KR102622857B1 - Black photo sensitive resin composition for a forming pixel defined layer of oled and qled - Google Patents

Abstract

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent, and the binder resin (B) is a compound (B1) represented by the following formula (1) A black photosensitive resin composition for forming a pixel defining layer (Pixel Defined Layer) of an organic light emitting device comprising a black photosensitive resin composition, an organic light emitting device comprising a pixel defining layer made of the black photosensitive resin composition, a quantum dot light emitting device, and the organic light emitting device or quantum dot. A display device including a light emitting element is provided.
[Formula 1]

In the above equation
R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, where the alkyl group may be substituted with a hydroxyl group;
R2 represents a C1 to C20 aliphatic or aromatic hydrocarbon with or without a simple bond or hetero atom.

Description

Black photosensitive resin composition for forming pixel defining layers of organic light emitting devices and quantum dot light emitting devices {BLACK PHOTO SENSITIVE RESIN COMPOSITION FOR A FORMING PIXEL DEFINED LAYER OF OLED AND QLED}

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

Organic light emitting devices, one of the flat panel display devices, are self-emitting, so they have superior viewing angles and contrast compared to liquid crystal displays, and do not require a backlight. Therefore, it is possible to be lightweight and thin, and it is also advantageous in terms of power consumption. In addition, it has the advantage of being capable of low-voltage direct current operation, fast response speed, and since all of its components are solid, it is resistant to external shocks, has a wide operating temperature range, and is also inexpensive in terms of manufacturing cost.

In particular, the manufacturing process of the organic light emitting device, unlike a liquid crystal display device or PDP (Plasma Display Panel), can be said to be all about repetition of the deposition/etching process and the encapsulation process. It has the advantage of being very simple.

The organic light emitting device must have good contrast and brightness, but when external light is bright, the contrast is not good. In the case of a bottom-emitting organic light-emitting device, the cathode of the device is made of a metal with excellent reflectivity, so the light entering the device from the outside is reflected on the cathode surface and mixed with the light coming from the light-emitting layer.

In order to solve the above problem, most current organic light emitting devices reduce reflection of external incident light by the cathode by forming a circular polarizer at the bottom of the transparent substrate. That is, when external light is incident on the circular polarizer, half of it is blocked, and the other half is blocked when it is reflected to the cathode, thereby suppressing a decrease in contrast caused by external light.

However, the organic light-emitting device in which a circularly polarizing plate is attached to the conventional transparent substrate described above significantly reduces the reflection of external incident light by the cathode and at the same time blocks light emitted to the outside from the organic light-emitting layer, so the contrast is improved, but the luminance is reduced by 50%. There were problems with the above reduction and problems with high costs.

Therefore, in order to solve the above problem, a black pixel definition film that absorbs external incident light and improves contrast can be formed. The black pixel defined layer is precisely patterned through a photolithography process, and reliability is required to ensure that gas components critical to device operation are not eluted during the high-pressure deposition process that produces organic light-emitting device pixels.

However, the photosensitive resin composition for BM (Black Matrix) used in conventional liquid crystal display devices elutes gas components that are fatal to the operation of organic light-emitting devices during the high-pressure deposition process of manufacturing organic light-emitting device pixels. It is difficult to apply to organic light-emitting devices because it has problems such as lowering luminance and, in severe cases, making it impossible to drive organic light-emitting devices.

Republic of Korea Patent Publication 10-2015-0072581

The present invention was devised to solve the problems of the prior art described above,

The purpose is to provide a black photosensitive resin composition for forming a pixel defining film of an organic light emitting device or a quantum dot light emitting device that can significantly reduce the amount of outgassed during the manufacture of an organic light emitting device or quantum dot light emitting device pixel, such as a high pressure deposition process.

Another object is to provide an organic light emitting device, a quantum dot light emitting device, and a display device including the organic light emitting device or the quantum dot light emitting device including a pixel defining film made of the black photosensitive resin composition.

In order to achieve the above purpose,

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent,

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

[Formula 1]

In the above equation

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

R2 represents a C1 to C20 aliphatic or aromatic hydrocarbon with or without a simple bond or hetero atom.

