KR20180094484A - Method of forming pattern for partition - Google Patents

Abstract

The present invention relates to a method of forming a pattern for partition of a display element where light emitting bodies per color are embedded in at least a part of a sub-pixel. The method comprises the following processes: (A) patterning a black resist on a transparent substrate; (B) forming a resist film by applying a positive resist composition having a thermosetting ability on the transparent substrate on which the black resist is patterned; (C) exposing the resist film from a side of the transparent substrate; and (D) developing a resist film after the exposure to form a resist pattern.

Description

[0001] METHOD OF FORMING PATTERN FOR PARTITION [

The present invention relates to a method of forming a pattern for a barrier rib of a display element in which a light emitting body for each color (color) is embedded in at least a part of subpixels.

The present application claims priority based on U.S. Provisional Application No. 62 / 459,066, filed on February 15, 2017, the United States of America, the contents of which are incorporated herein by reference.

A display element such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates facing each other. A color filter having pixels (pixels) of each color such as red (R), green (G), and blue (B) is formed on the inner side of one substrate. In the display device, a black matrix is formed so as to divide pixels (sub-pixels) of R, G, and B colors so as to emphasize the contrast of a normal image.

Generally, a color filter is formed by a lithography method. Specifically, first, a black photosensitive composition is coated on a substrate, exposed and developed to form a black matrix and a partition wall. After that, coating, exposure, and development are repeated for each of the R, G, and B color photosensitive compositions to form respective color patterns at predetermined positions to produce a color filter.

Patent Document 1 discloses a method of providing a light shielding wall between sub pixels of an organic EL display.

Japanese Patent Application Laid-Open No. 2004-335224

In the method described in Patent Document 1, since the light-shielding wall is disposed on the black matrix, there arises a problem in the alignment accuracy with the black matrix pattern.

In order to solve the problem of alignment accuracy with the black matrix pattern, the light-shielding wall itself may be configured to also serve as a black matrix. However, in the case of such a configuration, the transparency to ultraviolet rays also deteriorates as the light-shielding wall becomes higher. Therefore, there arises a problem that the lithography technique can not be applied at the time of forming the black matrix pattern.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and provides a method of forming a barrier rib pattern in which a barrier rib can be formed with good alignment accuracy with a black matrix pattern in a display element in which a color- .

According to one aspect of the present invention, there is provided a method of forming a pattern for a barrier rib of a display element in which color light emitting bodies are embedded in at least a part of subpixels, comprising the steps of: (A) patterning a black resist on a transparent substrate; (B) applying a resist composition to a surface of the transparent substrate on which the black resist is patterned to form a resist film; (C) exposing the resist film from the transparent substrate side; And a step (D) of forming a resist pattern.

According to the present invention, it is possible to provide a method of forming a barrier rib pattern capable of forming a barrier rib with good alignment accuracy with a black matrix pattern in a display element in which color luminescent materials are embedded in at least a part of subpixels.

1 is a schematic process diagram for explaining an embodiment of a pattern forming method for a barrier rib.

In the present specification and claims, the term " aliphatic " is defined as meaning a group, compound, or the like having no aromaticity as a relative concept to an aromatic.

The " alkyl group " is intended to include linear, branched and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The alkyl group in the alkoxy group is also the same.

The "alkylene group" is intended to include straight-chain, branched chain and cyclic divalent saturated hydrocarbon groups, unless otherwise specified.

The "halogenated alkyl group" is a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

"Constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

Includes the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH ₂ -) with a divalent group when describing "may have a substituent".

&Quot; Exposure " is a concept including the entire irradiation of radiation.

The term "(meth) acrylate" means either or both of acrylate and methacrylate.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, but can be appropriately modified within the scope of the object of the present invention.

[Method of forming pattern for barrier rib]

The method for forming a barrier rib pattern according to the present embodiment is a method for forming a barrier rib pattern of a display element in which a color light emitting body is embedded in at least a part of subpixels. The method includes the steps of: patterning a black resist on a transparent substrate; (B) applying a positive resist composition having curability to the transparent substrate on which the black resist is patterned to form a resist film; (C) exposing the resist film from the transparent substrate side; And a step (D) of developing the resist film to form a resist pattern.

Examples of the light emitting body for each color include those used for color filters of conventional display elements such as compound phosphors and quantum dot phosphors. Among them, a quantum dot fluorescent material is preferable as the color light emitting material from the viewpoint of increasing the purity of the fluorescent light emitting region of each color and the purity of red (R).

