TW201632989A - Device including light blocking layer and method of patterning the light blocking layer - Google Patents

Abstract

A device includes a substrate; a light blocking layer on the substrate; a passivation film covering the light blocking layer on the substrate; a thin film transistor on the passivation film; another passivation film covering the thin film transistor; color filter on another passivation film; and an insulation layer on the another passivation film and covering the color filter, wherein the light blocking layer is patterned using a composition including a heat resistance polymer, a cross-linking agent, a black colorant, and a solvent. A method of patterning the light blocking layer is also provided.

Description

Device comprising a light blocking layer and method of patterning the light blocking layer

This application claims the Korean Patent Application No. 10-2015-0031650 filed with the Korea Intellectual Property Office on March 6, 2015 and the 10-2015-0128444 filed with the Korea Intellectual Property Office on September 10, 2015. Priority and benefit of Korean Patent Application, the entire contents of which is hereby incorporated by reference.

The present disclosure is directed to a device comprising a light blocking layer and a method of patterning the light blocking layer.

The black photosensitive resin composition is necessary for producing a light blocking layer for a display device such as a color filter, a liquid crystal display material, an organic light emitting element (EL), a display panel material, or the like. For example, color filters (e.g., color liquid crystal displays, etc.) require a light blocking layer on the boundary in a colored layer (e.g., red, green, blue, etc.) to enhance display contrast or chromophore effects. This light blocking layer can be mainly formed of a black photosensitive resin composition. As a black pigment, carbon black is the most widely used, but it is also possible to use RGB mixed black, anthraquinone, cobalt oxide, indoleamine organic black, and the like.

On the other hand, the light blocking layer in the device such as a display device is patterned by an exposure and development process, but there is a problem that there is almost no uniform fine pattern and good and low heat resistance. Further, this conventional light blocking layer is formed only of a negative black photosensitive resin composition, and thus there is a problem of application to a narrow application range.

Accordingly, efforts have been made to develop novel methods of patterning light blocking layers to achieve fine patterns, and efforts have been made to develop devices including the light blocking layers.

An embodiment provides a device that includes a light blocking layer that is capable of implementing a fine pattern.

Another embodiment provides a method of patterning a light blocking layer.

An embodiment provides a device comprising: a substrate, a light blocking layer on the substrate, a passivation film overlying the light blocking layer on the substrate, a thin film transistor on the passivation film, another passivation film overlying the thin film transistor a color filter on the other passivation film and an insulating layer on the other passivation film and covering the color filter, wherein a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent are used. The composition is used to pattern the light blocking layer.

The heat resistant polymer may be a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, a siloxane. (siloxane-based) resin or a combination thereof.

The crosslinking agent may include at least one functional group represented by Chemical Formula 1. [Chemical Formula 1]

The crosslinking agent may further include at least one selected from the group consisting of Chemical Formula 2 to Chemical Formula 4. [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4]

In Chemical Formula 3 and Chemical Formula 4, R ² and R ^{3 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The composition may further comprise a base generator.

The base generator can be represented by Chemical Formula 5. [Chemical Formula 5]

In Chemical Formula 5, X is -CH ₂ - or -NH-, W is -O- or -S-, n is an integer of 0 or 1, and R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 An alkyl group, and L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The base generator can be represented by one of Chemical Formula 6 to Chemical Formula 9. [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

In Chemical Formula 6 to Chemical Formula 9, X is -CH ₂ - or -NH-, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ is a single bond or substituted or not Substituted C1 to C10 alkyl groups.

The base generator may include at least one selected from the group consisting of Chemical Formula 10 to Chemical Formula 22. [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22]

The black colorant may be carbon black, aniline black, perylene black, RGB black, cobalt oxide, titanium oxide or a combination thereof.

The composition may include 5 parts by weight to 40 parts by weight of the crosslinking agent, 10 parts by weight to 20 parts by weight of the black colorant, and 150 parts by weight to 4000 parts by weight of the solvent based on 100 parts by weight of the heat resistant polymer.

The alkali generating agent may be included in an amount of from 5 parts by weight to 40 parts by weight based on 100 parts by weight of the heat resistant polymer.

The composition may further comprise an additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, an anthrone-based surfactant, a radical polymerization initiator, or combination.

Another embodiment provides a method of patterning a light blocking layer comprising coating a composition comprising a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent on a substrate, applying a photoresist on the composition, and then The resultant is heated, exposed, and developed, the resultant is etched after development, the resultant is stripped with a stripping agent after the etching process, and the resultant is heated after the stripping process.

