KR20220122187A - Novel polymer and photosensitive resin composition comprising the same - Google Patents

Abstract

The purpose of the present invention is to provide a novel polymer and a photosensitive resin composition comprising the same. Specifically, the present invention provides a cured film having high transmittance and low reflectance properties while being capable of photo-patterning using the photosensitive resin composition. In addition, the cured film of the present invention is employed so that an organic light-emitting device with improved light extraction efficiency is provided.

Description

Novel polymer and photosensitive resin composition comprising the same

The present invention relates to a novel polymer and a photosensitive resin composition comprising the same.

The organic light emitting device is a self-luminous device, and unlike a liquid crystal display device, it does not require a separate light source, so it can be manufactured in a lightweight and thin form. In addition, the organic light emitting diode is not only advantageous in terms of power consumption because it can be driven at a low voltage, but also has excellent color realization, response speed, viewing angle, contrast ratio, and the like, and thus is in the spotlight as a next-generation display.

A typical organic light emitting device has a structure in which a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a reflective electrode are sequentially stacked on a glass substrate. , light is generated by the combination of electrons and holes in the light emitting layer.

The light generated from the light emitting layer can be divided into light emitted to the outside and light that is not emitted and is trapped inside. In the conventional organic light emitting device, most of the photons generated in the light emitting layer are trapped inside due to total reflection due to the difference in refractive index of the inner layer and do not contribute to the amount of light output, so the light extraction efficiency is only about 20%. . Therefore, it is necessary to study a method for improving the light extraction efficiency.

The light extraction effect can be obtained by attaching a microlens array to the outside of the glass substrate or coating a scattering layer. There are limits to In addition, a method for improving light extraction efficiency by using a light scattering layer including particles capable of scattering light has been studied, but the conventional light scattering layer is formed of a material that cannot be photo-patterned, and etching for patterning the light scattering layer Additional processing was required. However, since other elements around the light scattering layer may be damaged by such an etching process, there is a problem in that patterning of the light scattering layer is not practically possible.

Therefore, the development of a light extraction material capable of photo-patterning while satisfying all physical properties such as developability, sensitivity, and refractive index is required.

KR 10-2015-0136855

An object of the present invention is to provide a novel polymer and a photosensitive resin composition comprising the same.

Another object of the present invention is to provide a cured film having high transmittance and low reflectance characteristics while photo-patterning is possible using the photosensitive resin composition.

In addition, it is an object of the present invention to provide an organic light emitting device having improved light extraction efficiency by employing the cured film.

For the above purpose, the present invention provides a polymer comprising a repeating unit represented by the following Chemical Formulas 1 and 2, and comprising a moiety represented by the following Chemical Formula 3 at the terminal thereof.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3,

L ₁ and L ₃ are each independently (C1-C20)alkylene, (C6-C20)arylene or (C3-C20)heteroarylene;

L ₂ is -C(=O)- or -SO ₂ -;

L ₄ and L ₅ are each independently a single bond or (C1-C20)alkylene;

Ring A is a (C6-C20) aromatic ring or a (C3-C20) alicyclic ring;

, (C6-C20)아릴렌, (C3-C20)헤테로아릴렌, (C3-C20)시클로알킬렌 또는 (C2-C20)헤테로시클로알킬렌이고;Ar is

, (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;

Ar ^a and Ar ^b are each independently (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;

L ^a and L ₆ are each independently (C1-C20)alkylene;

R ₁ is hydrogen or (C1-C20)alkyl;

X ₁ to X ₃ are each independently a single bond, -C(=O)NH-, or -NHC(=O)-;

p to r are each independently an integer from 1 to 10;

Arylene, heteroarylene, cycloalkylene and heterocycloalkylene of Ar, Ar ^a and Ar ^b are further selected from (C1-C20)alkyl, (C1-C20)alkoxy, amino and halogen with one or more substituents may be substituted.)

According to an embodiment of the present invention, L ₁ and L ₃ are each independently (C1-C10)alkylene or (C6-C12)arylene; The A ring may be a (C6-C12) aromatic ring.

The repeating unit represented by Formula 1 according to an embodiment of the present invention may be represented by Formula 11 below.

[Formula 11]

(In Formula 11,

each L ₁ is independently (C1-C10)alkylene or (C6-C12)arylene;

p is an integer from 1 to 5.)

The repeating unit represented by Formula 2 according to an embodiment of the present invention may be represented by Formula 12 below.

[Formula 12]

(In Formula 12,

L ₃ is (C1-C10)alkylene or (C6-C12)arylene;

L ₄ and L ₅ are each independently a single bond or (C1-C10)alkylene;

또는 (C6-12)아릴렌이고;Ar is

or (C6-12)arylene;

Ar ^a and Ar ^b are each independently (C6-C12)arylene;

L ^a is (C1-C10)alkylene;

q and r are each independently an integer from 1 to 5;

Arylene of Ar, Ar ^a and Ar ^b may be further substituted with one or more substituents selected from (C1-C10)alkyl, (C1-C10)alkoxy, amino and halogen.)

