KR20170043084A - A self-light emitting photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a self-light emitting photosensitive resin composition comprising a photopolymerization initiator including one or more types selected from a group consisting of quantum dot particles, an alkali soluble resin, a photopolymerizable compound, an acylphosphine oxide and an oxime compound, and a solvent, and to a color filter and a display device comprising the same. The self-light emitting photosensitive resin composition has excellent light emitting properties while reverse taper does not occur.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-luminescent photosensitive resin composition, a color filter including the self-luminescent photosensitive resin composition,

The present invention relates to a self-luminescent photosensitive resin composition, a color filter and a display device comprising the same, and more particularly to a self-luminescent photosensitive resin composition comprising a self-luminescent photosensitive resin composition, A photopolymerization initiator comprising a photopolymerization initiator and a solvent, and a color filter and a display device containing the same.

BACKGROUND ART Color filters are widely used in image pickup devices, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding.

The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between each pixel having a size of several tens to several hundreds of micrometers and a plurality of colors Red, green, and blue) arranged in a predetermined order are stacked in order.

The color filter is prepared by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed by spin coating and then heating and drying (Hereinafter also referred to as " post-baking ") is repeated for each color to form pixels of each color It is mainly manufactured by the method. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

The pigment dispersion method, which is one of the methods of manufacturing the color filter, is a method of dispersing a photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an epoxy resin, a solvent and other additives on a transparent substrate provided with a black matrix A method of forming a colored thin film by repeating a series of processes such as coating, exposing a pattern to be formed, removing non-exposed portions with a solvent, and thermally curing, And is being actively applied.

In recent years, a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages is required not only excellent pattern characteristics but also high color reproducibility and further improved performance such as high brightness and high contrast ratio.

However, the color reproduction is realized when the light emitted from the light source is transmitted through the color filter. In this process, a part of the light is absorbed by the color filter to lower the light efficiency. Due to the pigment characteristics as a color filter, There are fundamental limitations.

As a method for solving such a problem, there is a method of manufacturing a color filter using a quantum dot photosensitive resin composition. When a quantum dot is used, a light emission waveform can be narrowed, a high color rendering capability can not be realized in a pigment, and an excellent luminance characteristic can be obtained. However, there is a problem that the light efficiency is lowered during the hard bake process, and further development is required.

It is an object of the present invention to provide a self-luminescent photosensitive resin composition which does not cause a decrease in light efficiency and a defective photosensitive property.

It is another object of the present invention to provide a color filter and a display device made of the self-luminescent photosensitive resin composition.

In order to achieve the above object,

The present invention relates to a self-luminescent photosensitive resin composition comprising a quantum dot particle, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the photopolymerization initiator comprises at least one member selected from the group consisting of an acylphosphine compound and an oxime compound.

The present invention also provides a color filter made of the self-luminescent photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

Since the self-luminescent photosensitive resin composition of the present invention can emit light by itself, it is possible to prevent deterioration of the light efficiency during the hard bake process, thereby realizing more excellent light efficiency.

Further, the self-luminescent photosensitive resin composition of the present invention is excellent in color reproducibility, has a wide viewing angle, and has no reverse taper.

In addition, the self-luminescent photosensitive resin composition of the present invention has high sensitivity and can form an excellent fine pattern.

In addition, the color filter and the display device manufactured using the self-luminescent photosensitive resin composition of the present invention have an extremely excellent luminance.

1 is a photograph showing a color filter in which no reverse taper is generated.
2 is a photograph showing a color filter in which a reverse taper occurs.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a self-luminescent photosensitive resin composition comprising a quantum dot particle, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the photopolymerization initiator comprises at least one selected from the group consisting of acylphosphine-based compounds and oxime-based compounds.

In a display device including a conventional color filter made of a photosensitive resin composition, the color is realized by transmitting white light through the color filter. However, in this process, there is a problem that a part of light is absorbed by the color filter and the light efficiency is lowered.

In order to solve the above-mentioned problems, the present invention provides a self-emitting photosensitive resin composition including quantum dot particles self-emitting by light of a light source and reducing loss of light to realize better light efficiency.