In the heating process after the stripping process, heating can be carried out at 200 ° C to 600 ° C.

Heating may be carried out at 70 ° C to 160 ° C in a heating process after the photoresist is applied to the composition.

The stripping agent may include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), γ-butyrolactone. (γ-butyrolactone; GBL), tetramethyl ammonium hydroxide (TMAH), potassium hydroxide (KOH), dimethylsulfoxide (DMSO), butyldiglycol (BDG) Monoethanolamine (MEA), N-methylpyrrolidone (NMP), hydroxy decanoic acid (HDA), catechol or a combination thereof.

The etch can be a wet etch.

The method may further include a bleaching process prior to the post-development etching process.

The method may further include a bleaching process prior to the stripping process after the etching process.

The heat resistant polymer may be a polybenzoxazole precursor, a polyimine precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, a decane-based resin, or a combination thereof.

The crosslinking agent may include at least one functional group represented by Chemical Formula 1.

The composition may further comprise a base generator.

The crosslinking agent and the base generating agent are the same as described above.

The black colorant may be carbon black, nigrosine, ruthenium black, RGB black, cobalt oxide, titanium oxide or a combination thereof.

The composition may include 5 parts by weight to 40 parts by weight of the crosslinking agent, 10 parts by weight to 20 parts by weight of the black colorant, and 150 parts by weight to 4000 parts by weight of the solvent based on 100 parts by weight of the heat resistant polymer.

The composition may further comprise an additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, an anthrone-based surfactant, a radical polymerization initiator, or combination.

Other embodiments of the invention are included in the following embodiments.

According to an embodiment, the device has a structure different from that of a device such as a conventional display device, and includes a light blocking layer formed by using a composition, wherein the composition includes a novel composition, and the light blocking layer is borrowed Patterned by a novel patterning process that achieves a uniform fine pattern, exhibits heat resistance, and can also be applied to both negative and positive compositions.

Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, and the disclosure is not limited thereto.

As used herein, when a specific definition is not otherwise provided, the term "alkyl" refers to C1 to C20 alkyl, the term "alkenyl" refers to C2 to C20 alkenyl, and the term "cycloalkenyl" refers to C3. To C20 cycloalkenyl, the term "heterocyclenyl" refers to C3 to C20 heterocycloalkenyl, the term "aryl" refers to C6 to C20 aryl, and the term "aralkyl" refers to C6 to C20 aralkyl. , the term "alkylene" refers to C1 to C20 alkyl, the term "extended aryl" refers to C6 to C20 extended aryl, and the term "alkyl aryl" refers to C6 to C20 alkyl aryl, The term "heteroaryl" refers to a C3 to C20 heteroaryl group, and the term "alkylene" refers to a C1 to C20 alkylene group.

As used herein, when a specific definition is not otherwise provided, the term "substituted" refers to substitution with a substituent selected from the group consisting of: replacing at least one hydrogen: a halogen atom (F, Cl, Br, I). , hydroxy, C1 to C20 alkoxy, nitro, cyano, amine, imido, azide, sulfhydryl, fluorenyl, fluorenylene, carbonyl, amine carbaryl, thiol, ester , an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 naphthenic group a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

As used herein, the term "hetero", when not specifically defined otherwise, refers to the inclusion of at least one heteroatom selected from the group consisting of N, O, S, and P in the formula.

As used herein, "(meth)acrylate" means both "acrylate" and "methacrylate" when not specifically defined otherwise, and "(meth)acrylic" means "Acrylic" and "methacrylic".

As used herein, the term "combination", when not specifically defined otherwise, refers to mixing or copolymerization.

As used herein, when a specific definition is not otherwise provided, "*" denotes a point at which the same or different atoms or chemical formulas are connected.

A device according to an embodiment comprises: a substrate, a light blocking layer on the substrate, a passivation film covering the light blocking layer on the substrate, a thin film transistor on the passivation film, another passivation film covering the thin film transistor, a color filter on the other passivation film and an insulating layer on the other passivation film and covering the color filter, wherein a composition including a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent is used To pattern the light blocking layer.

In general, a device such as a display device or the like includes a light blocking layer to prevent light leakage, and here, the light blocking layer is patterned by an exposure and development process. However, the patterning method rarely achieves a uniform fine pattern and brings low heat resistance and chemical resistance. Further, the light blocking layer can be formed by using only the negative type composition but hardly by using the positive type composition.

However, the device according to an embodiment includes a light blocking layer formed of a novel composition by a novel patterning process, which is capable of realizing a fine pattern and thus can use both negative and positive compositions and has excellent heat resistance With chemical resistance.