Ar according to an embodiment of the present invention may be selected from the following structures.

(In the above structure,

R ₁₁ is (C1-C6)alkyl;

R ₁₂ and R ₁₃ are each independently hydrogen or (C1-C6)alkyl;

L ₁₁ is (C1-C6)alkylene;

n is 1 or 2.)

The moiety represented by Formula 3 according to an embodiment of the present invention may be represented by Formula 13 below.

[Formula 13]

(In the formula 13,

R ₁ is hydrogen or (C1-C10)alkyl;

L ₆ is (C1-C10)alkylene.)

The polymer according to an embodiment of the present invention may be represented by the following Chemical Formula 14.

[Formula 14]

(In Formula 14,

R ₁ is hydrogen or (C1-C6)alkyl;

L ₁ , L ₃ and L ₁₂ are each independently (C1-C6)alkylene or (C6-C12)arylene;

L ₄ and L ₅ are each independently a single bond or (C1-C6)alkylene;

L ₆ is (C1-C6)alkylene;

또는

이고;Ar is

or

ego;

R ₂₁ to R ₂₃ are each independently hydrogen or (C1-C6)alkyl;

L ₂₁ is (C1-C6)alkylene;

p, q and s are each independently an integer from 1 to 3;

x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1.)

The polymer according to an embodiment of the present invention may be selected from the following structures.

(In the above structure,

x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1.)

The weight average molecular weight of the polymer according to an embodiment of the present invention may be 2000 g/mol to 10000 g/mol.

In addition, the present invention provides a photosensitive resin composition comprising the polymer.

The photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerizable monomer, a dispersion for light extraction, and a photoinitiator.

The photopolymerizable monomer according to an embodiment of the present invention may be a polyfunctional monomer having an ethylenically unsaturated bond.

The dispersion for light extraction according to an embodiment of the present invention is any one selected from zirconium oxide, titanium oxide, antimony oxide, cerium oxide, selenium oxide, aluminum oxide, yttrium oxide, zinc oxide, zinc sulfide, and mixtures thereof may be more than

The photoinitiator according to an embodiment of the present invention is at least one selected from an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, an imidazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime-based compound can

The photosensitive resin composition according to an embodiment of the present invention may have a solid content of 10 to 80 wt% based on the total photosensitive resin composition.

The photosensitive resin composition according to an embodiment of the present invention comprises 5 to 80% by weight of the polymer, 5 to 70% by weight of the photopolymerizable monomer, 0 to 50% by weight of the dispersion for light extraction, 1 to 15% by weight of the photoinitiator based on the solid content may be included as

Moreover, this invention provides the cured film obtained by hardening|curing the said photosensitive resin composition.

In addition, the present invention provides an organic electronic device comprising the cured film.

The photosensitive resin composition according to the present invention can be photo-patterned without a separate etching process, and can implement a precise pattern with excellent sensitivity and developability.

In addition, the photosensitive resin composition according to the present invention can form a cured film having excellent optical properties through photocuring. Specifically, since the cured film according to the present invention has high transmittance and refractive index, and low reflectance, it is possible to improve light extraction efficiency in the organic light emitting device.

In addition, the organic light emitting device employing the photosensitive resin composition according to the present invention not only improves light extraction efficiency, but also reduces power consumption and can implement excellent lifespan characteristics.

In addition, when the photosensitive resin composition according to the present invention is used, since an additional etching process is not required, the production cost and productivity can be improved by simplifying the process, and damage to surrounding materials due to the etching process can be prevented.

Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. Descriptions of possible known functions and configurations will be omitted.

As used herein, the term “comprises” is an open-ended description having an equivalent meaning to expressions such as “comprising”, “containing”, “having” or “characterized by”, and elements not listed in addition; Materials or processes are not excluded.

As used herein, the term “CA-CB” means “the number of carbon atoms is greater than or equal to A and less than or equal to B”.

As used herein, the term “alkyl” refers to a monovalent straight-chain or branched saturated hydrocarbon group composed of only carbon and hydrogen atoms. Examples of such alkyls include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and the like.

As used herein, the term “alkoxy” refers to an —O-alkyl radical, where “alkyl” is as defined above. Examples include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

As used herein, the term “alkylene” refers to a divalent organic radical derived from an aliphatic hydrocarbon in a straight-chain or pulverized form.

As used herein, the term “arylene” is a divalent organic radical of an aromatic ring derived from an aromatic hydrocarbon, and is preferably a single or fused ring system containing 4 to 7, preferably 5 or 6 ring atoms in each ring. It includes, and includes a form in which a plurality of aryls are connected by a single bond. Examples include, but are not limited to, phenylene, naphthylene, biphenylene, and the like.