In addition, there is a problem that a reverse taper occurs when a pattern is formed using a conventional self-emitting photosensitive resin composition.

In order to solve the above problems, the present invention uses a photopolymerization initiator containing at least one selected from the group consisting of an acylphosphine compound and an oxime compound to prevent occurrence of reverse taper and to form an excellent fine pixel pattern To provide a self-luminescent photosensitive resin composition.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Qdot  particle

A quantum dot is a nano-sized semiconductor material. The atoms form molecules, and the molecules form a cluster of small molecules called clusters to form nanoparticles. These nanoparticles are called quantum dots, especially when they have semiconductor properties.

The quantum dot emits energy according to the energy band gap itself when it reaches the excited state from the outside, and it is called self-luminescence.

The self-luminescent photosensitive resin composition of the present invention comprises such self-emission quantum dot particles, and the color filter produced therefrom can emit light by light irradiation.

In a typical display device including a color filter, white light is transmitted through a color filter to realize color, in which part of the light is absorbed by the color filter, resulting in a decrease in light efficiency.

However, in the case of including a color filter made of the self-luminescent photosensitive resin composition of the present invention, since the color filter emits light by the light of the light source, it is possible to realize more excellent light efficiency.

In addition, since color light is emitted, color reproducibility is better, and light is emitted in all directions due to optical luminescence, so that viewing angle can also be improved.

The quantum dot particle of the present invention is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation with light, and examples thereof include a II-VI semiconductor compound, a III-V semiconductor compound, an IV- And a Group IV element or a compound containing the group IV element.

Specifically, the II-VI group semiconductor compound may be, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, or a mixture thereof.

 Trivalent compounds which are CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; And

CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

Specifically, the III-V semiconductor compound may be, for example, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb and mixtures thereof.

Trivalent compounds which are GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; And

And gallium arsenide compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and mixtures thereof.

Specifically, for example, the IV-VI group semiconductor compound may be SnS, SnSe, SnTe, PbS, PbSe, PbTe, or a mixture thereof.

SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And

SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

The Group IV element or a compound containing the Group IV element is specifically an elemental compound, for example, Si, Ge and a mixture thereof; And

SiC, SiGe, and a mixture of these elements.

Further, the quantum dot particles may have a homogeneous single structure; A dual structure such as a core-shell structure and a gradient structure; Or a mixed structure thereof.

In the core-shell double structure, the material forming each shell and the core may be different semiconductor compounds.

For example, the core may comprise at least one material selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO.

For example, the shell may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe.

As the colored photosensitive resin composition used in the production of a typical color filter contains red, green, and blue colorants for color implementation, the quantum dot particles can be classified as red quantum dot particles, green quantum dot particles, and blue quantum dot particles, Includes at least one selected from the group consisting of red quantum dot particles, green quantum dot particles and blue quantum dot particles.

The quantum dot particles can be prepared by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy process (MBE) process.

The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent naturally coordinates to the surface of the quantum dot crystal to act as a dispersing agent to control crystal growth. It is possible to control the size growth of the quantum dot particles through a process that is easier and less expensive than the vapor deposition method such as a minute magnet epitaxy.

The quantum dot particles of the present invention are contained in an amount of 3 to 80% by weight, preferably 5 to 70% by weight, based on the total weight of the solid content of the self-luminescent photosensitive resin composition.

When the quantum dot particles are contained in an amount of less than 3% by weight, the light emitting efficiency may be insufficient. When the quantum dot particles are contained in an amount exceeding 80% by weight, the content of the other composition may be insufficient.

In the present invention, the solid content weight of the self-luminescent photosensitive resin composition means the total weight of the remaining components excluding the solvent of the self-luminescent photosensitive resin composition.

(B) an alkali-soluble resin

The alkali-soluble resin of the present invention is not particularly limited as long as it can make the non-exposed portion of the photosensitive resin layer formed using the self-luminescent photosensitive resin composition to be made soluble in alkali and can serve to retain the exposed region Do not.

