KR102174182B1 - A self-light emitting photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention is a self-luminous photosensitive resin composition comprising a photopolymerization initiator and a solvent comprising at least one selected from the group consisting of quantum dot particles, alkali-soluble resin, photopolymerizable compound, acylphosphine compound and oxime compound, comprising the same It relates to a color filter and a display device, wherein the self-luminous photosensitive resin composition of the present invention does not generate an inverse taper, and has an excellent effect in light emission characteristics.

Description

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

The present invention relates to a self-luminous photosensitive resin composition, a color filter and a display device including the same, and in more detail, 1 selected from the group consisting of quantum dot particles, alkali-soluble resins, photopolymerizable compounds, acylphosphine compounds, and oxime compounds. It relates to a self-luminous photosensitive resin composition comprising a photopolymerization initiator and a solvent comprising more than one species, a color filter and a display device comprising the same.

Color filters are widely used in imaging devices, liquid crystal displays (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 in order to block light at a boundary between each pixel having a size of about tens to hundreds of micrometers, and a plurality of colors (typically The pixel units in which the three primary colors (red, green, and blue) are arranged in a predetermined order are sequentially stacked.

In the color filter, a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue is uniformly coated on a substrate on which a black matrix is patterned by spin coating, followed by heating and drying (hereinafter,'preparative In some cases, the coating film formed by'baking') is exposed and developed, and if necessary, the operation of further heating and curing (hereinafter, sometimes 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, comprises a photosensitive resin composition including 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. It is a method of forming a colored thin film by repeating a series of processes of coating, exposing the pattern of the shape to be formed, removing the unexposed part with a solvent, and heat curing. LCDs such as mobile phones, notebook computers, monitors, and TVs are manufactured. It is being actively applied to

In recent years, even in the photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics, but also improved performance such as high luminance and high contrast ratio along with high color reproduction rate is required.

However, color reproduction is realized by transmitting the light irradiated from the light source through the color filter. In this process, part of the light is absorbed by the color filter, reducing the light efficiency, and due to the pigment characteristics as a color filter, perfect color reproduction is not possible. There is a fundamental limit to the impact.

As one of the methods for solving this problem, a method of manufacturing a color filter using a quantum dot photosensitive resin composition may be mentioned. Using quantum dots, it is possible to narrow the emission waveform, have a high color realization ability that cannot be realized in a pigment, and have excellent luminance characteristics. However, there is a problem in that the light efficiency decreases during the hard bake process, so further development is required.

An object of the present invention is to provide a self-luminous photosensitive resin composition in which light efficiency does not decrease and poor photosensitive properties do not occur.

In addition, an object of the present invention is to provide a color filter and a display device made of the self-luminous photosensitive resin composition.

To achieve the above object,

The present invention is a self-luminous photosensitive resin composition comprising a quantum dot particle, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,

The photopolymerization initiator provides a self-luminous photosensitive resin composition comprising at least one selected from the group consisting of an acylphosphine compound and an oxime compound.

In addition, the present invention provides a color filter made of the self-luminous photosensitive resin composition.

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

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

In addition, the self-luminous photosensitive resin composition of the present invention is excellent in color reproducibility, has a wide viewing angle, and has an effect that no reverse taper occurs.

In addition, the self-luminous photosensitive resin composition of the present invention can be highly sensitive to form an excellent fine pattern.

In addition, the color filter and display device manufactured by using the self-luminous photosensitive resin composition of the present invention has a very excellent effect of luminance.

1 is a photograph showing a color filter in which reverse taper does not occur.
2 is a photograph showing a color filter in which reverse taper has occurred.

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

The present invention is a self-luminous photosensitive resin composition comprising a quantum dot particle, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,

The photopolymerization initiator relates to a self-luminous photosensitive resin composition comprising at least one selected from the group consisting of an acylphosphine compound and an oxime compound.

In a display device including a conventional color filter made of a photosensitive resin composition, white light passes through the color filter to implement color. However, in this process, some of the light is absorbed by the color filter, thereby reducing the light efficiency.

In order to solve the above problems, the present invention aims to provide a self-luminous photosensitive resin composition capable of realizing more excellent light efficiency by reducing the loss of light including quantum dot particles that emit light by light of a light source.

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

In the present invention, in order to solve the above problems, a photopolymerization initiator containing at least one selected from the group consisting of acylphosphine compounds and oxime compounds is used to prevent reverse taper and to form an excellent fine pixel pattern with high sensitivity. It was intended to provide a self-luminous photosensitive resin composition capable of.