As used herein, the term "heteroarylene" is a divalent organic radical derived from an aromatic hydrocarbon by the removal of two hydrogens, and is selected from B, N, O, S. Si and P as a ring member (ring atom). contains 1 to 4 heteroatoms, and the remaining ring members are carbon.An example includes furanylene, thiophenylene, pyridinylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, and the like. However, the present invention is not limited thereto.

As used herein, the term “cycloalkylene” is a divalent organic radical derived from a fully saturated or partially unsaturated alicyclic hydrocarbon ring, and includes fused cyclic, bridged cyclic and spirocyclic groups, and the like. Examples include, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and the like.

The term “heterocycloalkylene” in the present specification refers to a divalent organic lycalo derived from a fully saturated and partially unsaturated hydrocarbon ring of 3 to 6 carbon atoms, B, N, O, S, -P(=O )-, -C(=O)-, Si and P, and the like.

As used herein, the term “single bond” refers to a case in which an atom does not exist at the corresponding site. For example, when Y is a single bond in the structure of X-Y-Z, X and Z are directly connected to form the structure of X-Z.

In the present specification, the number of carbon atoms according to the definition of the substituent described in Formula 1 does not include the number of carbon atoms of the substituent that may be further substituted.

Hereinafter, the present invention will be described in detail.

The present invention provides a polymer comprising repeating units represented by the following Chemical Formulas 1 and 2, and including a moiety represented by the following Chemical Formula 3 at the terminal thereof.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3,

L ₁ and L ₃ are each independently (C1-C20)alkylene, (C6-C20)arylene or (C3-C20)heteroarylene;

L ₂ is -C(=O)- or -SO ₂ -;

L ₄ and L ₅ are each independently a single bond or (C1-C20)alkylene;

Ring A is a (C6-C20) aromatic ring or a (C3-C20) alicyclic ring;

, (C6-C20)아릴렌, (C3-C20)헤테로아릴렌, (C3-C20)시클로알킬렌 또는 (C2-C20)헤테로시클로알킬렌이고;Ar is

, (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;

Ar ^a and Ar ^b are each independently (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;

L ^a and L ₆ are each independently (C1-C20)alkylene;

R ₁ is hydrogen or (C1-C20)alkyl;

X ₁ to X ₃ are each independently a single bond, -C(=O)NH-, or -NHC(=O)-;

p to r are each independently an integer from 1 to 10;

Arylene, heteroarylene, cycloalkylene and heterocycloalkylene of Ar, Ar ^a and Ar ^b are further selected from (C1-C20)alkyl, (C1-C20)alkoxy, amino and halogen with one or more substituents may be substituted.)

The moiety represented by Formula 3 according to an embodiment of the present invention may be included at one or more ends of the polymer. Preferably, when the polymer has two ends, two moieties are included, and when the polymer has a branched chain structure, it may include three or more moieties at three or more ends.

The polymer according to an embodiment of the present invention may be provided as an alkali-soluble resin.

The polymer according to an embodiment of the present invention has excellent sensitivity and alkali developability due to the above-described structural characteristics, and may increase adhesion to a substrate. In addition, the photosensitive resin composition employing the polymer can provide a cured film having an excellent refractive index.

According to an embodiment of the present invention, L ₁ and L ₃ may be each independently (C1-C10)alkylene or (C6-C12)arylene, and Ring A may be a (C6-C12)aromatic ring.

The repeating unit represented by Formula 1 according to an embodiment of the present invention may be more preferably represented by Formula 11 below.

[Formula 11]

(In Formula 11,

each L ₁ is independently (C1-C10)alkylene or (C6-C12)arylene;

p is an integer from 1 to 5.)

The repeating unit represented by Chemical Formula 2 according to an embodiment of the present invention may more preferably be represented by the following Chemical Formula 12.

[Formula 12]

(In Formula 12,

L ₃ is (C1-C10)alkylene or (C6-C12)arylene;

L ₄ and L ₅ are each independently a single bond or (C1-C10)alkylene;

또는 (C6-12)아릴렌이고;Ar is

or (C6-12)arylene;

Ar ^a and Ar ^b are each independently (C6-C12)arylene;

L ^a is (C1-C10)alkylene;

q and r are each independently an integer from 1 to 5;

Arylene of Ar, Ar ^a and Ar ^b may be further substituted with one or more substituents selected from (C1-C10)alkyl, (C1-C10)alkoxy, amino and halogen.)

Ar according to an embodiment of the present invention may be selected from the following structures.

(In the above structure,

R ₁₁ is (C1-C6)alkyl;

R ₁₂ and R ₁₃ are each independently hydrogen or (C1-C6)alkyl;

L ₁₁ is (C1-C6)alkylene;

n is 1 or 2.)