≪ Process (A) >

In the step (A), a black resist is patterned on the transparent substrate 1 (Figs. 1 (a) to (c)).

The method of patterning the black resist is not particularly limited, and conventionally known methods can be used. For example, the black resist is applied on a transparent substrate by using a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a curtain flow coater.

Then, the applied black resist is dried to form a coating film 2. The drying method is not particularly limited and includes, for example, (1) a method of drying on a hot plate at a temperature of 80 ° C to 120 ° C, preferably 90 ° C to 100 ° C for 60 seconds to 120 seconds, (2) (3) a method of removing the solvent by putting it for several hours in a warm air heater or an infrared heater for several hours may be used.

Then, the coating film 2 is irradiated with active energy rays such as ultraviolet rays and excimer laser beams through a mask to partially expose the coating film 2. The energy dose to be irradiated differs depending on the composition of the black resist, but is preferably, for example, about 30 mJ / cm ² to about 2000 mJ / cm ² .

Then, the exposed film is patterned into a desired shape by developing with a developing solution. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine; and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Then, post-baking is performed on the post-development pattern at about 200 to 250 占 폚.

Thus, the black resist can be patterned in a predetermined shape on the transparent substrate.

The thickness of the black resist pattern (black matrix 2a) patterned on the transparent substrate can be set within a range of usually 0.5 占 퐉 to 5 占 퐉, preferably 1 占 퐉 to 3 占 퐉, and more preferably 1 占 퐉 to 2 占 퐉.

Particularly, from the viewpoint of improving the resolution of the black matrix pattern, the thickness of the black matrix is preferably 3 m or less.

(Transparent substrate)

The transparent substrate is not particularly limited as long as it is a substrate having optical transparency, but a glass substrate is usually used.

(Black resist)

The black resist is not particularly limited and conventionally known ones can be used. For example, a photosensitive resin composition containing a black pigment and a resin component.

Examples of the black pigment include inorganic pigments such as metal oxides, complex oxides, metal sulfides, metal sulfates and metal carbonates such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, have. Among these black pigments, it is more preferable to use carbon black or titanium black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black, and lamp black can be used. Further, in order to improve the dispersibility into the black composition, resin-coated carbon black is more preferably used.

Examples of the resin component include polyimide resins such as epoxy resin, acrylic epoxy resin, acrylic resin, siloxane polymer resin, polyimide resin, silicon-containing polyimide resin, polyimide siloxane resin, and polymaleimide resin.

The black resist may be a positive photosensitive composition or a negative photosensitive composition.

When the black resist is a positive type, it is preferable that the black resist contains an alkali-soluble resin, a photosensitizer and a black pigment.

When the black resist is a negative-working photosensitive resin composition, the black resist preferably contains a photopolymerizable compound, a photopolymerization initiator, and a black pigment.

≪ Process (B) >

In the step (B), a positive resist composition having a thermosetting ability is applied on the transparent substrate on which the black resist is patterned to form a resist film 3 (Fig. 1 (d)).

For example, a positive resist composition having a thermosetting ability is applied by using a spinner, a spin coater, a roll coater, a spray coater, a slit coater or the like, followed by drying to form a resist film.

As the drying method, for example, a method of drying at a temperature of 80 to 120 DEG C for 120 to 500 seconds on a hot plate may be mentioned.

The thickness of the resist film 3 is not particularly limited, but it is preferably 6 탆 to 50 탆, more preferably 6 탆 to 20 탆, and still more preferably 6 탆 to 10 탆.

(Positive resist composition having thermosetting ability)

The positive resist composition having a thermosetting ability is not particularly limited, and examples thereof include a positive resist composition containing an alkali-soluble resin (A) and a photosensitizer (B).

[Alkali-soluble resin (A)]

As the alkali-soluble resin, any resin having an alkali-soluble group having solubility in alkali can be employed.

As the alkali-soluble resin (A) (hereinafter sometimes referred to as "copolymer (A)"), for example, an acrylic resin is suitably used.

As the acrylic resin, it is preferable to contain the constituent unit (A1) represented by the formula (a-1) or the alicyclic epoxy group-containing unit (A3).

[Constituent unit (A1)]

The structural unit (A1) is represented by the following general formula (a-1).

