Ltd., V-2311 ^®, etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid, Toagosei Chemical Industry Co., Ltd. Aronix M-210 ^® , Aronix M-240 ^® , Aronix M-6200 ^® and the like; Nippon Chemical Co., Ltd. KAYARAD HDDA ^® , KAYARAD HX-220 ^® , KAYARAD R-604 ^®, etc.; Osaka Yuki Chemical Industry Co., Ltd. V-260 ^® , V-312 ^® , V-335 HP ^® etc. are mentioned. Examples of the trifunctional ester of (meth)acrylic acid, Toagosei Chemical Industry Co., Ltd. Aronix M-309 ^® , Aronix M-400 ^® , Aronix M-405 ^® , Aronix M-450 ^® , Aronix M-710 ^® , Aronix M-8030 ^® , Aronix M-8060 ^® etc.; Nippon Chemical Co., Ltd. KAYARAD TMPTA ^® , KAYARAD DPCA-20 ^® , KAYARAD-30 ^® , KAYARAD-60 ^® , KAYARAD-120 ^®, etc.; ^{V-295 ®} , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^{® of} Osaka Yuki Chemical Industry Co., Ltd. may be mentioned. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used after treatment with an acid anhydride in order to provide better developability.

The photopolymerizable monomer may be included in an amount of 5 wt% to 15 wt%, for example, 5 wt% to 10 wt%, based on the total amount of the light-shielding barrier rib composition. When the photopolymerizable monomer is included within the above range, curing occurs sufficiently during exposure in the pattern forming process to provide excellent reliability and excellent developability in an alkali developer.

(C) photoinitiator

As the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof may be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso A propyl thioxanthone etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine; 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho1-yl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloro and romethyl)-6-piperonyl-s-triazine and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

Examples of the oxime-based compound include O-acyloxime-based compound, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one; 1-(3-cyclopentyl-1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)propylideneaminooxy)ethanone, 2-(benzoyloxyimino)-3 -cyclopentyl-1-(4-(phenylthio)phenyl)propan-1-one and the like can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione -2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate etc. can be used.

For example, in the barrier rib composition for light blocking according to an embodiment, a mixture of two different oxime-based compounds may be used as the photopolymerization initiator. For example, the mixture may be a mixture in which two different oxime-based compounds are each mixed in a weight ratio of 1:1.

As the photopolymerization initiator, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, or a fluorene-based compound may be used in addition to the above compound.

The photopolymerization initiator may be included in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 5 wt%, based on the total amount of the light-shielding barrier rib composition. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and thus the manufactured light blocking barrier rib has excellent sensitivity.

(D) shading agent

In order to easily implement black by increasing light blocking properties, the light blocking agent is at least three selected from the group consisting of 'inorganic black pigment', 'organic black pigment', 'red pigment, blue pigment, violet pigment, green pigment and orange pigment. It may include a 'mixture of pigments' or 'a combination of these'.

In general, inorganic black pigments such as carbon black, titanium black, etc. are used as a single light-shielding agent to improve light-shielding properties. When only inorganic black pigments such as carbon black are used alone, the optical density is excellent, but electrical properties other than the optical density Since other properties may be deteriorated, in the case of the barrier rib composition for light blocking according to an embodiment, it may be preferable not to use the inorganic black pigment alone.

On the other hand, in order to solve the above problem in the case of using the inorganic black pigment as the sole shading agent, the organic black pigment can be used as the sole shading agent. may decrease slightly, but it is possible to prevent deterioration of other characteristics such as electrical characteristics while still having sufficient light blocking performance.

In addition, black pigments through color mixing such as RGB black also have a function as a light blocking agent, and are also used in some black compositions. And a mixture of three or more pigments selected from the group consisting of an orange pigment may be used as a light blocking agent. More specifically, the light-shielding agent includes a mixture of a red pigment, a blue pigment, and a violet pigment, and the red pigment, the blue pigment and the violet pigment may be mixed in a weight ratio of 3 to 4: 2.5 to 3.5: 1, respectively. . That is, when the red pigment is contained in an amount of 3 to 4 times the content of the violet pigment, and the blue pigment is contained in an amount of 2.5 to 3.5 times the content of the violet pigment, the content ratio is not as described above. It is possible to achieve heat resistance and optical properties while maintaining superior photosensitivity properties compared to other cases.