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

(A) Quantum dots particle

Quantum dots are nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots.

Quantum dots receive energy from the outside and when they reach an excited state, they emit energy according to their own energy band gap, which is called self-luminescence.

The self-luminous photosensitive resin composition of the present invention includes such self-luminous quantum dot particles, and a color filter manufactured therefrom may emit light by irradiation with light.

In a typical display device including a color filter, white light passes through the color filter to realize color. In this process, a part of the light is absorbed by the color filter, so light efficiency is degraded.

However, in the case of including the color filter made of the self-luminous photosensitive resin composition of the present invention, since the color filter is self-emitted by light from a light source, more excellent light efficiency can be realized.

In addition, since light having a color is emitted, color reproducibility is more excellent, and since light is emitted in all directions by optical luminescence, the viewing angle can 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 of light, and for example, a group II-VI semiconductor compound, a group III-V semiconductor compound, a group IV-VI semiconductor compound, And it may include one or more selected from the group consisting of a group IV element or a compound containing the same.

Specifically, the II-VI group semiconductor compound is, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and a binary compound of a mixture thereof;

CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnTe and mixtures of these three elements; And

CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a quaternary compound that is a mixture thereof.

Specifically, the III-V group semiconductor compound includes, for example, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and a binary compound of a mixture thereof;

GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and a mixture of trielement compounds thereof; And

GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and quaternary compound compounds which are mixtures thereof.

The IV-VI semiconductor compound may specifically include, for example, the compound is a binary compound of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof;

SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and a three-element compound as a mixture thereof; And

SnPbSSe, SnPbSeTe, SnPbSTe, quaternary element compounds which are mixtures thereof, etc. are mentioned.

The group IV element or a compound containing the same may specifically include, for example, elemental compounds such as Si, Ge, and mixtures thereof; And

SiC, SiGe, and a binary compound such as a mixture thereof.

In addition, the quantum dot particles are homogeneous (homogeneous) single structure; A dual structure such as a core-shell structure and a gradient structure; Or it may be a mixed structure thereof.

In the core-shell dual structure, materials constituting each core and shell may be different semiconductor compounds.

For example, the core may include at least one material selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO, but is not limited thereto.

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, but is not limited thereto.

Just as the colored photosensitive resin composition used in the manufacture of a conventional color filter contains red, green, and blue colorants for color realization, quantum dot particles can also be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. In contains 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 may be manufactured by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process.

The wet chemical process is a method of growing particles by putting a precursor material in an organic solvent. When the crystal is grown, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. It is possible to control the size growth of quantum dot particles through an easier and inexpensive process than long-term deposition methods such as molecular stone epitaxy.

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

When the quantum dot particles are included in an amount of less than 3% by weight, the luminous efficiency may be insignificant, and when the amount of the quantum dot particles exceeds 80% by weight, the content of other compositions may be insufficient, making it difficult to form a pixel pattern.

In the present invention, the weight of the solid content in the self-luminous photosensitive resin composition refers to the total weight of the remaining components excluding the solvent of the self-luminous photosensitive resin composition.

(B) alkali-soluble resin

The alkali-soluble resin of the present invention is not particularly limited as long as it can be removed by making the non-exposed portion of the photosensitive resin layer formed using the self-luminous photosensitive resin composition alkali-soluble and can serve to retain the exposed area. Does not.

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

The monomer containing the carboxyl group specifically includes, for example, an unsaturated carboxylic acid containing at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid. .

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

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

The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, and specifically, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryl) Royloxyethyl), phthalic acid mono (2-acryloyloxyethyl), and phthalic acid mono (2-methacryloyloxyethyl), and the like.

In addition, the unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, and specifically, for example, ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacryl Rate, etc. are mentioned.

Of the above compounds, acrylic acid or methacrylic acid is preferable because it has excellent copolymerization reactivity and solubility in developability.