The device may be a display device such as a liquid crystal display, a light emitting diode, a plasma display, or an organic light emitting diode (OLED), but is not limited thereto.

2 is a schematic diagram showing the structure of a conventional device (for example, a display device or the like), and FIG. 3 is a schematic diagram showing the structure of a device (for example, a display device or the like) according to an embodiment.

As shown in FIG. 2 and FIG. 3, the conventional device 200 mostly includes a thin film transistor 240 on the top of the substrate 210 (or a passivation film 230 on the top of the substrate 210), a passivation film 250 covering the thin film transistor 240, and An insulating layer 270 on top of the passivation film 250, a light blocking layer 220 on the top of the insulating layer 270 and a color filter 260, and an upper substrate 280 on the top of the light blocking layer 220 and the color filter 260, but according to an implementation The device 100 of the example includes a light blocking layer 120 on the substrate 100 and a passivation film 130 covering the light blocking layer 120. Thus, the device 100 can achieve RGB light through the substrate 110 (eg, a lower glass side) and emit light through the substrate 110 (eg, a lower glass side), and thus minimize the space connecting the thin film transistor 140 to the PCB, thus Get a panel with a reduced bezel or narrow frame. Further, the device 100 according to an embodiment includes a passivation film 150 covering the thin film transistor 140, a color filter 160 on top of the passivation film 150, an insulating layer 170 covering the color filter 160, and a top portion of the insulating layer 170. Upper substrate 180.

On the other hand, the device according to an embodiment may further include ITO (not shown).

Hereinafter, each component in the composition for the light blocking layer in the patterning device according to an embodiment may be described in detail.

The composition for patterning the light blocking layer may include a heat resistant polymer, and the heat resistant polymer may include a polybenzoxazole precursor, a polyimide precursor, a novolac resin, a bisphenol A resin, and a bisphenol F resin, acrylate resin, decane-based resin or a combination thereof. For example, the heat resistant polymer can be a polybenzoxazole precursor, a polyimine precursor, or a combination thereof.

The polybenzoxazole precursor may include a structural unit represented by Chemical Formula 23, and the polyimine precursor may include a structural unit represented by Chemical Formula 24. [Chemical Formula 23]

In Chemical Formula 23, X ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, and Y ¹ is a substituted or unsubstituted C6 to C30 aromatic organic group, substituted or unsubstituted A divalent to hexavalent C1 to C30 aliphatic organic group or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group. [Chemical Formula 24]

In Chemical Formula 24, X ² is a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group or substituted or unsubstituted Substituted divalent to hexavalent C3 to C30 alicyclic organic groups, and Y ² is substituted or unsubstituted C6 to C30 aromatic organic groups, substituted or unsubstituted tetravalent to hexavalent a C1 to C30 aliphatic organic group or a substituted or unsubstituted tetravalent to hexavalent C3 to C30 alicyclic organic group.

In Chemical Formula 23, X ¹ is an aromatic organic group which may be a residue derived from an aromatic diamine.

An example of the aromatic diamine may be at least one selected from the group consisting of 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxyl Biphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)anthracene, bis(4-amino) 3-hydroxyphenyl)indole, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4- Amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-2-trifluoromethylbenzene Hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-6-three Fluoromethylphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-2-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyl -5-pentafluoroethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-amino-4-hydroxy-5-pentafluoro Ethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethyl Hexafluoropropane, 2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-6-trifluoromethylphenyl)hexafluoropropane , 2-(3-Amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-2-trifluoromethylphenyl)hexafluoropropane, 2-(3 -amino-4-hydroxy-2-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane and 2-(3-amino-4- Hydroxy-6-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane, but is not limited thereto.

An example of X ¹ may be a functional group represented by Chemical Formula 25 and Chemical Formula 26, but is not limited thereto. [Chemical Formula 25] [Chemical Formula 26]

In Chemical Formula 25 and Chemical Formula 26, A ¹ is a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, and R ⁴⁷ and R ^{48 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkane. a group, specifically a C1 to C30 fluoroalkyl group, each of R ⁵⁰ to R ⁵² independently being a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group Or a thiol group, and n10 is an integer of 0 to 2, and n11 and n12 are each independently an integer of 0 to 3.