However,

···(a-1)

(A-1)

[In the above general formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ra ⁰¹ represents a hydrogen atom or an organic group having a hydroxyl group.]

In the general formula (a-1), R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As the alkyl group having 1 to 5 carbon atoms, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and specifically, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, , Pentyl group, isopentyl group, neopentyl group and the like.

In the general formula (a-1), Ra ⁰¹ is an organic group having a hydrogen atom or a hydroxyl group.

Here, the organic group may be, for example, a branched, straight, or cyclic alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an aralkyl group which may have a substituent, A heteroaryl group, and Ra ⁰¹ has at least one hydroxyl group in its structure. The number of carbon atoms of the organic group is preferably 1 to 20, more preferably 6 to 12. A larger number of carbon atoms is preferable from the standpoint of storage stability, and a smaller number of carbon atoms results in better resolution.

When Ra ⁰¹ is a hydrogen atom, that is, when methacrylic acid or acrylic acid is selected as the constituent unit (A1), it is effective in enhancing the alkali developability of the copolymer. However, from the viewpoint of storage stability, the constituent unit It is preferable to employ an organic group having a hydroxyl group as described above.

A preferred example of the structural unit (A1) is a structural unit represented by the following general formula (a-1-1).

[Figure 2]

···(a-1-1)

(A-1-1)

[Wherein in the general formula, R denotes a hydrogen atom or an alkyl group having a carbon number of 1 ~ 5, Ya ⁰¹ represents an alkylene group of a single bond or a carbon number of 1 ~ 5, Ra ⁰⁰¹ represents an alkyl group having a carbon number of 1 ~ 5, a is B represents 0 or an integer of 1 to 4, and a + b is 5 or less. When two or more Ra ⁰⁰¹ are present, these Ra ⁰⁰¹ may be the same or different.]

In the general formula (a-1-1), R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, as described above. In the general formula (a-1-1), R is preferably a methyl group.

Ya ⁰¹ represents a single bond or a straight or branched alkylene group of 1 to 5 carbon atoms. Specific examples include methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, tert-butylene, pentylene, isopentylene and neopentylene. Among them, a single bond, a methylene group, and an ethylene group are preferable.

Ya ⁰¹ is preferably a single bond because it can improve the alkali solubility and further improves heat resistance when used as an interlayer insulating film.

Here, a represents an integer of 1 to 5, but it is preferable that a is 1 in view of ease of production. Further, when the bonding position of the hydroxyl group is (1 position) relative to the carbon atom bonded with Ya ⁰¹ in the benzene ring, it is preferably bonded at the 4-position.

Ra ⁰⁰¹ is a straight or branched alkyl group having 1 to 5 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl. Of these, methyl group or ethyl group is preferable from the viewpoint of easiness of production.

Here, b represents 0 or an integer of 1 to 4, but it is preferable that b is 0 in view of easiness of production.

More specific examples of the structural unit (A1) include o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate, o-hydroxybenzyl (Meth) acrylate, m-hydroxybenzyl (meth) acrylate, p-hydroxybenzyl (meth) acrylate, o- hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate, and p-hydroxyphenyl (meth) acrylate are preferred, and p- ) Acrylate is preferable.

The content of the structural unit (A1) in the copolymer is preferably 10 to 70 mol%. Further, it is preferably 15 to 60 mol%, and most preferably 20 to 50 mol%.

[Alicyclic epoxy group-containing unit (A3)]

The alicyclic epoxy group-containing unit (A3) is not particularly limited as far as it is a structural unit derived from a compound having an alicyclic epoxy group in its structure and having an ethylenic double bond. The alicyclic group of the alicyclic epoxy group preferably has about 5 to 10 carbon atoms.

Specific examples of the alicyclic epoxy group-containing units (A3) include those derived from alicyclic epoxy group-containing polymerizable unsaturated compounds represented by the following general formulas (1) to (31).

[Figure 3]

[Figure 4]

Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁶ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ represent May be the same or different and w represents an integer of 0 to 10.

Among these, those represented by the general formulas (1) to (6), (14), (16), (18), (21), (23) to (25) and (30) are preferable. More preferred are the general formulas (1) to (6).

The content of the alicyclic epoxy group-containing unit (A3) in the copolymer is preferably 5 to 40 mol%. Further, it is preferably 10 to 30 mol%, and most preferably 15 to 25 mol%.