Meanwhile, the mixture of the red pigment, the blue pigment and the violet pigment may not contain an inorganic black pigment such as carbon black in addition to the red pigment, the blue pigment and the violet pigment. That is, when a mixture of a red pigment, a blue pigment and a violet pigment is used as the light-shielding agent, other inorganic black pigments may not be additionally used. When an inorganic black pigment such as carbon black is used together, only the lower portion of the film is not photocured during exposure, development, and curing processes, which may cause severe undercutting, which may be undesirable.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 179, C.I. Red pigment 89 etc. are mentioned. Examples of the violet pigment include C.I. Violet Pigment 1, C.I. Violet Pigment 19, C.I. Violet Pigment 23, C.I. Violet pigment 27, C.I. Violet Pigment 29, C.I. Violet Pigment 30, C.I. Violet pigment 32, C.I. Violet pigment 37, C.I. Violet Pigment 40, C.I. Violet pigment 42, C.I. Violet pigment 50 etc. are mentioned. Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue pigment 15, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I. and phthalocyanine pigments such as blue pigment 16 and the like. However, the types of the red pigment, the violet pigment and the blue pigment are not limited thereto.

The light blocking agent may be used alone or together with a dispersing agent to disperse each pigment constituting the light blocking agent. Specifically, the single or each pigment may be surface-treated in advance with a dispersant, or a dispersant may be added and used together with the pigment when preparing the composition.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, etc. may be used. Specific examples of the dispersant include polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylate , alkyl amides, alkylene oxides, and alkyl amines, and these may be used alone or in combination of two or more.

Examples of commercially available products of the dispersant include BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemicals; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc. from Zeneka; Or Ajinomoto's PB711, PB821, and the like.

The dispersant may be included in an amount of 0.1 wt% to 15 wt% based on the total amount of the light-shielding barrier rib composition. When the dispersing agent is included within the above range, the composition has excellent dispersibility and thus has excellent stability, developability, and patternability when manufacturing a light-shielding barrier rib.

The pigment may be used after pre-treatment using a water-soluble inorganic salt and a wetting agent. When the pigment is pre-treated and used, the average particle diameter of the pigment can be refined.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be performed at a temperature of 40° C. to 100° C., and the filtration and washing may be performed by filtration after washing the inorganic salt with water or the like.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed and the pigment can be easily pulverized, for example, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc. alkylene glycol monoalkyl ethers; and alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and these may be used alone or in combination of two or more.

The pigment that has undergone the kneading step may have an average particle diameter of 5 nm to 200 nm, for example 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, the stability in the pigment dispersion is excellent, and there is no fear of a decrease in the resolution of the pixel.

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent such as PGMEA, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The solid content of the pigment may be included in an amount of 15 wt% to 40 wt%, for example, 20 wt% to 30 wt%, based on the total amount of the pigment dispersion.

The light-shielding agent may be included in an amount of 10 wt% to 30 wt%, for example 15 wt% to 25 wt%, based on the total amount of the light-shielding barrier rib composition. When the light-shielding agent is included within the above range, the black realization effect and the developing performance are excellent.

(F) solvent

The solvent is a water-repellent additive containing a fluorine atom (F) in the main chain, a cardo-based binder resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, a light blocking agent, and a light diffusing agent to be described later. can be used

Examples of the solvent include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactic acid esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxy acetate alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, and 3-ethoxymethylpropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as 2-oxy-2-methylpropionate and 2-oxy-2-methylpropionate ethyl, 2-methoxy-2-methylpropionate, 2-ethoxy-2- monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionate alkyls such as ethyl methylpropionate; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutanoate; Ketonic acid esters such as ethyl pyruvate, and the like, and N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, and N,N-dimethylacetamide. , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid and high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, 3-methylbenzoic acid, 3-methoxybutyl acetate, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, preferably, in consideration of compatibility and reactivity, ketones such as cyclohexanone; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate, 3-methylbenzoic acid, 3-methoxybutyl acetate, etc. can be used.