In Chemical Formula 23, Y ¹ may be an aromatic organic group, a divalent to hexavalent aliphatic organic group or a divalent to hexavalent alicyclic organic group, which may be a residue of a dicarboxylic acid or a dicarboxylic acid. The residue of the acid derivative. Specifically, Y ¹ may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specific examples of the dicarboxylic acid derivative may be 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis(phenylcarbonylchloro)phosphonium (diphenyloxycarbonyl) Bis(phenylcarbonylchloride)sulfone), bis(phenylcarbonyl chloride)ether, bis(phenylcarbonylchloride)phenone, phthaloyldichloride, Terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylatedibenzotriazole or combinations thereof, but not Limited to this.

An example of Y ¹ may be a functional group represented by Chemical Formula 27 to Chemical Formula 29, but is not limited thereto. [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29]

In Chemical Formula 27 to Chemical Formula 29, R ⁵³ to R ^{56 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and n13 and n14 are each independently an integer of 0 to 4, and n15 and n16 are each independently The ground is an integer from 0 to 3, and A ² is a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , CO, CONH, S or SO ₂ , wherein R ⁴⁷ and R ^{48 are} independently a hydrogen atom or a substituted or unsubstituted Substituted C1 to C30 alkyl groups, specifically C1 to C30 fluoroalkyl groups.

In Chemical Formula 24, X ² may be an aromatic organic group, a divalent to hexavalent aliphatic organic group or a divalent to hexavalent alicyclic organic group. Specifically, X ² may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specifically, X ² may be a residue derived from an aromatic diamine, an alicyclic diamine or a silicon diamine. Herein, the aromatic diamine, the alicyclic diamine and the decylene diamine may be used singly or in combination of two or more.

Examples of the aromatic diamine may be, but not limited to, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1 , 5-naphthalenediamine, 2,6-naphthalenediamine, bis[4-(4-aminophenoxy)phenyl]anthracene, bis(3-aminophenoxyphenyl)anthracene, bis(4-amino Phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, including an aromatic ring substituted by an alkyl group or a halogen A compound or a combination thereof, but is not limited thereto.

An example of the alicyclic diamine may be 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine or a combination thereof, but is not limited thereto.

Examples of the quinone diamine may be bis(4-aminophenyl)dimethyl decane, bis(4-aminophenyl)tetramethyl decane, bis(p-aminophenyl)tetramethyldioxane, Bis(γ-aminopropyl)tetramethyldioxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(γ-aminopropyldimethylsilylbenzene) 4-aminobutyl)tetramethyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, 1,3-bis(aminopropyl)tetramethyldioxane (1, 3-bis(aminopropyl)tetramethyldisiloxane) or a combination thereof, but is not limited thereto.

In Chemical Formula 24, Y ² is an aromatic organic group, a tetravalent to hexavalent aliphatic organic group or a tetravalent to hexavalent alicyclic organic group. Specifically, Y ² may be an aromatic organic group or a tetravalent to hexavalent alicyclic organic group.

Y ² may be a residue derived from an aromatic acid dianhydride or an alicyclic acid dianhydride. Herein, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used singly or in combination of two or more.

An example of the aromatic acid dianhydride may be pyromellitic dianhydride; benzophenone tetracarboxylic dianhydride, such as benzophenone-3, 3', 4, 4' - benzophenone-3,3',4,4'-tetracarboxylic dianhydride; oxydiphthalic dianhydride, such as 4,4'-oxydiphthalic anhydride (4 , 4'-oxydiphthalic dianhydride); diphthalic dianhydride, such as 3,3',4,4'-biphthalic dianhydride (3,3',4,4'-biphthalic dianhydride); Hexafluoroisopropylidene diphthalic dianhydride, for example, 4,4'-(hexafluoroisopropyledene) diphthalic dianhydride; naphthalene-1,4, 5,8-tetracarboxylic dianhydride (naphthalene-1,4,5,8-tetracarboxylic dianhydride); 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10- Perylenetetracarboxylic dianhydride), etc., but is not limited thereto.

Examples of the alicyclic acid dianhydride may be 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1,2,3,4-cyclopentane). Tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexane-1,2-dicarboxylic anhydride (5-(2,5-dioxotetrahydrofuryl)-3-methyl -cyclohexane-1,2-dicarboxylic anhydride), 4-(2,5-dioxotetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2-dicarboxylic anhydride (4-(2,5-dioxotetrahydrofuran-3) -yl)-tetralin-1,2-dicarboxylic anhydride), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, bicyclooctyl And the like, but not limited thereto, such as bicyclooctene-1 (2,4,5-tetracarboxylic dianhydride).

The heat resistant polymer may have a weight average molecular weight (Mw) of from 3,000 g/mol to 300,000 g/mol, and specifically a weight average molecular weight of from 5,000 g/mol to 30,000 g/mol. When the weight average molecular weight (Mw) is within the range, a sufficient film residue ratio can be obtained in the non-exposed region during development with an alkaline aqueous solution, and patterning can be performed efficiently.