In addition, the present invention

Provided is an organic light emitting device and a quantum dot light emitting device including a pixel defining film made of the black photosensitive resin composition.

In addition, the present invention

A display device including the organic light emitting device or quantum dot light emitting device is provided.

The black photosensitive resin composition for forming a pixel defining film of an organic light-emitting device and a quantum dot light-emitting device of the present invention significantly reduces the amount of outgassed during the manufacturing of an organic light-emitting device or a quantum dot light-emitting device pixel, such as through a high-pressure deposition process, thereby reducing the amount of outgassed due to outgassing. It provides an effect that does not cause a decrease in luminance or driving performance of the device being used.

Therefore, an organic light-emitting device, a quantum dot light-emitting device, including a pixel defining film made of the black photosensitive resin composition, and a display device including the organic light-emitting device or the quantum dot light-emitting device may provide excellent quality in terms of brightness, drivability, and durability. You can.

The present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent,

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

[Formula 1]

In the above equation

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

R2 represents a C1 to C20 aliphatic or aromatic hydrocarbon with or without a simple bond or hetero atom.

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

Colorant (A)

The colorant (A) is used to achieve black color and provides light blocking and external light reflection suppression properties to the pixel defining film.

The colorant can be any colorant known in the field, such as organic pigments, dyes, and black pigments, as long as it has light-blocking properties in visible light, but it is preferable to use black pigments.

As the black pigment, any known pigment may be used without particular limitation, and specifically, aniline black, lactam black, perylene black, carbon black, chromium oxide, iron oxide, and titanium black may be used. These may be used individually or in combination of two or more types. Examples of the carbon black include channel black, furnace black, thermal black, and lamp black.

If necessary, carbon black with a resin coating on the surface for electrical insulation may be used. To elaborate, since carbon black coated with resin has lower conductivity than carbon black not coated with resin, it can provide excellent electrical insulation when forming a black matrix and pixel defining film.

The colorant may include a black pigment and a blue pigment. In this case, the black pigment may be a black organic pigment and/or a black inorganic pigment.

When using a black pigment and a blue pigment, it is desirable because the transmittance in the visible light region and ultraviolet light region can be adjusted depending on the pigment ratio.

As the black organic pigment, black inorganic pigment, and blue pigment, any known pigment can be used, and examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). It can be done and may contain known dyes.

As a black organic pigment, one or more types selected from aniline black, lactam black, and perylene black can be used in combination, but are not limited thereto.

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

In addition, specific examples of the blue pigment include C.I Pigment Blue 15:6, C.I Pigment Blue 15:4, C.I Pigment Blue 60, and C.I Pigment Blue 16.

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

When the black organic pigment and the black inorganic pigment are used together, it may be preferable in that they have low dielectric properties and high coloring power at the same time.

Additionally, the colorant may optionally further include a color corrector as needed. As the color corrector, condensed polycyclic pigments such as anthraquinone-based pigments or perylene-based pigments, and organic pigments such as phthalocyanine pigments or azo pigments may be used.

The colorant may be contained in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, based on the total weight of the black photosensitive resin composition. If the content of the colorant is less than the above range, the light blocking effect is not sufficient and the above-mentioned effects cannot be secured. Conversely, if the content of the colorant exceeds the above range, there is a risk that the quality of the pattern obtained after patterning may deteriorate, so it can be appropriately used within the above range. .

Binder Resin (B)

The binder resin (B) is characterized in that it is a copolymer obtained through a copolymerization reaction containing a compound (B1) represented by the following formula (1):

[Formula 1]

In the above equation

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

R2 represents a C1 to C20 aliphatic or aromatic hydrocarbon with or without a simple bond or hetero atom.

In the above, R2 includes, for example, a C1-C10 straight-chain or branched alkylene group, a C2-C10 straight-chain or branched alkenylene group, a C3-C12 substituted or unsubstituted cycloalkylene group, and a C3-C12 straight-chain alkenylene group. Structures selected from the group consisting of substituted or unsubstituted cycloalkenylene groups, substituted or unsubstituted phenylene groups, and arylene groups may be mentioned.