The moiety represented by Chemical Formula 3 according to an embodiment of the present invention may more preferably be one represented by the following Chemical Formula 13.

[Formula 13]

(In the formula 13,

R ₁ is hydrogen or (C1-C10)alkyl;

L ₆ is (C1-C10)alkylene.)

The polymer according to an embodiment of the present invention, more preferably, may be represented by the following formula (14).

[Formula 14]

(In Formula 14,

R ₁ is hydrogen or (C1-C6)alkyl;

L ₁ , L ₃ and L ₁₂ are each independently (C1-C6)alkylene or (C6-C12)arylene;

L ₄ and L ₅ are each independently a single bond or (C1-C6)alkylene;

L ₆ is (C1-C6)alkylene;

또는

이고;Ar is

or

ego;

R ₂₁ to R ₂₃ are each independently hydrogen or (C1-C6)alkyl;

L ₂₁ is (C1-C6)alkylene;

p, q and s are each independently an integer from 1 to 3;

x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1.)

According to an embodiment of the present invention, L ₁ , L ₃ , and L ₁₂ are each independently (C6-C12)arylene. In addition, R ₁ may be (C1-C6)alkyl, more preferably (C1-C3)alkyl.

The polymer according to an embodiment of the present invention, more preferably, may be selected from the following structure.

(In the above structure,

x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1.)

The weight average molecular weight of the polymer according to an embodiment of the present invention may be from 2000 g/mol to 10000 g/mol, preferably from 2000 g/mol to 8000 g/mol, and more preferably from 4000 g/mol to 6000 g/mol. .

In addition, the present invention provides a photosensitive resin composition comprising the polymer.

The photosensitive resin composition according to the present invention is to improve the light extraction efficiency of the organic light emitting device, by including the polymer, it is possible to provide a cured film having a reliable pattern and excellent refractive index.

The photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerizable monomer, a dispersion for light extraction, and a photoinitiator.

The photopolymerizable monomer according to an embodiment of the present invention may be a polyfunctional monomer having an ethylenically unsaturated bond. In this case, the polyfunctional monomer having an ethylenically unsaturated bond is to improve the degree of crosslinking through crosslinking with the polymer, and may improve film strength, heat resistance, chemical resistance, stability over time, and the like depending on the purpose.

Non-limiting examples of the photopolymerizable monomer include 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol Dimethacrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol diacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexaacrylate, pentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, trimethylpropane triacrylate, pentaerythritol hexa (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylic Rate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate , may be at least one selected from sorbitol tri (meth) acrylate and trimethyl propane tri (meth) acrylate, but is not limited thereto.

The dispersion for light extraction according to an embodiment of the present invention includes dispersed particles for improving the light extraction efficiency of an organic light emitting device, and includes zirconium oxide, titanium oxide, antimony oxide, cerium oxide, selenium oxide, aluminum oxide. , may be any one or more selected from yttrium oxide, zinc oxide, zinc sulfide, and mixtures thereof. At this time, the dispersion is not particularly limited, but may have an average particle diameter of 200 nm or less, preferably 10 to 100 nm, and more preferably 1 to 50 nm.

The photoinitiator according to an embodiment of the present invention is at least one selected from an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, an imidazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime-based compound can In one embodiment, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine , 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, 2- (o-chlorophenyl) -4,5-diphenyl imidazole Dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2 -(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,4-di(p- Methoxy phenyl)-5-phenyl imidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methylmercaptophenyl)-4,5 -diphenyl imidazole dimer, [1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazolyl-3-yl]-1-(O-acetyloxime), benzophenone, p-( Diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-di Ethylthioxanthone, 2,2-bis2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, (E)-2-(acetoxyimino)-1- (9,9-diethyl-9H-fluorene-2-yl)butanone, (E)-1-(9,9-dibutyl-7-nitro-9H-fluorene-2-yl)ethanone O -Acetyl oxime, (Z)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluorene-2-yl)propanone, Irgacure 369 from Basf, Irgacure 651, Irgacure 907, Darocur One or more selected from the group consisting of TPO, Irgacure 819, OXE-01, OXE-02, OXE-03, OXE-04, Adeka's N-1919, NCI-831 and NCI-930 may be used, but limited thereto it's not going to be

The photosensitive resin composition according to an embodiment of the present invention may further include a solvent. The solvent is an organic solvent, and in one embodiment, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propellen glycol propyl ether acetate, propylene glycol butyl ether acetate) and the like propylene glycol alkyl ether acetates; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate ethyl, methyl hydroxyacetate, hydroxy Ethyl acetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methyl butanoate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, ethoxy acetic acid Butyl, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, 2-methoxypropionate propyl, 2-methoxybutylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-ethoxypropylpropionate, 2-ethoxybutylpropionate, Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate , 3-methyl ethoxypropionate, 3-ethoxy ethyl propionate, 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate ethyl, 3-propoxypropionate propyl, It may be one or more selected from esters such as 3-butylpropoxypropionate, 3-butoxypropionate methyl, 3-butoxypropionate ethyl, 3-butoxypropionate propyl, and 3-butoxypropionate butyl, but is limited thereto not.