The composition for patterning the light blocking layer includes a crosslinking agent, and the crosslinking agent may be a vinyl ether crosslinking agent. For example, the crosslinking agent may include one or more functional groups represented by Chemical Formula 1. [Chemical Formula 1]

For example, in addition to the functional group represented by Chemical Formula 1, the crosslinking agent may further include at least one selected from the group consisting of Chemical Formula 2 to Chemical Formula 4. [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4]

In Chemical Formula 3 and Chemical Formula 4, R ² and R ^{3 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, the crosslinking agent can be represented by one of Chemical Formula A to Chemical Formula M. [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] [Chemical Formula D] [Chemical Formula E] [Chemical Formula F] [Chemical Formula G] [Chemical Formula H] [Chemical Formula I] [Chemical Formula J] [Chemical Formula K] [Chemical Formula L] [Chemical Formula M]

The crosslinking agent may be included in an amount of from 5 parts by weight to 40 parts by weight based on 100 parts by weight of the heat resistant polymer. Herein, the cross-linking agent can strengthen the film and thus bring resistance against the solvent and the developing solution, and improve the tapped angle or heat resistance after curing.

The composition for patterning the light blocking layer includes a black colorant, and the black colorant may include carbon black, aniline black, perylene black, RGB black, cobalt oxide, titanium oxide, or a combination thereof. For example, the black colorant can be carbon black.

A dispersant can be used with it to disperse the black colorant. Specifically, the black colorant may be pretreated with a dispersing agent on the surface or added together to prepare a composition.

The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant or the like. Specific examples of the dispersing agent may be a polyalkylene glycol and an ester thereof, a polyoxyalkylene group, a polyhydric alcohol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate, a sulfonate. The acid salt, the carboxylic acid ester, the carboxylate, the alkyl decylamine alkylene oxide addition product, the alkylamine, and the like, and these may be used singly or as a mixture of two or more.

Specifically, a black colorant may be used as a dispersion solution including a dispersant and a solvent described later, and the dispersion solution may include a solid black colorant, a dispersant, and a solvent.

The black colorant may be included in an amount of 10 parts by weight to 20 parts by weight based on 100 parts by weight of the heat resistant polymer, for example, 20 parts by weight to 150 parts by weight of the black colorant. When the black colorant is included in the range, an excellent coloring effect and development performance can be obtained.

The composition for patterning the light blocking layer may further include a base generating agent. Since the alkali generating agent is further included, the absorption of the etchant in the film can be promoted, and the patterning time can be adjusted due to the etchant.

For example, the base generator can be represented by Chemical Formula 5. [Chemical Formula 5]

In the above Chemical Formula 5, X is -CH ₂ - or -NH-, W is -O- or -S-, n is an integer of 0 or 1, and R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl, and L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

For example, the base generator can be represented by one of Chemical Formula 6 to Chemical Formula 9. [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

In Chemical Formula 6 to Chemical Formula 9, X is -CH ₂ - or -NH-, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ is a single bond or substituted or not Substituted C1 to C10 alkyl groups.

For example, the base generator may include at least one selected from Chemical Formula 10 to Chemical Formula 22, but is not limited thereto. [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22]

The alkali generating agent may be used in an amount of 5 parts by weight to 40 parts by weight, for example, 7 parts by weight to 30 parts by weight based on 100 parts by weight of the heat resistant polymer. When the alkali generating agent is included in the range, the pattern can be quickly formed to the bottom without lifting.

The composition for patterning the light blocking layer may include a solvent capable of easily dissolving each component (for example, a heat resistant polymer, a crosslinking agent, a black coloring agent, an alkali generating agent, etc.).

The solvent may be, but not limited to, an organic solvent, and specifically N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl hydrazine, digan Alcohol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl -1,3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethylpyruvate, methyl 3-methoxypropionate (methyl- 3-methoxy propionate) or a combination thereof.

The solvent can be appropriately selected in accordance with a process of forming a photosensitive resin film such as spin coating or slit die coating.

The solvent may be used in an amount of 150 parts by weight to 4000 parts by weight, for example, 200 parts by weight to 3,000 parts by weight based on 100 parts by weight of the heat resistant polymer. When a solvent is used within the range, the film may have a sufficient thickness and also has excellent solubility and coating characteristics.

The composition for patterning the light blocking layer may further include other additives.