In addition, the binder resin (B) is characterized in that it is a copolymer obtained through a copolymerization reaction containing the compound (B1) and at least one of the compounds (B2) and (B3) below.

(B2): Monomer containing unsaturated carboxyl group

(B3): Compound having an unsaturated bond capable of copolymerization with (B1) and (B2)

The ratio of the structural units derived from (B1) to the total number of moles of structural units of the binder resin (B) is preferably 20 to 90 mol%, and more preferably 40 to 70 mol%. If (B1) is included in less than 20 mol%, the effect of reducing the amount of outgassing is insufficient, and if it exceeds 90 mol%, the solubility in the developer is lowered, making pattern formation difficult, which is not desirable. .

It is more preferable that the proportion of structural units derived from (B1) above exceeds 50 mol% with respect to the total number of moles of structural units of the binder resin (B).

When the binder resin (B) contains the above (B2), the ratio of the structural units derived from the above (B2) to the total number of moles of the structural units of the binder resin (B) is preferably greater than 0 and not more than 70 mol%. do. When the above (B3) is contained, the ratio of the structural units derived from the above (B3) to the total number of moles of the structural units of the binder resin (B) is preferably greater than 0 and not more than 70 mol%.

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

Examples of the unsaturated carboxyl group-containing monomer (B2) include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. there is.

Examples of the unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

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

The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate. ), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), etc. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both ends, and examples include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc.

The above carboxyl group-containing monomers can be used individually or in combination of two or more types.

Compounds (B3) having an unsaturated bond capable of copolymerization with the above (B1) and (B2) include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and p-chloro. Styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, Aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butylacrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Latex, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Latex, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Nyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate unsaturated carboxylic acid esters such as; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate. acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecule chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butylacrylate, poly-n-butyl methacrylate, and polysiloxane. Examples include large monomers with These monomers can be used individually or in combination of two or more types.

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

The binder resin (B) may be used in an amount of 5 to 80% by weight, preferably 5 to 50% by weight, based on the total weight of the black photosensitive resin composition. This content is a range selected based on various considerations such as solubility in the developer and pattern formation. When used within the above range, the solubility in the developer is sufficient so that pattern formation is easy, and the film of the pixel portion of the exposed area is used during development. Decrease is prevented, and missingness of non-pixel parts becomes good.

photopolymerizability Compound (C)

The photopolymerizable compound (C) is not particularly limited, but is one selected from the group consisting of a polymer of an unsaturated monomer containing a carboxyl group, a copolymer of an unsaturated monomer containing a carboxyl group and a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof. The above can be used.

As the carboxyl group-containing unsaturated monomer, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, etc. can be used. Specifically, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids include fumaric acid, mesaconic acid, itaconic acid, and citraconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, unsaturated polyhydric carboxylic acids include mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, monomethylmaleic acid, and 5-norbornene-2- Carboxylic acid, mono-2-((meth)acryloyloxy)ethyl phthalate, mono-2-((meth)acryloyloxy)ethyl succinate, etc. are possible. These compounds having an unsaturated carboxyl group can be used individually or in combination of two or more, and among them, acrylic acid and methacrylic acid are preferably used because they have excellent copolymerization reactivity and solubility in a developer.

In addition, monomers that can be copolymerized with carboxyl group-containing unsaturated monomers include aromatic vinyl compounds, unsaturated carboxylate compounds, unsaturated aminoalkylcarboxylate compounds, vinyl cyanide compounds, and unsaturated oxetane carboxylate compounds. One type can be used alone or in combination of two or more types.

Specifically, the copolymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate unsaturated carboxylate compounds such as crylates; Unsaturated aminoalkylcarboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. unsaturated oxetane carboxylate compounds, etc.