The alkali-soluble resin may be a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer.

Examples of the monomer containing a carboxyl group include unsaturated carboxylic acids containing at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, and the like .

Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride. Specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride.

The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof. Specific examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-acryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), and phthalic acid mono (2-methacryloyloxyethyl).

Further, the unsaturated polycarboxylic acid may be mono (meth) acrylate of the dendritic dicarboxylic polymer, and specifically includes, for example, ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate And the like.

Among these compounds, acrylic acid or methacrylic acid is preferred because of excellent solubility in copolymerization reactivity and developability.

The carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- And unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as aminoethyl (meth) acrylate;

(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as a carboxylate, a carboxylate, a carboxylate, a pyranyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate and pinenyl (meth) acrylate;

3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds containing thermosetting substituents such as oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane;

Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;

Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile;

Acrylates such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methyl glycidyl 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- 3- (methacryloyloxyethyl) -3-ethyloxetane, 2 (methacryloyloxyethyl) oxetane, 2- 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxy) (Methacryloyloxyethyl) -2-phenyloxetane, 2, 2-difluoro-3- (methacryloyloxyethyl) oxetane, 2- 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) Oxyethyl) oxetane, 3- (acryloyloxyethyl) -2-t 2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3 - (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4 (Meth) acrylate, 3,4-epoxytricyclodecan-8-yl (meth) acrylate, 3,4-epoxytricyclodecan- (Meth) acrylate, epoxylated dicyclopentanyloxyethyl (meth) acrylate (2- (3,4-epoxytricyclodecan-9-yloxy) An aliphatic polycyclic compound having an unsaturated bond with an epoxy group such as tricyclodecan-8-yloxy) ethyl (meth) acrylate and epoxidized dicyclopentanyloxyhexyl (meth) acrylate;

Epoxy compounds such as dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, cyclononane, bicycloundecane, tricyclododecane, bicyclododecane and tricyclododecane;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Maleimide caproate, N-succinimidyl-3-maleimide propionate, and N- (9-acridinyl) maleimide.

These monomers may be used alone or in combination of two or more.

The alkali-soluble resin preferably has an acid value (KOH mg / g) of 30 to 150. When the acid value is in the above range, the solubility in the developer is improved, the unexposed portions are easily dissolved and the sensitivity is increased, and consequently the pattern of the exposed portion remains at the time of development to improve the film remaining raio.

Acid value is a value measured as potassium hydroxide (KOH) necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The weight average molecular weight of the alkali-soluble resin measured by gel permeation chromatography (GPC, using tetrahydrofuran as an elution solvent) in terms of polystyrene is 3000 to 100000.

When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

The content of the alkali-soluble resin of the present invention is 5 to 80% by weight, preferably 10 to 70% by weight based on the total weight of the solid content of the self-luminescent photosensitive resin composition.

When the content of the alkali-soluble resin is in the range of 5 to 80% by weight, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion The dropout of the pixel portion is improved.

(C) Photopolymerization  compound

The photopolymerizable compound contained in the self-luminescent photosensitive resin composition of the present invention should be a compound capable of polymerizing under the action of the photopolymerization initiator (D) to be described later. A monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional photopolymerizable compound, and the like, but are not limited thereto.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- And vinyl pyrrolidone. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo).

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like. Commercially available products include Aronix M-210, M-1100 and 1200 KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

The polyfunctional photopolymerizable compound having three or more functional groups is specifically exemplified by trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, Propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

Also, it may include at least one member selected from the group consisting of compounds represented by the following formulas (22) and (23) which are dipentaerythritol (poly) acrylates having a hydroxyl group or a carboxyl group.