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

Other monomers copolymerizable with the carboxyl group-containing monomer are specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate And unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as aminoethyl (meth)acrylate;

Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, menthyl (meth)acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as rate, pinanyl (meth)acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, and pinenyl (meth)acrylate;

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

Monosaturated 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, α-methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile;

Glycidyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, methylglycidyl(meth)acrylate, 3-(meth) Acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyl Oxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacrylo Yloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-3-ethyloxetane, 2 -Ethyl-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxyethyl)-2-penta Fluoroethyloxetane, 3-(methacryloyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloyloxyethyl)oxetane, 3-(methacrylo Yloxyethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane, 3-(acryloyloxymethyl )Oxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-2-triflo Romethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)- 2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4- Tetrafluorooxetane, 3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxyethyl)-2- Phenyloxetane, 2,2-difluoro-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2,2,4-trifluoro Oxetane, 3-(acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane, epoxidized dicyclodecanyl (meth)acrylate, 3,4-epoxytricyclodecane-8- Mono(meth)acrylate, 3,4-epoxytricyclodecane-8-yl(meth)acrylate, epoxidized dicyclopentanyloxyethyl(meth)acrylate (2-(3,4-epoxytricyclodecane- 9-yloxy)ethyl (meth)acrylate, 2-(3,4-epoxytricyclodecane-8-yloxy)ethyl (meth)acrylate and epoxidized dicyclopentanyloxyhexy (meth)acrylate, etc. Aliphatic polycyclic compounds having an unsaturated bond with an epoxy group of;

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

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl- 3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonyl imide derivatives, such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide, are mentioned.

Each of the above monomers may be used alone or in combination of two or more.

It is preferable that the alkali-soluble resin has an acid value of 30 to 150 (KOH mg/g). When the acid value is in the above range, the solubility in the developer is improved, the unexposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining raio.

The acid value is a value measured as potassium hydroxide (KOH) required to neutralize 1 g of an acrylic polymer, and can usually be determined by titration using an aqueous potassium hydroxide solution.

Further, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, tetrahydrofuran is used as an elution solvent) of the alkali-soluble resin is 3000 to 100,000.

If the molecular weight is within the above range, the hardness of the coating film is improved, the film remaining ratio is high, the solubility of the unexposed 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 contained in an amount of 5 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of solids in the self-luminous photosensitive resin composition.

When the content of the alkali-soluble resin is contained in an amount of 5 to 80% by weight, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate in the non-pixel part, and it is difficult to reduce the film in the pixel part of the exposed part during development. The omission property of the pixel portion becomes good.

(C) Photopolymerization compound

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

The monofunctional monomer is specifically, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone, etc. are mentioned, and commercially available products include Aronics M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).

Specifically, the bifunctional monomer is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc., and commercially available products include Aaronix M-210, M-1100, 1200 (Toagosei ), KAYARAD HDDA (Nippon Kayaku), Viscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagaku).

The trifunctional or higher polyfunctional photopolymerizable compound is specifically, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) )Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, thipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, Propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., and commercially available products include Aaronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

In addition, dipentaerythritol (poly) acrylate containing a hydroxy group or a carboxyl group may include at least one selected from the group consisting of compounds of Formulas 22 and 23 below.

[Formula 22]

[Formula 23]

The R ₆ to R ₁₀ are each independently an acrylate group or a methacrylate group,

R ₁₁ is hydrogen, acryloyl group or methacryloyl group,

The R ₁₂ to R ₁₄ are each independently a hydroxy 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 the R ₁₂ to R ₁₅ is an acrylate group or a methacrylate group,

R ₁₆ is a compound of Formula 24 below.

[Formula 24]

R ₁₇ and R ₁₈ are each independently an acrylate group or a methacrylate group,

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

Among the photopolymerizable compounds exemplified above, it is preferable to use a polyfunctional monomer having a bifunctional or higher function, and it is more preferable to use a polyfunctional monomer having a polyfunctional or higher function including a carboxyl group.

When a photopolymerizable compound having a 5-functional or higher function is used, the formation of the pixel pattern becomes more excellent.In particular, when a polyfunctional monomer having a 5-functional or higher function containing a carboxyl group is used, there is no decrease in luminescence characteristics due to agglomeration of the quantum dot particles, and the photoreactivity is excellent. A pixel pattern excellent in light emission can be formed.

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

The photopolymerizable compound facilitates the formation of a pixel pattern for a light source in the range of 5 to 70% by weight, so that the intensity and smoothness of the pixel portion are good.

On the other hand, when the photopolymerizable compound is included in an amount of less than 5% by weight, the photocurability is lowered, making it difficult to form a pixel pattern, and when it is included in an amount exceeding 70% by weight, the pattern may be peeled off.