The amount of the solvent is not limited to implement the desired viscosity, but may be included in an amount of 20 to 80% by weight, more preferably 40 to 80% by weight, based on the total photosensitive resin composition.

The photosensitive resin composition according to an embodiment of the present invention may have a solid content of 10 to 80 wt% with respect to the total photosensitive resin composition. The solid content is excluding the solvent, and is preferably included in an amount of 10 to 70 wt%, more preferably 20 to 50 wt%, based on the total photosensitive resin composition. In the above-mentioned numerical range, the desired effect in the present invention without impairing the stability of the composition, that is, it is more preferable because it is remarkable in use.

The photosensitive resin composition according to an embodiment of the present invention comprises 5 to 80% by weight of the polymer, 5 to 70% by weight of the photopolymerizable monomer, 0 to 50% by weight of the dispersion for light extraction, 1 to 15% by weight of the photoinitiator based on the solid content may be included. Preferably, 10 to 60 wt% of the polymer, 10 to 60 wt% of the photopolymerizable monomer, 10 to 40 wt% of the dispersion for light extraction, and 1 to 10 wt% of the photoinitiator may be included. More preferably, 20 to 60% by weight of the polymer, 10 to 40% by weight of the photopolymerizable monomer, 20 to 40% by weight of the dispersion for light extraction, and 1 to 5% by weight of the photoinitiator may be included.

Of course, the photosensitive resin composition according to an embodiment of the present invention may further include any additives commonly used in the art. In this case, the optional additives may be silane coupling agents, surfactants, fillers, curing agents, leveling agents, adhesion aids, antioxidants, ultraviolet absorbers, aggregation inhibitors, chain transfer agents, solvents, etc., preferably silane coupling agents, surfactants and It may be one or more selected from solvents.

In addition, the present invention provides a cured film obtained by curing the photosensitive resin composition and an organic electronic device including the same.

Of course, the cured film according to an embodiment of the present invention and a method for manufacturing an organic electronic device including the same can be any known method within a range that can be recognized by those skilled in the art.

Hereinafter, a method for forming a cured film using the photosensitive resin composition according to the embodiment will be described.

Specifically, the cured film using the photosensitive resin composition according to an embodiment of the present invention is formed by applying the photosensitive resin composition according to the present invention on a substrate and removing the solvent by prebaking to form a coating film; and photo-curing by irradiating the coating film with light.

According to an embodiment of the present invention, the application may use a conventional coating method, and may include a spray method, a roll coater method, a rotation coating method, a spin coater method, etc. as an example, but is not limited thereto.

According to an embodiment of the present invention, the pre-bake may be performed under normal temperature conditions, and in one embodiment, may be performed at a temperature of 50 to 200° C. for 1 to 5 minutes, but is not limited thereto.

According to an embodiment of the present invention, the light may be selected from visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., and a predetermined pattern may be formed using a pattern prepared in advance on the coating film. . In one embodiment, the ultraviolet rays can use g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), etc., of course, the irradiation amount of these ultraviolet rays can be appropriately selected as needed. .

In addition, the substrate according to an embodiment of the present invention may use silicon, quartz, glass, silicon wafer, polymer, metal, metal oxide, etc., but is not limited thereto. The polymer substrate is triacetyl cellulose, acetyl cellulose butyrate, ethylene vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide Mid, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl A film substrate such as methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polycarbonate may be used, but is not limited thereto.

After the photocuring step according to the present invention, the step of developing with a developer may be further included. The developing step is a process for removing the unexposed portion after photocuring through a mask for forming a target pattern, and may be performed by a conventional method such as a liquid addition method, a dipping method, and a spraying method.

In one embodiment, the step of developing according to the present invention may be performed by dipping the substrate in a developer by tilting the substrate at an arbitrary angle.

At this time, the developer is not limited as long as it is an aqueous alkali solution, but non-limiting examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate; primary amines such as n-propylamine; secondary amines such as diethylamine and n-propyldiamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; It may be an aqueous solution of one or more alkaline compounds selected from the like. In this case, the developing solution may be an aqueous solution containing the above-described alkaline compound in an amount of 0.1 to 10% by weight, but is not limited thereto.

In addition, after the developing step, the step of washing and drying with ultrapure water for 30 to 300 seconds may be further performed.

In addition, after the washing and drying step, the step of thermosetting in the range of 200 to 300 ℃ using a heating device such as an oven may be further performed.