The solvent may be included in a balance, for example, 40 wt% to 75 wt%, such as 45 wt% to 70 wt%, such as 50 wt% to 65 wt%, based on the total amount of the light-shielding barrier rib composition. When the solvent is included within the above range, since the light-shielding barrier rib composition has an appropriate viscosity, processability in manufacturing the barrier rib is excellent.

Diffuser (or Diffuser Dispersion)

The barrier rib composition for light blocking according to an embodiment may further include a diffusing agent.

For example, the diffusing agent may include barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), or a combination thereof.

The diffusing agent reflects light not absorbed by the quantum dots included in the aforementioned ink, and enables the quantum dots to absorb the reflected light again. That is, the diffusion agent increases the amount of light absorbed by the quantum dots, thereby increasing the luminous efficiency of the light-shielding barrier rib-containing display device manufactured using the light-shielding barrier rib composition.

The diffusing agent may have an average particle diameter (D ₅₀ ) of 150 nm to 250 nm, specifically 180 nm to 230 nm. When the average particle diameter of the diffusing agent is within the above range, a more excellent light diffusion effect may be obtained, and luminous efficiency of the display device may be increased.

The diffusing agent may be included in an amount of 0.1 wt% to 20 wt%, for example, 0.1 wt% to 5 wt%, based on the total amount of the light blocking barrier composition. When the diffusion agent is included in an amount of less than 0.1% by weight based on the total amount of the light-shielding barrier rib composition, it is difficult to expect an effect of improving luminous efficiency by using the diffusion agent, and when it is included in an amount exceeding 20% by weight, the pattern characteristics may be deteriorated. there is concern

other additives

Meanwhile, the light blocking barrier composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, or a combination thereof.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, and an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycan Cydoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

The silane-based coupling agent may be included in an amount of 0.01 to 10 parts by weight based on the total amount of the light-shielding barrier rib composition. When the silane-based coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the light-shielding barrier rib composition may further include a surfactant, such as a fluorine-based surfactant and/or a silicone-based surfactant, to improve coating properties and prevent defect formation, if necessary.

As the fluorine-based surfactant, BM-1000 ^® of BM Chemie, BM-1100 ^®, etc.; ^{Mechapack F 142D ®} , Mechapack F 172 ^® , Mechapack F 173 ^® , Mechapack F 183 ^® , Mechapack F 554 ^® and the like of Dai Nippon Inki Chemical Co., Ltd.; Prorad FC-135 ^® , Prorad FC-170C ^® , Prorad FC-430 ^® , Prorad FC-431 ^®, etc. from Sumitomo Re.M.; Asahi Grass Co., Ltd.'s Saffron S-112 ^® , Saffron S-113 ^® , Saffron S-131 ^® , Saffron S-141 ^® , Saffron S-145 ^®, etc.; Toray Silicon Co., Ltd.'s SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , SF-8428 ^®, etc. can be used.

As the silicone-based surfactant, BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, What is marketed under the name of BYK-325 etc. can be used.

The surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on the total amount of the light-shielding barrier rib composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wettability to IZO substrates or glass substrates is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the barrier rib composition for light blocking within a range that does not impair physical properties.

The barrier rib composition for light blocking according to an embodiment may be of a positive type or a negative type, but after exposure and development of the composition having light blocking properties, in order to more completely remove residues in the region where the pattern is exposed, the negative type is preferred. more preferably.

Another embodiment provides a barrier rib prepared by exposing, developing, and curing the above-described barrier rib composition for light blocking.

The manufacturing method of the barrier rib for light blocking is as follows.

(1) Application and coating film formation step

After applying the light-shielding barrier composition to a desired thickness using a method such as a spin or slit coating method, a roll coating method, a screen printing method, or an applicator method on a substrate such as a glass substrate or an ITO substrate that has been subjected to a predetermined pretreatment, 70 A coating film is formed by heating (pre-baking) at °C to 110 °C for 1 minute to 10 minutes to remove the solvent.