For example, the composition for patterning the light blocking layer may include additives such as malonic acid, 3-amino-1,2-propanediol, a crosslinking agent containing a vinyl group or a (meth)acryloxy group. , leveling agent, fluorosurfactant, anthrone surfactant, surfactant, free radical polymerization initiator to prevent stains or spots during coating to adjust leveling, or to prevent undeveloped patterns the remains. The amount of additive can be controlled depending on the desired characteristics.

Further, the composition for patterning the light blocking layer may further include an epoxy compound as an additive to improve a close-contacting force or the like. The epoxy compound may comprise an epoxy novolac propylene carboxylate resin, an o-cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetramethylbiphenyl epoxy resin, a bisphenol A epoxy resin, an alicyclic epoxy resin or Its combination.

When the epoxy compound is further included, it may further include a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator.

The epoxy compound may be used in an amount of from 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the composition for patterning the light blocking layer. When an epoxy compound is used within the range, storage ability, close contact force, and other properties can be economically improved.

The composition for patterning the light blocking layer may further include a late thermal acid generator. Examples of latent thermal acid generators may be arylsulfonic acids such as p-toluenesulfonic acid or benzenesulfonic acid; perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid or trifluorobutanesulfonic acid; alkylsulfonic acids, for example Methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid; or a combination thereof, but is not limited thereto.

According to another embodiment, a method of patterning a light blocking layer includes: coating a composition including a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent on a substrate, coating a photoresist on the composition, and then The resultant is heated, exposed, and developed, the resultant is etched after development, the resultant is stripped with a stripping agent after the etching process, and the resultant is heated after the stripping process.

Unlike the conventional method of patterning the light blocking layer, the method of patterning the light blocking layer according to the embodiment can realize a fine pattern by an etching and stripping process after the exposure and development process.

In the heating process after the stripping process, heating may be carried out at 200 ° C to 600 ° C, for example 220 ° C to 450 ° C. Conventionally, the post-baking process can be carried out at a temperature ranging from 120 ° C to 240 ° C after the formation of the light blocking layer, but according to the embodiment, the post-baking process can maintain the temperature at 250 ° C to 600 ° C, for example 300 ° C to 450. In the range of °C, and thus after forming the light blocking layer, outgassing can be reduced and heat resistance can be improved at a high temperature during the TFT process.

In the heating process after the photoresist is applied to the composition, heating may be carried out at 70 ° C to 160 ° C, for example, at 80 ° C to 150 ° C.

For example, the photoresist can be novolac-based or naphthoquinone diazide-based. For example, the photoresist can be a chemically amplified photoresist.

For example, the etch can be a wet etch. Herein, the etching solution used during etching may be acidic.

For example, the stripping agent may include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), γ-butyrolactone (GBL), tetramethylammonium hydroxide. (TMAH), potassium hydroxide (KOH), dimethyl hydrazine (DMSO), butyl diglycol (BDG), monoethanolamine (MEA), N-methylpyrrolidone (NMP), hydroxydecanoic acid ( HDA), catechol or a combination thereof.

The method may further include a bleaching process prior to the post-development etching process. Alternatively, the method may further comprise a bleaching process prior to the stripping process after the etching process. Herein, the bleaching process promotes dissolution of the photoresist or causes the photosensitive material in the lower film to react.

The heat resistant polymer may be a polybenzoxazole precursor, a polyimine precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, a decane-based resin, or a combination thereof. The heat resistant polymer is the same as described above.

The crosslinking agent may include at least one functional group represented by Chemical Formula 1. The crosslinking agent is the same as described above.

The composition may further include a base generator. The base generator is the same as described above.

The black colorant may be carbon black, aniline black, perylene black, RGB black, cobalt oxide, titanium oxide or a combination thereof. The black colorant is the same as described above.

The composition may include 5 parts by weight to 40 parts by weight of the crosslinking agent, 10 parts by weight to 20 parts by weight of the black colorant, and 150 parts by weight to 4000 parts by weight of the solvent based on 100 parts by weight of the heat resistant polymer.

The composition may further comprise an additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, a decane-based resin, a radical polymerization initiator, or a combination thereof .

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are not to be construed as limiting the scope of the invention in any way. (Example) (Preparation of heat resistant polymer)

In a four-necked flask equipped with a stirrer, temperature controller, nitrogen syringe, and condenser, 12.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3 3-Fluorofluoropropane was dissolved in 125 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through it.