[Chemical Formula 22]

(23)

Each of R ₆ to R ₁₀ is independently an acrylate group or a methacrylate group,

Wherein R < ₁₁ > is hydrogen, an acryloyl group or a methacryloyl group,

Each of R ₁₂ to R ₁₄ is independently a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group or OR ₁₆ ,

R ₁₅ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group, R ₁₆ or -C (═O) CH ₂ CH ₂ C (═O) OH,

At least one of R ₁₂ to R ₁₅ is an acrylate group or a methacrylate group,

Wherein R < ₁₆ >

≪ EMI ID =

Each of R ₁₇ and R ₁₈ is independently an acrylate group or a methacrylate group,

R ₁₉ is hydrogen, an acryloyl group, a methacryloyl group or -C (= O) CH ₂ CH ₂ C (= O) OH.

Among the photopolymerizable compounds exemplified above, it is preferable to use a bifunctional or higher functional polyfunctional monomer, and more preferably a pentafunctional or higher functional monomer containing a carboxyl group.

The use of a photopolymerizable compound having five or more functional groups makes the formation of a pixel pattern more excellent. In particular, when a polyfunctional monomer having five or more functional groups including a carboxyl group is used, there is no deterioration in luminescence characteristics due to aggregation of the quantum dots, A pixel pattern excellent in luminance can be formed.

The photopolymerizable compound is contained in an amount of 5 to 70% by weight, and preferably 7 to 45% by weight based on the total weight of the solid content of the self-luminescent photosensitive resin composition of the present invention.

In the photopolymerizable compound, the pixel pattern for the light source is easily formed in the range of 5 to 70% by weight, and the strength and smoothness of the pixel portion are improved.

On the other hand, if the photopolymerizable compound is contained in an amount of less than 5% by weight, the degree of photo-curability is lowered to form a pixel pattern, and if it exceeds 70% by weight, the pattern may be peeled off.

(D) Light curing Initiator

The photopolymerization initiator contained in the self-luminescent photosensitive resin composition of the present invention is characterized by containing at least one selected from the group consisting of acylphosphine-based compounds and oxime-based compounds.

The inclusion of such a compound can prevent the occurrence of a reverse taper at the time of pattern formation.

The acylphosphine-based compound includes at least one selected from the group consisting of a monoacylphosphine-based compound and a bisacylphosphine-based compound.

The monoacylphosphine-based compound includes a compound represented by the following formula (1).

[Chemical Formula 1]

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,

R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,

The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Examples of the compound corresponding to the compound of Formula 1 include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure TPO, Basf) and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate Irgacure TPO-L, Basf).

The bisacylphosphine-based compound includes a compound represented by the following general formula (2).

(2)

And R ₄ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, An aryloxy group having 5 to 30 carbon atoms,

Each R ₅ is the same or different and is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, An aryloxy group having 1 to 30 carbon atoms,

The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Examples of the compound corresponding to the compound of Formula 2 include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819, manufactured by Basf).

The oxime compound is a compound containing at least one member selected from the group consisting of a fluorene group, a carbazole group and a diphenylsulfide group.

The oxime compound preferably includes at least one selected from the group consisting of the following chemical formulas (3) to (21). It is also possible to use two or more oxime compounds in combination.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The photopolymerization initiator may further include an acetophenone-based compound.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Methyl-1- [4- (1-methylvinyl) phenyl] propane, and 2-hydroxy-2- -1-one oligomers and the like.

In addition, the photopolymerization initiator may further include a triazine-based compound or a non-thiol-based compound in order to improve the strength and the contact hole property.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5- triazine and 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the non-imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole and phenyl groups in the 4,4', 5,5 ' An imidazole compound substituted by a carboalkoxy group, and the like. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

As long as the effect of the present invention is not impaired, other photopolymerization initiators commonly used in this field may be further used in combination.

Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-di (N, N'-dimethylamino) -benzophenone.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone .

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

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

On the other hand, when the photopolymerization initiator (D1) is used in combination with the photopolymerization initiator (D) in the present invention, the colored photosensitive resin composition containing the photopolymerization initiator (D1) has a higher sensitivity and productivity can be improved when forming the color filter.

As the photopolymerization initiator, an amine compound or a carboxylic acid compound can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine;

4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- And aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, and aromatic amine compounds are preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The photopolymerization initiator is contained in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight based on the total weight of the solid content of the self-luminescent photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in the range of 0.1 to 20% by weight, the self-light-sensitive photosensitive resin composition may have a high sensitivity and the formation of a fine pixel pattern may be improved.