The photopolymerizable compound may be used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight, based on the total weight of the black photosensitive resin composition. This content range is a range selected by taking into account various aspects such as the tendency for the final pixel defining film to have good strength and smoothness. If the content is less than the above range, the strength and smoothness are insufficient, and if the content exceeds the above range, the strength and smoothness are insufficient. Since patterning is not easy due to high strength, it is appropriately used within the above range.

light curing initiator (D)

The photopolymerization initiator (D) includes photopolymerization initiators commonly used in photosensitive resin compositions, such as acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, anthracene-based, anthraquinone-based, and biimide. Dazole-based compounds, etc. can be used, and they can be used alone or in combination of two or more types.

The acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxy Toxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Oligomers of benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. can be mentioned.

The benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'- Bis(diethylamino)benzophenone, etc. can be mentioned.

The triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethyl Toxy styryl)-4,6-bis(trichloro methyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloro methyl)-s-triazine, 2 -(p-methoxy phenyl)-4,6-bis(trichloro methyl)-s-triazine, 2-(p-tryl)-4,6-bis(trichloro methyl)-s-triazine, 2 -Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6 -bis(trichloro methyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloro methyl)-s-triazine, 2,4-trichloro methyl (piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, and the like.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. there is.

The oxime-based compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include OXE-01 and OXE-02 from Ciba.

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

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

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone.

The biimidazole-based compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) )-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4',5,5' position is attached to the carboalkoxy group. and imidazole compounds substituted by .

This photopolymerization initiator can be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the black photosensitive resin composition. This content range takes into account the photopolymerization speed of the photopolymerizable compound and the physical properties of the final coating film. If it is less than the above range, the polymerization rate may be low and the overall process time may be prolonged. Conversely, if it exceeds the above range, the physical properties of the coating film may be damaged due to excessive reaction. Since this may actually decrease, it should be used appropriately within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. The combined use of a photopolymerization initiator is preferable because the black photosensitive resin composition becomes more sensitive and productivity improves. As the photopolymerization opening aid used, one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds may be preferably used.

The photopolymerization initiation aid is typically used in an amount of 10 mol or less, preferably 0.01 to 5 mol, per mole of photopolymerization initiator. When a photopolymerization initiation aid is used within the above range, productivity improvement effects can be expected by increasing polymerization efficiency.

(F)Solvent

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

Typically, usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate. Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

The solvent may be included in a residual amount so that the black photosensitive resin composition satisfies 100% by weight. This content is a range selected in consideration of the dispersion stability of the composition and ease of processing in the manufacturing process (e.g., applicability).

(G) Additives

The black photosensitive resin composition of the present invention may further include additives known in the art for various purposes. Such additives are used to increase adhesion to the substrate and include silane coupling agents having a reactive substituent selected from the group consisting of carboxyl group, methacryloyl group, isocyanate group, epoxy group, and combinations thereof. Examples of silane coupling agents include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl. Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be used individually or in combination of two or more. To improve coating properties, surfactants can be used: BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA/- A fluorine-based surfactant such as 190/SZ-6032 (Doray Silicone Co., Ltd.) can be used.

In addition, the present invention

It relates to an organic light emitting device and a quantum dot light emitting device including a pixel defining film made from the black photosensitive resin composition.

In addition, the present invention

It relates to a display device including the organic light emitting device or quantum dot light emitting device.

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

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

b) prebake step of drying the solvent;

c) curing the exposed area by placing a photo mask on the obtained film and irradiating actinic light;

d) performing a development process to dissolve the unexposed area using an aqueous alkaline solution; and

e) Drying and post-bake performance steps

The application may be performed by a wet coating method using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet to obtain the desired thickness.

Prebaking is performed by heating using an oven, hot plate, etc. At this time, the heating temperature and heating time in the prebake are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 80 to 150°C for 1 to 30 minutes.

Additionally, exposure performed after prebaking is performed by an exposure machine and exposed through a photo mask to expose only the portion corresponding to the pattern. At this time, the light irradiated may be, for example, visible light, ultraviolet rays, X-rays, and electron beams.