[Constituent unit (A2)]

It is preferable that the copolymer has the structural unit (A2) represented by the general formula (a-2).

[Figure 5]

···(a-2)

(A-2)

[R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Rb is a hydrocarbon group]

In the general formula (a-2), R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is the same as described above.

The hydrocarbon group of Rb includes, for example, a branched, straight-chain or cyclic alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20. The branched or straight chain alkyl group preferably has 1 to 12 carbon atoms, and most preferably 1 to 6 carbon atoms. The cyclic alkyl group preferably has 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms. The aralkyl group which may have a substituent or the aralkyl group which may have a substituent preferably has 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms.

Specific examples of the structural unit (A2) include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, Linear or branched alkyl acrylates; Alicyclic alkyl acrylates such as cyclohexyl acrylate, dicyclopentanyl acrylate, 2-methylcyclohexyl acrylate and isobornyl acrylate; Benzyl acrylate, aryl acrylate (e.g., phenyl acrylate), and the like.

Or a copolymer of two or more monomers selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, Straight chain or branched chain alkyl methacrylates such as acrylate, octyl methacrylate and the like; Alicyclic alkyl methacrylates such as cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl methacrylate and isobornyl methacrylate; Benzyl methacrylate, aryl methacrylate (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.) and the like.

By introducing the structural unit (A2) into the copolymer, the dissolution speed of the copolymer can be adjusted. As the constituent unit (A2), it is particularly preferable to be derived from a monomer having an alicyclic group.

The content of the constituent unit (A2) in the copolymer (A) is preferably 5 to 50 mol%.

[Structural unit (A4)]

The copolymer (A) may contain a structural unit (A4) other than the structural units (A1) to (A3) within limits not contradictory to the object of the present invention. This constituent unit is not particularly limited as long as it is a constituent unit derived from a compound having an ethylenic double bond. Examples of such a structural unit include structural units selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like.

Specific examples of the acrylamides include acrylamide and N-alkyl acrylamide (the number of carbon atoms of the alkyl group is preferably 1 to 10, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, a heptyl group, (For example, a phenyl group, a tolyl group, a nitrophenyl group, a naphthyl group, and a hydroxyphenyl group as the aryl group), N, N < RTI ID = 0.0 > (Alkyl group having 1 to 10 carbon atoms is preferable), N, N-aryl acrylamide (for example, phenyl group is an aryl group), N-methyl-N-phenylacrylamide, N-methylacrylamide, N-2-acetamidoethyl-N-acetyl acrylamide.

Specific examples of the methacrylamides include methacrylamide, N-alkylmethacrylamide (the alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, t-butyl, N, N-dialkylmethacrylamide (examples of the alkyl group include an ethyl group, a propyl group, a butyl group, and the like), an N-arylmethacrylamide (an aryl group includes a phenyl group and the like) , N, N-diarylmethacrylamide (examples of the aryl group include a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl- And phenylmethacrylamide.

Specific examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, , Allyloxyethanol, and the like.

Specific examples of the vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1- Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl Vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (e.g., vinylphenyl ether, vinyltolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinylnaphthyl ether, vinyl anthranyl Ether, etc.).

Specific examples of the vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Specific examples of the styrenes include styrene, alkylstyrenes (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, (E.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (e.g., methoxystyrene, (For example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Methylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.). Also, acrylonitrile, methacrylonitrile and the like can be mentioned.

In the present embodiment, the copolymer (A) is preferably composed of the structural units (A1), (A2) and (A3).

The mass average molecular weight (Mw: value measured by gel permeation chromatography (GPC) in terms of polystyrene conversion) of the copolymer (A) is preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. By setting the molecular weight to 2000 or more, it becomes possible to easily form a film. When the molecular weight is 50,000 or less, appropriate alkali solubility can be obtained.

The copolymer can be produced by a known radical polymerization. That is, it can be produced by dissolving a polymerizable monomer which induces the above-mentioned constituent units (A1) to (A3) and the like, and a known radical polymerization initiator in a polymerization solvent, followed by heating and stirring.

The alkali-soluble resin (A) may contain at least one other copolymer in addition to the copolymer containing the constituent units (A1) to (A3). The copolymer is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A). The mass average molecular weight (Mw: value measured by gel permeation chromatography (GPC) in terms of polystyrene conversion) of this copolymer is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000.