The cured film according to an embodiment of the present invention can be effectively used in electronic devices such as display devices, semiconductor devices, or optical waveguide materials, specifically, thin film transistor (TFT) substrates such as liquid crystal display devices or organic EL display devices. It can be used as a core or clad material of an optical waveguide such as a planarization film for use, a protective film or insulating film for touch panel sensor elements, etc., an interlayer insulating film for semiconductor elements, a planarization film for a solid-state imaging element, a microlens array pattern, or an optical semiconductor element. .

In this case, the thickness of the cured film may be suitably changed according to the purpose, but may preferably be formed to a thickness of 100 nm to 50 µm, and more preferably be formed to a thickness of 500 nm to 10 µm.

Hereinafter, the present invention will be described in detail by way of Examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples. At this time, if there is no other definition in the technical terms and scientific terms used, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

[Example 1]

Step 1: Preparation of Polymer A-1

While injecting nitrogen into a four-neck flask equipped with a stirrer, temperature control device, and nitrogen gas injection device, 47.6 g of tetrahydrofuran (THF) was put, and 6.9 g (0.028 mol) of 4,4'-thiobisbenzenethiol was added. dissolved. When the solid is completely dissolved, 0.2 g of triethylamine (TEA) is added and stirred, 2.2 g (0.012 mol) of 3,5-dichlorobenzoic acid is added, and after stirring at high temperature for 5 hours, m-xylene diisocyanate ( XDI) 1.72 g (0.009 mol) was added and stirred at room temperature (25° C.) for 3 hours. Then, 1.07 g of isocyanatoethyl methacrylate (MOI, Showa Denko) was added and stirred for 5 hours. The reaction mixture was poured into water to form a precipitate, and the precipitate was filtered, washed thoroughly with water, and dried under reduced pressure at 50° C. for 24 hours or more to prepare Polymer A-1. The weight average molecular weight of Polymer A-1 calculated|required by GPC method standard polystyrene conversion was 4,700 g/mol, and the dispersion degree was 1.75.

Step 2: Preparation of photosensitive composition 1

After mixing with a composition corresponding to Example 1 of Table 1 and dissolving at room temperature (25° C.), it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition 1.

Step 3: Preparation of cured film 1-1

The photosensitive resin composition 1 was coated on a glass substrate using a spin coater (TOP-8, Dong-A Trading Co.), and then heated on a hot plate at 100° C. for 2 minutes to form a coating film with a thickness of 3.5 micrometers. The substrate coated with the coating film was exposed with a change in exposure amount using a mask engraved with patterns of various sizes using an exposure machine (MPA-600FA) manufactured by Canon Corporation. Thereafter, it was developed at room temperature (25° C.) with 2.38 wt% of a developer (tetraammonium hydroxide) for 150 seconds to dissolve and remove the unexposed parts, washed with pure water for 60 seconds to form a pattern, and then a high-temperature oven at 230° C. A cured film 1-1 in which a pattern was formed was prepared by baking for 30 minutes.

Step 4: Preparation of cured film 1-2

The photosensitive resin composition 1 was coated on a glass substrate using a spin coater (TOP-8, Dong-A Trading), and then heated on a hot plate at 100° C. for 2 minutes to form a coating film. The substrate coated with the coating film was irradiated with light on the entire surface without a mask at an exposure amount of 50 mJ/cm ² using an exposure machine (MPA-600FA) manufactured by Canon Corporation. Thereafter, a cured film 1-2 having a thickness of 1.5 micrometers was prepared by baking in a high temperature oven at 230° C. for 30 minutes.

[Example 2]

Step 1: Preparation of Polymer A-2

Polymer A-2 was prepared in the same manner as in Example 1, except that 2.29 g (0.009 mol) of 4,4'-methylenediphenyl diisocyanate (MDI) was used instead of m-xylene diisocyanate (XDI). prepared. The weight average molecular weight of Polymer A-2 calculated|required by GPC method standard polystyrene conversion was 5,200 g/mol, and the dispersion degree was 1.82.

Step 2: Preparation of photosensitive composition 2

After mixing with a composition corresponding to Example 2 of Table 1 and dissolving at room temperature (25° C.), it was filtered through a 0.2 μm filter to prepare a photosensitive resin composition 2.

Steps 3 and 4: Preparation of cured film

In the same manner as in steps 3 and 4 of Example 1, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, the patterned cured film 2-1 and the patterned cured film 2-2 was not formed was prepared.

[Example 3]

Step 1: Preparation of Polymer A-3

Polymer A-3 was prepared in the same manner as in Example 1, except that 1.59 g (0.009 mol) of 2,4-toluene diisocyanate (TDI) was used instead of m-xylene diisocyanate (XDI). The weight average molecular weight of Polymer A-3 calculated|required by GPC method standard polystyrene conversion was 5,800 g/mol, and the dispersion degree was 1.85.

Step 2: Preparation of photosensitive composition 3

After mixing with a composition corresponding to Example 3 of Table 1 and dissolving at room temperature (25° C.), the photosensitive resin composition 3 was prepared by filtration through a 0.2 μm Millipore filter.