(2) exposure step

After interposing a mask to form a pattern required for the obtained coating film, exposure is performed by irradiating actinic rays of 200 nm to 500 nm. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used.

Although the exposure amount varies depending on the type of each component of the composition, the compounding amount and the dry film thickness, when a high-pressure mercury lamp is used, it is 500 mJ/cm ² (by a 365 nm sensor) or less.

(3) development step

By dissolving and removing unnecessary parts using an alkaline aqueous solution as a developer, only the exposed parts remain to form a pattern.

(4) post-processing step

There is a post-heating process for the image pattern obtained by development to obtain an excellent pattern in terms of heat resistance, adhesion, chemical resistance, and the like. For example, after development, an image pattern obtained by development may be placed in a convection oven at 250° C., followed by heating (post-baking) for 1 hour.

The light blocking barrier rib may have a surface energy of 10 dyne/cm to 25 dyne/cm, for example, a surface energy of 18 dyne/cm to 23 dyne/cm. Since the light-shielding barrier rib, specifically, the surface of the upper surface of the light-shielding barrier rib has a surface energy within the above range, it is possible to effectively prevent color mixing between inks due to excellent liquid repellency.

Another embodiment provides a display device including the light blocking barrier rib.

The display device may further include a light source and an overcoat layer, and quantum dots may be positioned between the light blocking barrier ribs.

The light source may be an organic light emitting diode, for example, a blue organic light emitting diode. The quantum dots positioned between the barrier ribs exist in the form of a composition, and the quantum dot-containing composition may be cured to constitute a quantum dot-containing layer. That is, a quantum dot-containing layer may be positioned between the barrier ribs. For example, in the display device, a quantum dot-containing layer may be present on an organic light emitting diode (light source), a light blocking barrier may be positioned on both sides of the quantum dot-containing layer, and an overcoat layer may be positioned between the light source and the quantum dot-containing layer. In addition, in the display device, a quantum dot-containing layer may be present on an organic light emitting diode (light source), light-shielding barrier ribs may be positioned on both sides of the quantum dot-containing layer, and an overcoat layer may be positioned on the quantum dot-containing layer. (See FIGS. 1 to 3)

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited by the following examples.

(Preparation of photosensitive resin composition)

With the composition shown in Table 1 below, light-shielding barrier rib compositions according to Examples 1 to 6 and Comparative Examples 1 to 4 were prepared. Specifically, the photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Here, a water repellent additive, a cardo-based binder resin, and an acrylic photopolymerizable monomer were added and stirred at room temperature for 2 hours. Then, after the light-shielding agent was added, the mixture was stirred at room temperature for 1 hour, and other additives (surfactants) were added and stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare a light-shielding barrier rib composition.

(Unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Cardo-based binder resin 18 18 18 18 18 18 15 18 18 18 (B) acrylic photopolymerizable monomer 8 8 8 8 8 8 7 8 8 8 (C) photoinitiator (C-1) 2 2 2 2 2 2 2 2 2 2 (C-2) 2 2 2 2 2 2 2 2 2 2 (D) shading agent 20 20 20 20 20 20 20 20 20 20 (E) water repellent additive (E-1) 0.3 - - 0.3 - - - - - - (E-2) - 0.6 - - 0.6 - - - - - (E-3) - - 1.8 - - 1.8 - 0.3 0.6 1.8 (F) solvent (F-1) 35 35 35 35 35 35 35 35 35 35 (F-2) 20 20 20 20 20 20 20 20 20 20 other additives 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

(A) Cardo-based binder resin

KBR-101 (Kyungin Corporation)

(B) acrylic photopolymerizable monomer

Dipentaerythritol hexa(meth)acrylate (DPHA, sartomer)

(C) photoinitiator

(C-1) PBG-304 (Tronly)

(C-2) PBG-305 (Tronly)

(D) shading agent

Organic black pigment (CIM-126) dispersion (SAKATA company; organic black pigment solid content 21% by weight)

(E) water repellent additive

(E-1) AD-1700 (solvay) (including a fluorine atom in the main chain)

(E-2) MD-700 (solvay) (including a fluorine atom in the main chain)