[Photosensitive Agent (B)]

The photosensitizer (B) in the present embodiment is not particularly limited as long as it is a compound that can be used as a photosensitive component, and a quinone diazide group-containing compound is a preferable example.

Specific examples of the quinone diazide group-containing compound include a phenol compound (also referred to as a phenolic hydroxyl group-containing compound) and a complete esterified product or partial esterified product of a naphthoquinone diazidesulfonic acid compound.

Specific examples of the phenol compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4- hydroxyphenylmethane, bis (4-hydroxy- Dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis Dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl- Hydroxyphenylmethane, bis (5-cis Hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxyphenyl) Methylphenyl) -3,4-dihydroxyphenylmethane, 4,4 '- [(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexyl- ) And the like;

Bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, and the like. Linear type 3-core phenol compounds; Bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5- 4-hydroxyphenyl] methane, bis [3- (3,5-dimethylphenyl) methane, bis [ Methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxybenzyl] Methylbenzyl) methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxyphenyl] Hydroxyphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-3- Methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy- 3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane; Bis [4-hydroxy-3- (4-hydroxyphenyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4- Methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4- Linear type pentene compounds such as linear phenolic compounds such as methylphenol;

Bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- ( (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) propane, 2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) propane, 2- Hydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) -2- (4'- Bisphenol-type compounds such as propane; 1- [1- (3-methylphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] ) Isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; And condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane. These may be used alone or in combination of two or more.

Examples of the naphthoquinone diazidesulfonic acid compound include naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid.

Other nucleoside derivatives such as orthobenzoquinone diazide, orthonaphthoquinone diazide, orthoanthraquinone diazide, and orthonaphthoquinone diazide sulfonate esters, which are other quinonediazide group-containing compounds, have. A compound having a hydroxyl group or an amino group (for example, a phenol, a p-methoxyphenol, a dimethylphenol, a hydroquinone, a bisphenol A, a naphthol, a pyrocatechol, a pyrogallol, a pyrogallol monomethyl Ether, pyrogallol-1, 3-dimethyl ether, gallic acid, esterified or etherified gallic acid, aniline, p-aminodiphenylamine, etc., with some hydroxyl groups remaining). These may be used alone or in combination of two or more.

These quinonediazide group-containing compounds can be obtained, for example, by reacting a trisphenol-type compound with naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide 4-sulfonyl chloride In the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogen carbonate or the like in a suitable solvent such as tetrahydrofuran, dioxane, and the like, to complete esterification or partial esterification.

As the component (B), it is preferable to use a quinonediazide group-containing compound of the non-benzophenone type, and it is preferable to use a polynuclear branched compound. It is also preferable that the phenolic hydroxyl group-containing compound has a gram extinction coefficient of 1 or less at a wavelength of 350 nm. As a result, a higher sensitivity can be obtained in the photosensitive resin composition.

As the component (B), a quinone diazide group-containing compound is preferable, and a naphthoquinone diazide sulfonic acid ester compound is particularly preferable. Among them, 4,4 '- [(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol) And naphthoquinonediazidesulfonic acid ester such as 4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene can be suitably used.

The content of the component (B) is preferably from 10 to 40 mass%, more preferably from 15 to 30 mass%, based on the total solid component. When the content of the component (B) is 10 mass% or more, it is possible to improve the resolution. In addition, it is possible to reduce the film reduction amount of the pattern after forming the pattern. When the content of the component (B) is 40 mass% or less, appropriate sensitivity or transmittance can be imparted.

[Organic solvent (S)]

The positive resist composition according to the present embodiment preferably contains an organic solvent (S) in order to improve the applicability or adjust the viscosity.

Examples of the component (S) include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol (MA), 3-methoxybutanol (BM), 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether pro Propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate or the like There may be mentioned compounds and the like. Among them, it is preferable to use PGME, PGMEA, MA, a mixed solvent of PGME and PGMEA, a mixed solvent of MA and BM, and the like.

The amount of the organic solvent (S) to be used is not particularly limited, but is appropriately set in accordance with the coating film thickness at a concentration applicable to a substrate or the like. Specifically, it is preferable that the solid content concentration of the photosensitive resin composition is in the range of 10 to 50 mass%, particularly 15 to 35 mass%.

[Optional ingredients]

(Black pigment)

In the present embodiment, the positive resist composition may contain a black pigment in order to enhance the light absorption of the partition wall.