(D) Light polymerization Initiator

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

By including the compound, it is possible to prevent occurrence of reverse taper during pattern formation.

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

The monoacylphosphine-based compound includes a compound of Formula 1 below.

[Formula 1]

R ₁ and R ₂ are each 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 with or without a substituent, or a substituent It is a C5 to C30 aryloxy group containing or not including,

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 with or without a substituent 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.

Compounds 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, etc.

The bisacylphosphine-based compound includes a compound of Formula 2 below.

[Formula 2]

The R ₄ is 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, including or not including a substituent, or a substituent group. It is a C5 to C30 aryloxy group,

Each of R ₅ , identically or differently, 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 5 to carbon atoms with or without a substituent. Is an aryloxy group of 30,

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.

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

In addition, the oxime compound is a compound containing at least one selected from the group consisting of a florene group, a carbazole group, and a diphenyl sulfide group.

It is preferable that the oxime-based compound contains at least one selected from the group consisting of the following Chemical Formulas 3 to 21. In addition, it is possible to mix and use two or more types of oxime compounds.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

In addition, the photoinitiator may further include an acetophenone-based compound.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2 -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane And 1-one oligomers.

In addition, the photopolymerization initiator may further include a triazine-based compound or a biidazole-based compound in order to improve strength or contact hole characteristics.

Examples of the triazine-based 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-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran- 2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloro Romethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole and the phenyl group at the 4,4',5,5' position And imidazole compounds substituted with a carboalkoxy group. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole is preferably used.

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

As other photoinitiators, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, etc. are mentioned, for example. These may be used alone or in combination of two or more.

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

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenyl benzophenone, 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-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone. Can be mentioned.

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

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campoquinone, phenylclioxylic acid Methyl, titanocene compounds, etc. are mentioned as other photoinitiators.

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

An amine compound or a carboxylic acid compound may be preferably used as the photopolymerization initiator auxiliary agent.

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

4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4 Aromatic amine compounds such as'-bis(dimethylamino)benzophenone (common name: 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, Aromatic heteroacetic acids, such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid, are mentioned.

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

When the photopolymerization initiator is included in the range of 0.1 to 20% by weight, the self-luminous photosensitive resin composition is highly sensitive, so that the formation of a fine pixel pattern can be improved.

(E) solvent

As long as the solvent is effective in dissolving other components included in the self-luminous photosensitive resin composition, the solvent used in the ordinary self-luminous photosensitive resin composition may be used without particular limitation, and in particular, ethers, acetates, aromatic hydrocarbons, Ketones, alcohols, esters, and the like are preferable.

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;

Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

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 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methocypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- 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, diethylene 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, propylene carbonate, and the like.

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

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include 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 γ-butyrolactone.

Each of the above solvents may be used alone or in combination of two or more.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coating properties and drying properties. For example, alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, 3-methyl Esters such as methyl oxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxy ethyl propionate, and 3 -Methyl methoxypropionate, etc. are mentioned.

The solvent is included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the self-luminous photosensitive resin composition. If the solvent is contained in the range of 60 to 90% by weight, coating properties are good when applied with 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) and inkjet. Can be set.

(F) additive

The additive may be selectively added as needed, and may include, for example, at least one selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents. have.

In addition, among the additives, it is most preferable to include a surfactant.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be lifted.

The curing agent is used to increase deep curing and mechanical strength, and 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, noblock type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( Co)polymer epoxidation products, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, and the like.

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

The curing agent may be used in combination with a curing agent and 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.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adeka Hadona EH-700 (manufactured by Adeka Industries Co., Ltd.), Rika Shiddo HH (manufactured by Shin Nippa Ewha Corporation), and MH-700 (manufactured by Shin Nihon Ewha Corporation). The curing agent exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the self-luminous photosensitive resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, etc. may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicones as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF of GE Toshiba Silicones. -4460 and TSF-4452.

Examples of the fluorine-based surfactant are commercially available products such as Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dai Nippon Ink Chemical Co., Ltd.

In addition, other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), and MEGAFAC. (Dai Nippon Ink Kagaku High School Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto), Disperbyk-series (BYK-chemi), and the like.

The cationic surfactant may be, for example, an amine salt such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or a quaternary ammonium salt.

The anionic surfactants are, for example, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

The nonionic surfactant is, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

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

The type of adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N-(2-aminoethyl) )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy And propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxy silane, and 3-isocyanate propyl triethoxy silane.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included 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-luminous photosensitive resin composition.