(E-3) F-570 (DIC Corporation) (contains a fluorine atom only in the side chain, not the main chain)

(F) solvent

(F-1) propylene glycol monomethyl ether acetate (PGMEA, Sigma-aldrich)

(F-2) 3-methoxybutyl acetate (3-MBA, Sigma-aldrich)

other additives

Surfactant (DIC, F-554 (10% dilution used))

(evaluation)

Surface energy evaluation

The light blocking barrier composition according to Examples 1 to 6 and Comparative Examples 1 to 4 was applied to 10 cm * 10 cm bare glass, heated on a hot plate at 100 ° C. for 1 minute in a proxy type, and contacted again for 1 minute Type was heated to form a coating film with a thickness of 10 μm. The substrate coated with the coating film was exposed using a mask engraved with patterns of various sizes with Ushio's UX-1200SM-AKS02 at varying exposure doses, and then developed with a 2.38% TMAH solution at room temperature to dissolve and remove the exposed parts. Then, wash with pure water for 50 seconds, drop DIW 1.0uL ~ 3.0uL and Ethylene Glycol (EG) 1.0uL ~ 3.0uL with a contact angle measuring instrument (KRUSS DSA100) to measure each contact angle, and then measure the contact angle of DIW/EG The surface energy was calculated by the KRUSS surface energy measurement method, and the results are shown in Table 2 below. (Contact angle measurement method: ASTM D 5946 / Surface energy calculation method: ASTM D 7490) In order for the light-shielding barrier rib surface to have liquid repellency, the surface energy value must be 28 dyne/cm or less.

(Unit: dyne/cm) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 surface energy 20 18 18 23 21 20 45 44 40 38

From Table 2, it can be seen that the surface energy of the light-shielding barrier rib (above) according to an embodiment is 28 dyne/cm or less, and more specifically, 23 dyne/cm or less, which is implemented as a bar, and has very excellent liquid repellency.

The present invention is not limited to the above embodiments, but can be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains can take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented as Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (15)

(A) cardo-based binder resin,
(B) an acrylic photopolymerizable monomer;
(C) a photoinitiator;
(D) a shading agent;
(E) a water repellent additive comprising a structural unit represented by the following formula (1) in the main chain, and
(F) solvent
including,
The water-repellent additive is included in an amount of 0.1 wt% to 2 wt% based on the total amount of the light-shielding barrier rib composition:
[Formula 1]

In Formula 1,
m and n are each independently an integer greater than or equal to 0, provided that 5 < m+n < 100.
delete According to claim 1,
The water repellent additive is a light blocking barrier composition comprising a (meth) acrylate group at the terminal.
According to claim 1,
The water repellent additive is a light-shielding barrier rib composition having a weight average molecular weight of 5000 g/mol to 100000 g/mol.
delete According to claim 1,
The light blocking agent is a light blocking barrier composition comprising an inorganic black pigment or an organic black pigment.
According to claim 1,
The light blocking agent is a light blocking barrier composition comprising a mixture of three or more pigments selected from the group consisting of a red pigment, a blue pigment, a violet pigment, a green pigment and an orange pigment.
8. The method of claim 7,
The light-shielding agent includes a mixture of a red pigment, a blue pigment and a violet pigment,
The red pigment, the blue pigment and the violet pigment are each mixed in a weight ratio of 3 to 4: 2.5 to 3.5: 1 for blocking light.
According to claim 1,
The light-shielding barrier rib composition further comprises a diffusing agent.
10. The method of claim 9,
The light-shielding barrier rib composition comprising the diffusing agent barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.
According to claim 1,
The light blocking barrier composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, or a combination thereof.
A light blocking barrier rib manufactured using the light blocking barrier rib composition of any one of claims 1, 3, 4, and 6 to 11.
13. The method of claim 12,
The light blocking barrier rib has a surface energy of 10 dyne/cm to 25 dyne/cm.
A display device comprising the barrier rib of claim 12 .
15. The method of claim 14,
The display device further includes a light source and an overcoat layer, wherein quantum dots are positioned between the light blocking barrier ribs.

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