Steps 3 and 4: Preparation of cured film

In the same manner as in steps 3 and 4 of Example 1, except that the photosensitive resin composition 3 was used instead of the photosensitive resin composition 1, the patterned cured film 3-1 and the patterned cured film 3-2 was not formed was prepared.

[Example 4]

After mixing with a composition corresponding to Example 4 of Table 1 and dissolving at room temperature (25° C.), it was filtered through a 0.2 μm Millipore filter to prepare a photosensitive resin composition 4 . In addition, in steps 3 and 4 of Example 1, cured films 4-1 and 4-2 were prepared in the same manner except that the photosensitive resin composition 4 was used instead of the photosensitive resin composition 1.

[Comparative Examples 1 and 2]

After mixing the compositions corresponding to Comparative Examples 1 and 2 in Table 1 and dissolving them at room temperature (25° C.), they were filtered through a 0.2 μm Millipore filter to prepare photosensitive resin compositions 5 and 6. In addition, in steps 3 and 4 of Example 1, the cured films 5-1, 5-2, and 6-1 using the same method except that the photosensitive resin compositions 5 and 6 were used instead of the photosensitive resin composition 1. and 6-2.

Unit (wt%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 alkali
availability
Suzy A-1 10 10 A-2 10 A-3 10 A-4 ^(a) 10 10 photopolymerizable monomer ^(b) 3 3 3 3 3 3 photoinitiator ^(c) 1.5 1.5 1.5 1.5 1.5 1.5 Dispersion for light extraction ^(d) 15 15 15 0 15 0 solvent ^(e) 70.5 70.5 70.5 85.5 70.5 85.5 (a) : Cardo-based binder (KBR-101, Kyungin Corporation)
(b): dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku)
(c): Oxime-based initiator (Irgacure OXE-04, BASF)
(d): ZrO ₂ 40% by weight dispersion (SP40C, KC tech)
(e): propylene glycol monomethyl ether acetate (sigma Aldrich)

[Experimental Example 1] Sensitivity measurement

The pattern sizes and sensitivities of the cured films 1-1 to 6-1 prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured. As for the sensitivity, based on the size of the 10um hole pattern measured using a Hitachi S-9260, the energy to realize a 10 micro hole was confirmed, and the sensitivity measurement results are listed in Table 2 below. did.

[Experimental Example 2] Measurement of refractive index

Using an ellisometer (M-2000, J.A. Woollam), the refractive indices of the cured films 1-2 to 6-2 prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured, and the results are shown in the table below. 2 is described.

[Experimental Example 3] Measurement of transmittance and reflectance

Using a reflectometer (CM-3600A, Konica Minolta), the transmittance and reflectance of the cured films 1-2 to 6-2 prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured. The transmittance was measured using the transmittance mode, and the reflectance was measured using the reflection mode to measure the SCE value, and the results are shown in Table 2 below.

Sensitivity (mJ/cm ² ) refractive index Permeability (%) Reflectance (%)_SCE Example 1 30 1.71 93.2 3.27 Example 2 40 1.72 93.9 3.25 Example 3 40 1.70 92.5 3.32 Example 4 25 1.68 92.2 3.12 Comparative Example 1 - 1.67 91.5 3.62 Comparative Example 2 40 1.61 90.2 3.58

As shown in Table 2, the cured film prepared with the photosensitive resin composition according to Examples 1 to 4 has significantly improved transmittance and reflectance compared to Comparative Examples 1 and 2, and improved refractive index can be realized even when the dispersion of the same content is used. confirmed that there is.

In addition, as in Comparative Examples 1 and 2, it was found that the photosensitive resin composition using the conventional alkali-soluble resin could not realize a pattern when the dispersion for light extraction was used together.

Therefore, the photosensitive resin composition according to the present invention can provide a cured film having excellent optical properties while realizing a precise pattern, and can provide an organic light emitting device with improved light extraction efficiency.

Although the embodiments of the present invention have been described in more detail with reference to the accompanying drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be made within the scope without departing from the technical spirit of the present invention. . Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technical ideas within the equivalent range should be construed as being included in the scope of the present invention.