The black pigment may be the same as the black pigment in the black resist.

When a black pigment is used, the content of the black pigment is preferably 1% to 10% with respect to the nonvolatile component.

By making the content of the black pigment fall within the above range, the light absorption of the partition wall can be sufficiently enhanced.

(Yellow pigment)

In the present embodiment, the positive resist composition may contain a yellow pigment in order to prevent deterioration of color purity due to incorporation into subpixels in addition to blue (B).

As the yellow pigment, C.I. 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185, .

When a yellow pigment is used, the content of the yellow pigment is preferably 1% to 10% with respect to the nonvolatile component.

By making the content of the yellow pigment fall within the above range, it is possible to sufficiently prevent the deterioration of the color purity due to incorporation into the sub pixels in addition to the blue (B) color.

(Inorganic particles)

In the present embodiment, the positive resist composition may contain inorganic particles in order to impart light scattering property to the partition wall.

As the inorganic particles, for example, glass, ceramics (cordierite, etc.), metals and the like can be used. Specifically, the PbO-SiO _{2 based, PbO-B 2 O 3 -SiO} 2 type, ZnO-SiO _{2 type, ZnO-B 2 O 3 -SiO} 2 based, BiO-SiO ₂ based, BiO-B ₂ O ₃ - Glass powders such as SiO ₂ -based lead borosilicate glass, zinc borosilicate glass and bismuth borosilicate glass; glass powders such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, Zn, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ SiO ₅ : Ce, etc., oxides of Na, K, Mg, Ca, Ba, Ti, Zr and Al, _{CaWO 4: Pb, BaMgAl 14 O} 23: Eu, ZnS: (Ag, Cd), Y 2 O 3: Eu, Y 2 SiO 5: Eu, Y 3 A 15 O 12: Eu, YBO 3: Eu, (Y , Gd) BO ₃ : Eu, GdBO ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₃ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn SrBiO ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO: Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ C ₁₄ : Eu, ZnS: (Cu, Phosphor powders such as Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO ₃ : Eu and BaMgAl ₁₂ O ₂₃ : Eu, iron, nickel, palladium, tungsten, And metal powders such as iron, aluminum, silver, gold, and platinum.

Among them, silica and titanium dioxide (TiO ₂ ) are preferable.

The average particle size of the inorganic particles is preferably from 0.1 to 1 mu m, more preferably from 0.2 to 0.5 mu m. When the average particle diameter of the inorganic particles is within the above range, sufficient light scattering property can be imparted to the partition wall.

When the inorganic particles are used, the content of the inorganic particles is preferably 2 to 20%, more preferably 5 to 10%, based on 100 parts by mass of the alkali-soluble resin (A).

When the content of the inorganic particles is within the above range, sufficient light scattering properties can be imparted to the partition wall while maintaining the lithography performance.

[Urethane oligomer (U)]

In the present embodiment, the positive resist composition may contain a urethane oligomer (U) having two or more polymerizable functional groups.

As the urethane oligomer (U), a (meth) acrylate compound having a urethane bond is preferable, and a urethane (meth) acrylate having a functional group number of 3 or more is more preferable.

The urethane (meth) acrylate having a functional group number of 3 or more refers to a compound having a urethane bond (-NH-CO-O-) and three or more (meth) acryloyloxy groups in the molecule. The number of functional groups of the urethane (meth) acrylate is preferably 3 or more, more preferably 3 to 10, still more preferably 3 to 5, particularly preferably 3 or 4, and most preferably 3 (that is, 3 (urethane (meth) acrylate).

When the urethane oligomer (U) is used, the content of the urethane oligomer (U) is preferably 5% by mass or more, more preferably 10 to 60% by mass, and still more preferably 10% Is 20 to 50% by mass.

[Component (F)] [

In the present embodiment, in order to impart water repellency to the resist film, the positive resist composition may contain a fluorine additive (hereinafter referred to as "component (F)").

When the resist film has water repellency, it is possible to prevent the ink jet from being mixed into other subpixels in the case of forming a color filter by an inkjet method.

Examples of the component (F) include those described in Japanese Patent Application Laid-Open Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 Fluorinated polymer compounds may be used.

In addition to the positive resist composition of the present embodiment, various components such as a reaction promoter, a silane coupling agent, a surfactant, a thermal acid generator, a crosslinking agent, a sensitizer, and a defoaming agent may be mentioned as optional components.