(E) Solvent

The solvent may be any solvent that is effective in dissolving other components contained in the self-luminescent photosensitive resin composition without any particular limitation, and may be selected from ethers, acetates, aromatic hydrocarbons, Ketones, alcohols or esters.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

These solvents may be used alone or in combination of two or more.

The solvent is preferably an organic solvent having a boiling point in the range of 100 ° C to 200 ° C in terms of coatability and dryness, and examples thereof include alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, Propyleneglycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and 3-ethoxypropionate, and more preferably propyleneglycol monomethylether acetate, -Methoxypropionate, and the like.

The solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the self-luminescent photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

(F) Additive

The additive may be optionally added as needed. For example, the additive may include at least one selected from the group consisting of another polymer compound, a hardener, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- have.

Among these additives, it is most preferable to include a surfactant.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane .

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

The curing auxiliary compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant can be used for further improving the film formation of the self-luminescent photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like can be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF- -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

The above-exemplified surfactants may be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content in the self-luminescent photosensitive resin composition.

Examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol .

The ultraviolet absorber is not particularly limited, but specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone .

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The present invention also provides a color filter made of the self-luminescent photosensitive resin composition of the present invention.

When the color filter of the present invention is applied to an image display device, the color filter can emit light by the light of the display device light source and thus exhibit higher light efficiency.

In addition, since color light is emitted, color reproducibility is better and light is emitted in all directions due to self-emission, so that the viewing angle can also be improved.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a substrate of a color filter itself, or may be a portion where a color filter is placed on a display device or the like, and the substrate is not particularly limited.

The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer containing the self-luminescent photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminescent photosensitive resin composition and exposing, developing and thermally curing the self-luminescent photosensitive resin composition in a predetermined pattern.

The pattern layer formed of the self-luminescent photosensitive resin composition may include a red pattern layer including red quantum dot particles, a green pattern layer including green quantum dot particles, and a blue pattern layer including blue quantum dot particles. During the light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

When the pattern layer is applied to an image display apparatus, the light emitted from the light source is not particularly limited, but a light source that emits blue light in terms of better color reproducibility can be used.

According to another embodiment of the present invention, the pattern layer may include only a pattern layer of two colors selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer may further include a transparent pattern layer not containing quantum dot particles.

In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, thereby exhibiting blue color.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix. Further, it may further comprise a protective film formed on the pattern layer of the color filter.

Further, the present invention provides a display device including the color filter.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

The display device of the present invention may include a color filter including a red pattern layer including red quantum dot particles, a green pattern layer including green quantum dot particles, and a blue pattern layer including blue quantum dot particles. In such a case, the emitted light of the light source is not particularly limited when applied to a display device, but a light source that emits blue light is preferable from the viewpoint of better color reproducibility.

According to another embodiment of the present invention, the display device of the present invention may include a color filter including only a pattern layer of two colors selected from the group consisting of a red pattern layer, a green pattern layer and a blue pattern layer. In such a case, the color filter further includes a transparent pattern layer not containing quantum dot particles.

In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, thereby exhibiting blue color.

INDUSTRIAL APPLICABILITY The display device of the present invention is excellent in light efficiency, exhibits high luminance, excellent in color reproducibility, and has a wide viewing angle.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example  One. Qdot  Particle manufacturing

0.4 mmol of CdO, 4 mmol of zinc acetate and 5.5 mL of oleic acid were placed in a reactor together with 20 mL of 1-octadecene and heated to 150 ° C to react.

The reaction was then left under vacuum at 100 mTorr for 20 minutes to remove the acetic acid formed by the displacement of oleic acid into zinc. Then, a transparent mixture was obtained by applying heat at 310 DEG C, and after maintaining the temperature at 310 DEG C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine, and Se And S solution were rapidly injected into a reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions.