Claims (18)

A polymer comprising repeating units represented by the following Chemical Formulas 1 and 2, and including a moiety represented by the following Chemical Formula 3 at the terminal thereof.
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
L ₁ and L ₃ are each independently (C1-C20)alkylene, (C6-C20)arylene or (C3-C20)heteroarylene;
L ₂ is -C(=O)- or -SO ₂ -;
L ₄ and L ₅ are each independently a single bond or (C1-C20)alkylene;
Ring A is a (C6-C20) aromatic ring or a (C3-C20) alicyclic ring;
Ar is

, (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;
Ar ^a and Ar ^b are each independently (C6-C20)arylene, (C3-C20)heteroarylene, (C3-C20)cycloalkylene or (C2-C20)heterocycloalkylene;
L ^a and L ₆ are each independently (C1-C20)alkylene;
R ₁ is hydrogen or (C1-C20)alkyl;
X ₁ to X ₃ are each independently a single bond, -C(=O)NH-, or -NHC(=O)-;
p to r are each independently an integer from 1 to 10;
Arylene, heteroarylene, cycloalkylene and heterocycloalkylene of Ar, Ar ^a and Ar ^b are further selected from (C1-C20)alkyl, (C1-C20)alkoxy, amino and halogen with one or more substituents may be substituted. The method of claim 1,
wherein L ₁ and L ₃ are each independently (C1-C10)alkylene or (C6-C12)arylene;
The A ring is a (C6-C12) aromatic ring, the polymer. The method of claim 1,
The repeating unit represented by the formula (1) is a polymer represented by the following formula (11).
[Formula 11]

In the above formula (11),
each L ₁ is independently (C1-C10)alkylene or (C6-C12)arylene;
p is an integer from 1 to 5; The method of claim 1,
The repeating unit represented by the formula (2) is a polymer represented by the following formula (12).
[Formula 12]

In the above formula (12),
L ₃ is (C1-C10)alkylene or (C6-C12)arylene;
L ₄ and L ₅ are each independently a single bond or (C1-C10)alkylene;
Ar is

or (C6-12)arylene;
Ar ^a and Ar ^b are each independently (C6-C12)arylene;
L ^a is (C1-C10)alkylene;
q and r are each independently an integer from 1 to 5;
Arylene of Ar, Ar ^a and Ar ^b may be further substituted with one or more substituents selected from (C1-C10)alkyl, (C1-C10)alkoxy, amino and halogen. The method of claim 1,
Wherein Ar is selected from the following structure, the polymer.

In the above structure,
R ₁₁ is (C1-C6)alkyl;
R ₁₂ and R ₁₃ are each independently hydrogen or (C1-C6)alkyl;
L ₁₁ is (C1-C6)alkylene;
n is 1 or 2. The method of claim 1,
The moiety represented by the formula (3) is a polymer represented by the following formula (13).
[Formula 13]

In Formula 13,
R ₁ is hydrogen or (C1-C10)alkyl;
L ₆ is (C1-C10)alkylene. The method of claim 1,
The polymer is represented by the following formula (14), the polymer.
[Formula 14]

In the formula (14),
R ₁ is hydrogen or (C1-C6)alkyl;
L ₁ , L ₃ and L ₁₂ are each independently (C1-C6)alkylene or (C6-C12)arylene;
L ₄ and L ₅ are each independently a single bond or (C1-C6)alkylene;
L ₆ is (C1-C6)alkylene;
Ar is

or

ego;
R ₂₁ to R ₂₃ are each independently hydrogen or (C1-C6)alkyl;
L ₂₁ is (C1-C6)alkylene;
p, q and s are each independently an integer from 1 to 3;
x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1. The method of claim 1,
The polymer is selected from the following structure.

In the above structure,
x and y are each independently real numbers greater than 0 and less than 1 as a mole fraction, and x+y=1. According to any one of claims 1 to 8 selected from,
The polymer has a weight average molecular weight of 2000 g/mol to 10000 g/mol. 10. A photosensitive resin composition comprising a polymer according to any one of claims 1 to 9. 11. The method of claim 10,
The photosensitive resin composition further comprises a photopolymerizable monomer, a dispersion for light extraction, and a photoinitiator. 12. The method of claim 11,
The photopolymerizable monomer is a polyfunctional monomer having an ethylenically unsaturated bond, the photosensitive resin composition. 12. The method of claim 11,
The light extraction dispersion is at least one selected from zirconium oxide, titanium oxide, antimony oxide, cerium oxide, selenium oxide, aluminum oxide, yttrium oxide, zinc oxide, zinc sulfide, and mixtures thereof, the photosensitive resin composition. 12. The method of claim 11,
The photoinitiator is at least one selected from an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a benzoin-based compound, an imidazole-based compound, a xanthone-based compound, a phosphine-based compound, and an oxime-based compound, the photosensitive resin composition. 12. The method of claim 11,
The photosensitive resin composition, wherein the solid content is 10 to 80% by weight based on the total photosensitive resin composition. 16. The method of claim 15,
The photosensitive resin composition comprises 5 to 80% by weight of the polymer according to any one of claims 1 to 9, 5 to 70% by weight of the photopolymerizable monomer, 0 to 50% by weight of the dispersion for light extraction based on the solid content, 1 to 15% by weight of the photoinitiator, the photosensitive resin composition. The cured film obtained by hardening|curing the photosensitive resin composition of Claims 11-16. An organic electronic device comprising the cured film according to claim 17 .