≪ Process (C) >

In the step (C), the resist film 3 is exposed from the transparent substrate 1 side (Fig. 1 (e)). The black matrix 2a functions as a mask to expose only the region where the black matrix 2a is not formed between the resist film 3 and the transparent substrate 1, The alkali soluble region 3a can be formed.

The exposure is carried out, for example, by irradiating the resist film 3 with active energy rays such as ultraviolet rays and excimer laser beams from the transparent substrate 1 side.

Examples of the light source of the active energy beam include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, an excimer laser generator, a UV laser such as triple YAG and doubled wave of semiconductor laser.

The energy dose to be irradiated differs depending on the composition of the positive resist composition, but may be, for example, 30 to 2000 mJ / cm ² .

≪ Process (D) >

In step (D), the exposed resist film 3 is developed to form a resist pattern. By the development, the alkali soluble region 3a is removed, and the resist pattern 3b (the partition wall pattern 3b) is formed on the black matrix 2a.

Examples of the developing solution used for the alkali development include an aqueous solution of an organic alkali such as an aqueous solution of tetramethylammonium hydroxide (TMAH), or an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium metasilicate and sodium phosphate.

<Optional Process>

&Lt; Process (E) &gt;

The method for forming a barrier rib pattern according to the present embodiment may further include a step (E) of thermally curing the resist pattern 3b.

The heating of the resist pattern is carried out at a temperature of, for example, 300 ° C or less, preferably 90 to 250 ° C. In the present embodiment, it is possible to easily cure at a lower temperature condition, and can be easily cured at 220 DEG C or lower.

From the viewpoint of maintaining the perpendicularity of the resist pattern, it is preferable that the thermal curing of the step (E) is performed in two or more stages. In the case of conducting two or more steps of heat curing, it is preferable to increase the heat curing temperature every step. For example, after heating at 90 to 150 ° C for 20 to 40 minutes, heating at 180 to 300 ° C may be performed for 50 to 70 minutes.

&Lt; Process (C1) &gt;

The method for forming a pattern for a barrier rib according to the present embodiment may include a step (C1) of performing a heat treatment (post-exposure heat treatment) between the step (C) and the step (D), if necessary.

In the present embodiment, a positive resist composition having a thermosetting ability is applied on a black matrix pattern and exposed from the transparent substrate side. Therefore, the black matrix pattern functions as a mask, and a resist pattern (partition wall) can be formed with good alignment accuracy with the black matrix pattern.

The method of forming a barrier rib pattern according to the present embodiment is particularly useful because it forms a barrier rib pattern of a display element in which a quantum dot phosphor is embedded.

When a quantum dot fluorescent material is used, dissolution resistance to an organic liquid is required. In the present embodiment, since a positive resist composition having a thermosetting ability is used, the formed barrier rib pattern is excellent in dissolution resistance to an organic liquid.

According to the present embodiment, it is possible to form a barrier rib pattern having a shape highly perpendicular to the transparent substrate.

[ Example ]

Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)

<Adjustment of Resist>

40 parts by weight of 4-hydroxyphenyl methacrylate, 40 parts by weight of methyl methacrylate, and 20 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate were mixed and polymerized in an organic solvent (PGMEA) Polymer A was obtained.

To 75 parts by weight of the solid content of the polymer solution obtained above was added naphthoquinonediazide-5 (4,4 '- [(3,4-dihydroxyphenyl) methylene] bis (Esterification ratio: 80%) and PGMEA and PGME were added to 200 parts by mass of PGMEA / PGME as a solvent at a ratio of PGMEA / PGME = 60/40.

&Lt; Formation of pattern &

A black resist (product name: CFPR BK-461; manufactured by Tokyo Ohka Kogyo Co., Ltd.) was coated on a glass substrate to a film thickness of 2.0 m by spin coating and baked at 100 캜 for 2 minutes. The substrate was exposed to light through a photomask at a light amount of 150 mJ / cm ^{2 using} an ultra-high pressure mercury lamp, developed with 0.04% KOH aqueous solution, washed and thermally cured to obtain a substrate having a light shielding layer (black matrix pattern) . Coating a resist on one side A to form a light shielding layer to a thickness 10μm by spin coating, followed by irradiation 1000 mJ / cm ² ultraviolet radiation is obtained from a high pressure mercury lamp from the substrate side. Thereafter, development was carried out in a 2.38% aqueous solution of TMAH twice for 1 minute, and (3) 200 ° C. and 60 minutes of (3) heating at 100 ° C. for 30 minutes, It was baked. As a result, the resist A had a high perpendicularity and was resolved to a pattern dimension of 5 mu m. In addition, the resist pattern had a good alignment accuracy with the black matrix pattern.