When the solid was completely dissolved, 4.2 g of pyridine as a catalyst was added thereto, and the temperature was maintained at 0 ° C to 5 ° C by dissolving 9.4 g of 4,4 '-oxybenzhydryl chloride in 100 g of NMP. The solution obtained in the solution was added dropwise to a four-necked flask for 30 minutes. When the addition was completed, the reaction mixture was reacted at 0 ° C to 5 ° C for 1 hour, and then the mixture was reacted at room temperature (15 ° C to 25 ° C) for 1 hour by raising the temperature.

Next, 1.1 g of 5-norbornene-2,3-dicarboxyl anhydride was added thereto, and the resulting mixture was stirred at 70 ° C for 24 hours to complete the reaction. The reaction mixture was added to a mixed solution of water/methanol = 10/1 (volume ratio) to produce a precipitate, and the precipitate was filtered, washed with water, and then dried at 80 ° C for 24 hours or more in a vacuum to obtain 24 hours. Polybenzoxazole precursor. Preparation Example 1 for Patterning a Light Barrier Layer

10 g of polybenzoxazole precursor was added to and mixed with 10 g of γ-butyrolactone (GBL), 140 g of propylene glycol monomethyl ether (PGME) and 40 g of ethyl lactate (EL). After dissolving, 8 g of carbon black and 2.5 g of a crosslinking agent represented by Chemical Formula B were added thereto and dissolved therein, and the solution was filtered by a 0.45 μm fluororesin filter to obtain a composition for patterning the light blocking layer. [Chemical Formula B] Example 2

A composition for patterning the light blocking layer was prepared in the same manner as in Example 1 except that 2.5 g of the alkali generating agent represented by Chemical Formula 10 and carbon black and the crosslinking agent in Example 1 were used. [Chemical Formula 10] Example 3

A composition for patterning the light blocking layer was prepared in the same manner as in Example 1 except that 2.5 g of the alkali generating agent represented by Chemical Formula 21 and carbon black and the crosslinking agent in Example 1 were used. [Chemical Formula 21] Comparative example 1

A composition for patterning the light blocking layer was prepared in the same manner as in Example 1 except that the crosslinking agent in Example 1 was not used. (Evaluation) Assessment 1 : Resistance to Chemical Resistance

Each composition for patterning the light blocking layer according to Examples 1 to 3 and Comparative Example 1 was used by using a K-rotator (manufactured by SEMES Co.) as a spin coater It was coated on an 8 Å wafer and heated on a hot plate at 140 ° C for 3 minutes to form a 1.5 μm thick light blocking layer. The thickness variation of the light blocking layer was examined by immersing the light blocking layer in PGMEA for 1 minute, and the results are provided in Table 1 below.

Reference for chemical resistance evaluation No thickness change: ○ Thickness change: × [Table 1]

As shown in Table 1, the composition for patterning the light blocking layer according to Examples 1 to 3 has excellent chemical resistance as compared with the composition for patterning the light blocking layer according to Comparative Example 1. And thus providing a light blocking layer capable of realizing a fine pattern. (Evaluation) Evaluation 2 : Pattern formation and taper angle in the light blocking layer

Each composition for patterning the light blocking layer according to Examples 1 to 3 and Comparative Example 1 was used by using a K-rotator (manufactured by SEMES Co.) as a spin coater It was coated on an 8 Å wafer and then heated on a hot plate at 160 ° C for 3 minutes to form a 1.5 μm thick light blocking layer. Next, the light blocking layer was applied by i-line PR (HKT-501), and the light blocking layer was heated on a hot plate at 100 ° C for 1 minute to form a photoresist layer having a thickness of 1.0 μm. Then, a fine pattern of 5 μm was realized by splitting energy with i10C (manufactured by Nikon Co.). The patterned wafer was exposed at 30 ° C and immersed in an Al etchant for 300 seconds (with bleaching; 1000 mL/cm ² ). The patterned (glass) substrate was cured at 350 ° C for 1 hour, and the taper angle was measured by using S-4300 (manufactured by Hitachi Co., Ltd.), and the results are shown in Table 2. . [Table 2]

As shown in Table 2, the composition for patterning the light blocking layer according to Examples 1 to 3 forms a pattern having a suitable taper angle as compared with the composition for patterning the light blocking layer according to Comparative Example 1. .

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not limited to the disclosed embodiments, but instead is intended to cover the scope of the appended claims. Various modifications and equivalent arrangements within the spirit and scope. Therefore, the above embodiments are to be considered as illustrative, but not limiting in any way.