The resulting mixture was grown at 310 ° C for 5 minutes, and growth was stopped using an ice bath. Thereafter, the precipitate was precipitated with ethanol, and the quantum dots were separated using a centrifugal separator. The excess impurities were washed with chloroform and ethanol to obtain particles having a core particle size and shell thickness summed to 3 to 5 nm Green CdSe (core) / ZnS (shell) structures were prepared.

Synthetic example  1. Alkali-soluble resin synthesis

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were put and stirred to prepare a monomer dropping tank. 6 parts by weight of n-dodecanethiol And 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropwise.

Then, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours each. After 1 hour, the temperature was elevated to 110 DEG C and maintained for 3 hours. Then, a gas introduction tube was introduced to mix oxygen / nitrogen = 5 / Gas bubbling was started.

Then, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were charged into a flask, The reaction was continued and then cooled to room temperature to obtain an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000 and an acid value of 114 mgKOH / g.

< Self-luminous  Preparation of Photosensitive Resin Composition &gt;

Example  1 to 26 and Comparative Example  1 to 5.

The solid contents in the self-luminescent photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were prepared with the compositions shown in Tables 1 and 2 below.

The self-light-sensitive photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were finally prepared by mixing 20% by weight of the solid content and 80% by weight of propylene glycol monomethyl ether acetate as a solvent.

(Unit: wt%) division Qdot Alkali-soluble resin Photopolymerization
compound Photopolymerization initiator C-1 C-2 D-1 D-2 D-3 D-4 D-5 D-6 D-7 D-8 D-9 D-10 D-11 D-12 Example 1 30 30 20 15 5 - - - - - - - - - - - Example 2 30 30 20 15 - 5 - - - - - - - - - - Example 3 30 30 20 15 - - 5 - - - - - - - - - Example 4 30 30 20 15 2.5 2.5 - - - - - - - - - - Example 5 30 30 20 15 2.5 - 2.5 - - - - - - - - - Example 6 30 30 20 15 - 2.5 2.5 - - - - - - - - - Example 7 30 30 20 15 - - - - - - 5 - - - - - Example 8 30 30 20 15 3 - - 2 - - - - - - - - Example 9 30 30 20 15 3 - - - 2 - - - - - - - Example 10 30 30 20 15 3 - - - - 2 - - - - - - Example 11 30 30 20 15 - - - 2 - - 3 - - - - - Example 12 30 30 20 15 - - - - 2 - 3 - - - - - Example 13 30 30 20 15 - - - - - 2 3 - - - - - Example 14 30 30 20 15 3 - - - - - 2 - - - - - Example 15 30 30 20 15 - - - - - - - 5 - - - - Example 16 30 30 20 15 - - - - - - - - 5 - - - Example 17 30 30 20 15 - - - - - - - - - 5 - - Example 18 30 30 20 15 - - - - - - 2.5 2.5 - - - - Example 19 30 30 20 15 - - - - - - 2.5 - 2.5 - - - Example 20 30 30 20 15 - - - - - - 2.5 - - 2.5 - - Example 21 30 30 20 15 3 - - - - - - - - - 2 - Example 22 30 30 20 15 3 - - - - - - - - - - 2 Example 23 30 30 20 15 - - - - - - - - - - 2 - Example 24 30 30 20 15 - - - - - - 3 - - - - 2 Example 25 30 30 20 15 3 - - One - - One - - - - - Example 26 30 30 20 15 3 - - - - - One One - - - - Comparative Example 1 30 30 20 15 - - - 5 - - - - - - - Comparative Example 2 30 30 20 15 - - - - 5 - - - - - - - Comparative Example 3 30 30 20 15 - - - - - 5 - - - - - - Comparative Example 4 30 30 20 15 - - - - - - - - - - 5 - Comparative Example 5 30 30 20 15 - - - - - - - - - - - 5

Quantum dots: CdSe (core) / ZnS (shell) structure green quantum dot particles prepared in Production Example 1

Alkali-soluble resin: The alkali-soluble resin prepared in Synthesis Example 1

Photopolymerizable compound

C-1: dipentaerythritol pentaacrylate succinic acid monoester (5-functional photochemically synthesized compound containing carboxylic acid, TO-1382, produced by Donga Chemical Co., Ltd.)