Alkaline development after exposure is performed for the purpose of removing the photosensitive resin composition from the non-removed portion of the unexposed portion, and a desired pattern is formed by this development. As a developer suitable for this alkaline development, for example, an aqueous solution of carbonate of an alkali metal or an alkaline earth metal can be used. In particular, use a slightly alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, and use a developer or ultrasonic cleaner at a temperature of 10 to 50 ℃, preferably 20 to 40 ℃. and perform it.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220°C for 10 to 120 minutes. Post-bake, like pre-bake, is performed using an oven, hot plate, etc.

The pixel defining film manufactured from the black photosensitive resin composition of the present invention not only has excellent physical properties such as optical density, adhesion, electrical insulation, and light blocking, but also has excellent heat resistance and solvent resistance, and is used in organic light-emitting devices, quantum dot light-emitting devices, and the above. The reliability of a display device including an organic light emitting device or a quantum dot light emitting device can be improved.

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

Manufacturing example 1: Synthesis of binder resin A

A flask equipped with a stirrer, thermometer reflux cooling pipe, dropping lot, and nitrogen introduction pipe was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecan-8-yl(meth)acrylate and 3,4-epoxytricyclodecan-9-yl(meth)acrylate at a molar ratio of 50:50 177 Stirring was prepared by adding 23 parts of acrylic acid, 4 parts of t-butylperoxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (PGMEA). As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Afterwards, 395 parts of PGMEA was added to the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. After that, the monomer and chain transfer agent were started dropwise from the dropping lot. The dropping was carried out for 2 hours while maintaining 90℃, and after 1 hour, the temperature was raised to 110℃ and maintained for 5 hours to obtain a resin with a solid acid value of 80mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 9,000, and the molecular weight distribution (Mw/Mn) was 2.2.

Manufacturing example 2: Synthesis of binder resin B

A flask equipped with a stirrer, thermometer reflux cooling pipe, dropping lot, and nitrogen introduction pipe was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecan-8-yl(meth)acrylate and 3,4-epoxytricyclodecan-9-yl(meth)acrylate at a molar ratio of 20:50. 30 parts acrylic acid, 110 parts cyclohexylmaleimide, 40 parts 2-hydroxymethacrylate, 4 parts t-butylperoxy-2-ethylhexanoate, and 40 parts propylene glycol monomethyl ether acetate (PGMEA). Stirring was prepared. As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Afterwards, 395 parts of PGMEA was added to the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. After that, the monomer and chain transfer agent were started dropwise from the dropping lot. Dropping was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and maintained for 5 hours to obtain a resin with a solid acid value of 110 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 8,000, and the molecular weight distribution (Mw/Mn) was 2.2.

Manufacturing example 3: Synthesis of binder resin C

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

Manufacturing example 4: Synthesis of binder resin D

40 parts of propylene glycol monomethyl ether acetate and 140 parts of propylene glycol monomethyl ether were introduced into a flask equipped with a stirrer, thermometer reflux cooling pipe, dropping funnel, and nitrogen introduction pipe, and the atmosphere in the flask was changed from air to nitrogen, and then 100% After raising the temperature to ℃, a solution containing 10 parts of benzylmaleimide, 60 parts of methyl methacrylate, 30 parts of methacrylic acid, and 136 parts of propylene glycol monomethyl ether acetate was added and 4 parts of azobisisobutyronitrile was added from the dropping lot. It was added dropwise to the flask over 2 hours, and stirring was continued at 80°C for an additional 4 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 15 parts of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol, and 0.1 part of hydroquinone were added into the flask, reaction was continued at 110°C for 6 hours, and the solid acid value was 110 mg. Resin A with KOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000, and the molecular weight distribution (Mw/Mn) was 2.5.