100, 200‧‧‧ devices
110, 180, 210, 280‧‧‧ substrates
120, 220‧‧‧Light barrier
130, 150, 230, 250‧‧‧ passivation film
140, 240‧‧‧film transistor
160, 260‧‧‧ color filters
170, 270‧‧‧ insulation

1 is a flow chart showing a method of patterning a light blocking layer in accordance with an embodiment of the present invention. 2 is a schematic view showing the structure of a conventional display device. FIG. 3 is a schematic diagram showing the structure of a device according to an embodiment of the invention.

Claims (19)

An apparatus comprising a light blocking layer, comprising: a substrate; a light blocking layer on the substrate; a passivation film covering the light blocking layer on the substrate; a thin film transistor on the passivation film; a passivation film covering the thin film transistor; a color filter on the other passivation film; and an insulating layer on the other passivation film and covering the color filter; wherein the composition is used The light blocking layer is patterned to include a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent. A device comprising a light blocking layer according to claim 1, wherein the heat resistant polymer is a polybenzoxazole precursor, a polyimine precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, acrylate resin, decane-based resin or a combination thereof. A device comprising a light blocking layer according to claim 1, wherein the crosslinking agent comprises at least one functional group represented by Chemical Formula 1: [Chemical Formula 1] . A device comprising a light blocking layer according to claim 3, wherein the crosslinking agent further comprises at least one selected from the group consisting of Chemical Formula 2 to Chemical Formula 4: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] Wherein in Chemical Formula 3 and Chemical Formula 4, R ² and R ^{3 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. A device comprising a light blocking layer according to claim 1, wherein the composition further comprises a base generating agent. A device comprising a light blocking layer according to claim 5, wherein the alkali generating agent is represented by Chemical Formula 5: [Chemical Formula 5] Wherein in Chemical Formula 5, X is -CH ₂ - or -NH-, W is -O- or -S-, n is an integer of 0 or 1, and R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl, and L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group. A device comprising a light blocking layer according to claim 5, wherein the alkali generating agent is represented by one of Chemical Formula 6 to Chemical Formula 9: [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] Wherein in Chemical Formula 6 to Chemical Formula 9, X is -CH ₂ - or -NH-, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ is a single bond or substituted or not Substituted C1 to C10 alkyl groups. A device comprising a light blocking layer according to claim 5, wherein the alkali generating agent comprises at least one selected from the group consisting of Chemical Formula 10 to Chemical Formula 22: [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] [Chemical Formula 22] . A device comprising a light blocking layer according to claim 1, wherein the black colorant is carbon black, aniline black, perylene black, RGB black, cobalt oxide, titanium oxide or a combination thereof. A device comprising a light blocking layer according to claim 1, wherein the composition comprises: 5 parts by weight to 40 parts by weight of the crosslinking agent based on 100 parts by weight of the heat resistant polymer; Parts by weight to 20 parts by weight of the black colorant; 150 parts by weight to 4000 parts by weight of the solvent. A device comprising a light blocking layer according to claim 5, wherein the alkali generating agent is included in an amount of 5 parts by weight to 40 parts by weight based on 100 parts by weight of the heat resistant polymer. The device comprising a light blocking layer according to claim 1, wherein the composition further comprises an additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a leveling agent, and a fluorine compound. A surfactant, a decane-based resin, a radical polymerization initiator, or a combination thereof. A method of patterning a light blocking layer, comprising: coating a composition on a substrate, wherein the composition comprises a heat resistant polymer, a crosslinking agent, a black colorant, and a solvent; coating a photoresist on the composition, Then, heating and exposing the resultant; performing an etching process after development; performing a stripping process with a stripping agent after the etching process; and performing a heating process after the stripping process. The method of patterning a light-blocking layer according to claim 13, wherein the heating is performed at 200 ° C to 600 ° C in the heating process after the stripping process. The method of patterning a light blocking layer according to claim 13, wherein the heating is performed at 70 ° C to 160 ° C in the heating process after the photoresist is applied to the composition. . The method of patterning a light blocking layer according to claim 13, wherein the stripping agent comprises propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL). , γ-butyrolactone (GBL), tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH), dimethyl hydrazine (DMSO), butyl diglycol (BDG), monoethanolamine (MEA) N-methylpyrrolidone (NMP), hydroxydecanoic acid (HDA), catechol or a combination thereof. The method of patterning a light blocking layer according to claim 13, wherein the patterned light blocking layer is formed before the etching process after development or before the stripping process after the etching process The method further includes a bleaching process. The method of patterning a light-blocking layer according to claim 13, wherein the crosslinking agent comprises at least one functional group represented by Chemical Formula 1: [Chemical Formula 1] . The method of patterning a light blocking layer according to claim 13, wherein the composition further comprises a base generating agent.