The patterned substrate was immersed in PGMEA for 1 minute, but no change in resist shape was observed.

(Example 2)

<Adjustment of Resist>

100 parts by weight of the non-volatile component of the resist A, 100 parts by weight of the silica particles (particle diameter of 300 nm), and 100 parts by weight of PGME were mixed with the resist A prepared in Example 1, followed by stirring with a planetary mixer to obtain a resist B.

&Lt; Formation of pattern &

Resist B was coated on a substrate having black resist patterned in the same manner as in Example 1, and exposure, development, and thermal curing were performed at 700 mJ / cm ² . As a result, the resist B was resolved to a minimum dimension of 8 탆. In addition, the resist pattern had a good alignment accuracy with the black matrix pattern.

(Comparative Example 1)

A positive resist (product name: PMER P-7130, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied by spin coating to a substrate having a black resist pattern formed thereon in the same manner as in Example 1, and ultraviolet rays obtained from a high- To 300 mJ / cm &lt; ² &gt; for development, and development was carried out in a TMAH 2.38% aqueous solution. The patterned substrate was immersed in PGMEA for 1 minute, and the resist completely peeled off.

(Comparative Example 2)

A high density product (solid content concentration of 35%) of a positive type resist (product name: PMER P-7130; manufactured by Tokyo Oka Kogyo Co., Ltd.) was applied by a spin coat to a substrate having a black resist pattern as in Example 1, The ultraviolet rays obtained from the high-pressure mercury lamp were irradiated from the substrate surface side at 1000 mJ / cm ² , and development was carried out in a TMAH 2.38% aqueous solution. Then, as a thermal cure, (1) baking was carried out at 100 ° C for 30 minutes, (2) at 120 ° C for 30 minutes, and (3) at 200 ° C for 60 minutes. As a result, the resist shape became a lens shape having a strong taper angle from the substrate interface.

The patterned substrate was immersed in PGMEA for 1 minute, and it was confirmed that the resist film thickness was reduced.

(Comparative Example 3)

The resist B prepared in Example 2 was applied to a substrate on which a black resist was patterned in the same manner as in Example 1. The resist B was exposed at 700 mJ / cm ² from the side of the resist B surface (the side opposite to the substrate surface) through a mask patterned with a black resist, and developed in a TMAH 2.38% aqueous solution for 1 minute. Thereafter, as in Example 1, development and thermal curing were performed. As a result, the pattern of the maximum size of 100 mu m in the mask was not resolved.

When the resist B is exposed, alignment of the black resist pattern and the mask is attempted. However, since the resist B is strong white, it is difficult to align the black resist pattern with the mask.

Claims (7)

A method of forming a pattern for a barrier of a display element in which a color light emitting body is embedded in at least a part of subpixels,
(A) patterning a black resist on a transparent substrate,
(B) forming a resist film by applying a positive resist composition having a thermosetting ability on the transparent substrate on which the black resist is patterned,
(C) exposing the resist film from the transparent substrate side,
(D) developing the resist film after the exposure to form a resist pattern;
Of the barrier rib pattern. The method according to claim 1,
(E) of thermally curing the resist pattern. The method according to claim 1,
Wherein the light emitting body for each color is a quantum dot fluorescent material. The method according to claim 1,
Wherein the positive resist composition contains an alkali-soluble resin (A) and a photosensitizer (B). The method of claim 4,
Wherein the alkali-soluble resin (A) is at least one compound selected from the group consisting of a structural unit (A1) represented by the following general formula (a-1) and an alicyclic epoxy group- Way.
However,

(A-1)
[In the above general formula, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Ra ⁰¹ represents a hydrogen atom or an organic group having a hydroxyl group.] The method according to claim 1,
Wherein the film thickness of the resist film is 6 占 퐉 or more. The method according to any one of claims 1 to 6,
Wherein the positive resist composition further contains inorganic particles having an average particle diameter of 0.1 to 1 占 퐉.

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