Example 1~7 and Comparative example 1-2: Preparation of black photosensitive resin composition

After adding the solvent to the mixer, the colorant, binder resin, photopolymerizable compound, photopolymerization initiator, and additives were added and mixed uniformly through stirring to prepare a black photosensitive resin composition. At this time, the composition followed the composition in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative example 2 Colorant (A) carbon black 8.00 8.00 8.00 8.00 8.00 A-1 A-2 8.00 8.00 Binder Resin (B) Resin A (Production Example 1) 7.24 3.62 3.62 7.24 2.10 Resin B (Production Example 2) 7.24 3.62 7.24 Resin C (Production Example 3) 7.24 3.62 Resin D (Production Example 4) 7.24 5.14 Photopolymerizable compound (C) Dipentaerythritol hexaacrylate
(Kayarad DPHA: Nippon Kayaku Co., Ltd.)) 3.12 3.12 3.12 3.12 3.12 3.12 3.12 3.12 3.12 Photopolymerization initiator (D) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime) (Irgacure OXE-02: Ciba) 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 0.31 Solvent (E) Propylene glycol monomethyl ether acetate 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 additive Pigment dispersant (polyester type) 1.33 1.33 1.33 1.33 1.33 1.33 1.33 1.33 1.33

(Unit: weight%)

main)

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

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

Test example 1: Outgas characteristic evaluation

(1) Production of colored substrate

A 5cm x 5cm glass substrate (Corning) was washed with neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in the Examples and Comparative Examples above was spin-coated on the glass substrate so that the final film thickness was 2.0㎛, pre-baked at 80 to 120°C, and dried for 1 to 2 minutes to remove the solvent. did. Then, it was exposed at an exposure dose of 40 to 100 mJ/cm ² to form a 1cm Subsequently, post-baking was performed at 220°C for 20 minutes to prepare a colored substrate.

(2) Outgas evaluation

Outgas evaluation was conducted by thermally decomposing the colored substrate prepared above at 230°C for 30 minutes and analyzing the collected compounds using Py-GC/MS. The analysis results are shown in Table 2 below.

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

As can be seen in Table 2, in the case of the example pattern made with the black photosensitive composition of the present invention, the amount of outgassing is significantly reduced compared to the comparative example pattern.

Claims (10)

A black photosensitive resin composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent,
The colorant (A) includes a black pigment, and the black pigment includes only carbon black,
The binder resin (B) includes a compound (B1) represented by the following formula (1),
The pattern made from the black photosensitive resin composition is a pixel definition film (pixel definition film) of an organic light-emitting device and a quantum dot light-emitting device with an outgassing amount of 8,282,034 or less when the compound collected by thermal decomposition at 230° C. for 30 minutes is analyzed by Py-GC/MS. Black photosensitive resin composition for forming Pixel Defined Layer:
[Formula 1]

In the above equation
R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, where the alkyl group may be substituted with a hydroxyl group;
R2 represents a C1 to C20 aliphatic or aromatic hydrocarbon with or without a simple bond or hetero atom. In claim 1,
Based on the total weight of the black photosensitive resin composition, (A) 1 to 50% by weight of colorant, (B) 5 to 80% by weight of binder resin, (C) 1 to 30% by weight of photopolymerizable compound, (D) 0.01 to 10% by weight of photopolymerization initiator. %, (F) A black photosensitive resin composition comprising a residual amount of solvent. In claim 1,
The binder resin (B) is a black photosensitive resin composition, characterized in that the ratio of the structural units of the compound (B1) represented by Chemical Formula 1 is 20 to 90 mol% with respect to the total number of moles of the structural units of the binder resin (B). In claim 1,
A black photosensitive resin composition, wherein the binder resin (B) has a weight average molecular weight of 5,000 to 50,000. In claim 3
A black photosensitive resin composition, characterized in that the ratio of the structural units of the compound (B1) represented by the above formula (1) exceeds 50 mol% with respect to the total number of moles of the structural units of the binder resin (B). In claim 1,
The photopolymerization initiator (D) is one selected from the group consisting of acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, anthracene-based, anthraquinone-based, and biimidazole-based compounds. A black photosensitive resin composition characterized by the above. An organic light emitting device comprising a pixel defining layer made of the black photosensitive resin composition of any one of claims 1 to 6. A quantum dot light emitting device comprising a pixel defining film made of the black photosensitive resin composition of any one of claims 1 to 6. A display device including the organic light emitting element of claim 7. A display device including the quantum dot light emitting device of claim 8.