C-2: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator

D-1: monoacylphosphine-based compound, Irgacure TPO (manufactured by Basf)

D-2: monoacylphosphine compound, Irgacure TPO-L (manufactured by Basf)

D-3: Bisacylphosphine-based compound, Irgaquer-819 (manufactured by Basf)

D-4: Acetophenone compound, Irgaquer-907 (manufactured by Basf)

D-5: Acetophenone compound, Irgaquer-651 (manufactured by Basf)

D-6: Acetophenone compound, Irgaquer-184 (manufactured by Basf)

D-7: oxime compound, Irgaure 0XE01 (manufactured by Basf)

D-8: Oxime compound, [Formula 8]

D-9: oxime compound,

D-10: oxime compound,

D-11: a non-imidazole-based compound, CZ-HABI (Tronisizer)

D-12: Triazine compound, TAZ-101 (Midori Chemical)

Experimental Example  1. Physical property measurement

Each of the self-luminescent photosensitive resin compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 5 was coated on a glass substrate by a spin coating method and then placed on a heating plate and maintained at a temperature of 100 for 3 minutes to form a thin film. Then, a test photomask having a transmittance of 20 mm × 20 mm square and a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with light (365 nm) at an exposure dose of 200 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI CO., LTD.

The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 캜 for 10 minutes to prepare a color filter pattern. The film thickness of the self-emission color pattern prepared above was 3.0 mu m.

1-1. Taper  Angle measurement

Each of the color filters prepared above was measured for taper angle using SEM. The results are shown in Table 2 below.

If the taper angle is 0 to 90 degrees or less, it is a net taper, and if it is more than 90 degrees, it is an inverse taper.

1-2. Measurement of intensity

In each of the color filters prepared above, a photo-converted region was measured through a 365 nm tube type 4W UV illuminator (VL-4LC, VILBER LOURMAT) on a pattern portion formed in a 20 mm x 20 mm square pattern. In Comparative Examples 1 to 5, the light intensities in the 550 nm region were measured using a spectrum meter (manufactured by Ocean Optics).

It can be judged that the higher the intensity of light measured, the better the self-luminescence characteristic. The luminescence intensity measurement result is shown in Table 2 below.

The hard bake was conducted at a temperature of 230 DEG C for 60 minutes to measure the intensity before hard bake and the intensity after hard bake to confirm the level at which the luminous efficiency was maintained. And was expressed by the light emission intensity retention ratio.

division Taper angle (°) Emission intensity Emission intensity
Retention rate (%) Example 1 31 Sun Taper 53614 56.4 Example 2 30 Sun Taper 55696 55.8 Example 3 34 Sun Taper 56211 54.9 Example 4 32 Sun Taper 54215 58.2 Example 5 32 Sun Taper 55904 52.7 Example 6 32 Sun Taper 55821 58.5 Example 7 39 Sun Taper 52352 53.2 Example 8 38 Sun Taper 52333 57.4 Example 9 35 Sun Taper 53603 55.5 Example 10 36 Sun Taper 53595 53.3 Example 11 34 Sun Taper 53200 54.3 Example 12 32 Sun Taper 52234 51.2 Example 13 32 Sun Taper 54083 55.0 Example 14 40 Sun Taper 51023 50.2 Example 15 41 Sun Taper 51385 52.8 Example 16 39 Sun Taper 56204 54.2 Example 17 42 Sun Taper 52343 53.4 Example 18 38 Sun Taper 56852 52.5 Example 19 39 Sun Taper 52521 55.2 Example 20 40 Sun Taper 55321 54.3 Example 21 41 Sun Taper 43035 41.4 Example 22 38 Sun Taper 43520 39.8 Example 23 38 Sun Taper 44054 42.3 Example 24 39 Sun Taper 42606 43.1 Example 25 38 Sun Taper 56488 53.3 Example 26 40 Sun Taper 55870 54.1 Comparative Example 1 130 Reverse taper 51324 53.2 Comparative Example 2 133 Reverse taper 53218 55.7 Comparative Example 3 135 Reverse taper 54286 52.1 Comparative Example 4 40 Sun Taper 29499 28.4 Comparative Example 5 40 Sun Taper 23852 28.8

From the results shown in Table 2, it was observed that Examples 1 to 26, which are the self-luminescent photosensitive resin compositions of the present invention, did not generate reverse taper, and that the luminescence intensity and the luminescence intensity maintenance rate were both excellent.

On the other hand, the self-luminescent photosensitive resin compositions of Comparative Examples 1 to 5, which did not contain an acylphosphine compound or an oxime compound as a photopolymerization initiator, showed poor results in at least one of the above three items.

More specifically, the self-luminescent photosensitive resin compositions of Comparative Examples 1 to 3 containing only an acetophenone-based compound as a photopolymerization initiator were excellent in luminescence intensity and luminescence intensity retention, but showed a problem of inversion taper due to incomplete curing.

In addition, the self-luminescent photosensitive resin compositions of Comparative Examples 4 and 5 including a nonimidazole-based compound and a triazine-based compound had a high degree of curing and did not cause reverse taper. However, the problem of poor luminescence intensity and luminescence intensity retention rate of quantum dots in the POB process Respectively.

Accordingly, it has been found that the self-luminescent photosensitive resin composition of the present invention comprising at least one selected from the group consisting of an acylphosphine-based compound and a oxime-based compound as a photopolymerization initiator does not generate reverse taper and exhibits excellent luminescent properties there was.

Claims (14)

A self-luminescent photosensitive resin composition comprising a quantum dot particle, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
Wherein the photopolymerization initiator comprises at least one selected from the group consisting of acylphosphine-based compounds and oxime-based compounds. The self-luminescent photosensitive resin composition according to claim 1, wherein the quantum dot particles comprise at least one selected from the group consisting of red quantum dot particles, green quantum dot particles and blue quantum dot particles. The self-luminescent photosensitive resin composition according to claim 1, wherein the acylphosphine-based compound comprises at least one selected from the group consisting of a monoacylphosphine-based compound and a bisacylphosphine-based compound. The self-luminescent photosensitive resin composition according to claim 3, wherein the monoacylphosphine-based compound comprises a compound represented by the following formula (1).
[Chemical Formula 1]

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,
R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,
The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The self-luminescent photosensitive resin composition according to claim 3, wherein the bisacylphosphine-based compound comprises a compound represented by the following formula (2).
(2)

And R ₄ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, An aryloxy group having 5 to 30 carbon atoms,
Each R ₅ is the same or different and is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, An aryloxy group having 1 to 30 carbon atoms,
The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The self-luminescent photosensitive resin composition according to claim 1, wherein the oxime-based compound has at least one structure selected from the group consisting of a fluorene group, a carbazole group, and a diphenyl sulfide group. The self-luminescent photosensitive resin composition according to claim 1, wherein the oxime compound comprises at least one selected from the group consisting of the following formulas (3) to (21).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The self-luminescent photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises two or more acylphosphine-based compounds. The self-luminescent photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises two or more oxime compounds. The self-luminescent photosensitive resin composition according to claim 1, wherein the photopolymerization initiator includes both an acylphosphine-based compound and an oxime-based compound. The self-luminescent photosensitive resin composition according to claim 1, wherein the photopolymerization initiator further comprises an acetone-based compound. The self-emitting photosensitive resin composition according to claim 1, wherein the self-emitting photosensitive resin composition comprises 3 to 80% by weight of quantum dot particles, 5 to 80% by weight of an alkali soluble resin, 5 to 70% by weight of a photopolymerizable compound, 0.1 to 20% by weight of a photopolymerization initiator % Of the total weight of the self-luminescent photosensitive resin composition, and 60 to 90% by weight of a solvent based on the total weight of the self-luminescent photosensitive resin composition. A color filter made of the self-luminescent photosensitive resin composition of claim 1. A display device comprising the color filter of claim 13.

Images