The kind of the antioxidant is not particularly limited, but may include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like. .

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole, alkoxybenzophenone, and the like. .

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

In addition, the present invention provides a color filter made of the self-luminous photosensitive resin composition of the present invention.

When the color filter of the present invention is applied to an image display device, since it emits light by light from a light source of the display device, it can exhibit more excellent light efficiency.

In addition, since light having a color is emitted, color reproducibility is more excellent, and light is emitted in all directions by self-luminescence, so that the viewing angle can be improved.

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

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

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

The pattern layer is a layer comprising the self-luminous photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminous photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern.

The pattern layer formed of the self-luminous 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. When irradiated with light, 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 device, the light emitted from the light source is not particularly limited, but a light source emitting blue light may be used in view of better color reproducibility.

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 further includes a transparent pattern layer that does not contain quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included may be used. For example, when the red pattern layer and the green pattern layer are included, a light source emitting blue light may 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, resulting in blue color.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix. In addition, a protective layer formed on the pattern layer of the color filter may be further included.

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

The color filter of the present invention can be applied not only to an ordinary liquid crystal display device, but also to various image display devices such as an electroluminescent 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 light emitted from the light source is not particularly limited when applied to a display device, but a light source that emits blue light may be preferably used in terms of more excellent color reproducibility.

According to another embodiment of the present invention, the display device of the present invention may include a color filter including only pattern layers 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 that does not contain quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included may be used. For example, when the red pattern layer and the green pattern layer are included, a light source emitting blue light may 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, resulting in blue color.

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

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and examples within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such modifications and modifications fall within the scope of the appended claims.

Manufacturing example One. Quantum dots Particle manufacturing

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

Thereafter, in order to remove acetic acid generated by substitution of oleic acid in zinc, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr. Then, heat at 310°C to obtain a transparent mixture, and after maintaining this at 310°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 S solution was rapidly injected into the reactor containing the Cd(OA) ₂ and Zn(OA) ₂ solutions.

The resulting mixture was grown at 310° C. for 5 minutes, and then the growth was stopped using an ice bath. After that, the quantum dots are separated by sedimentation with ethanol, and the excess impurities are washed with chloroform and ethanol, stabilized with oleic acid, and the sum of the core particle diameter and the shell thickness is 3 to 5 nm. The green quantum dot particles of the CdSe (core)/ZnS (shell) structure were prepared.

Synthesis example 1. Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction 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, and t-butyl 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 added and mixed with stirring to prepare a monomer dropping lot, and n-dodecanethiol 6 parts by weight And 24 parts by weight of PGMEA were added and mixed with stirring to prepare a chain transfer agent dropping lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Next, dropping of the monomer and chain transfer agent was started from the dropping lot. Dropping, while maintaining 90℃, proceeds for 2 hours each, heated to 110℃ after 1 hour, maintained for 3 hours, and then introduced a gas introduction tube, and oxygen/nitrogen = 5/95 (v/v) mixed Gas bubbling was initiated.

Then, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were added to the flask, and at 110° C. for 8 hours. 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-luminescence Photosensitive resin composition manufacturing>

Example 1 to 26 and Comparative example 1 to 5.

A solid content of the self-luminous photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 was prepared using the compositions of Tables 1 and 2 below.

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

(Unit: wt%) division Quantum dots 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: Green quantum dot particles of CdSe (core)/ZnS (shell) structure prepared in Preparation Example 1 Alkali-soluble resin: Alkali-soluble resin prepared in Synthesis Example 1

Photopolymerizable compound

C-1: dipentaerythritol pentaacrylate succinic acid monoester (5-functional photopolymerizable compound containing carboxylic acid, TO-1382, manufactured by Dong-A Synthesis)

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

Photopolymerization initiator

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

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

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

D-4: acetophenone compound, Irgaqure-907 (manufactured by Basf)

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

D-6: acetophenone compound, Irgaqure-184 (manufactured by Basf)

D-7: oxime compound, Irgaure 0XE01 (manufactured by Basf) [Chemical Formula 3]

D-8: oxime compound, [Chemical Formula 8]

D-9: oxime compound, [Chemical Formula 11]

D-10: oxime compound, [Chemical Formula 16]

D-11: Biimidazole-based compound, CZ-HABI (manufactured by Tron Lisa)

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

Experimental example 1. Measurement of physical properties

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

At this time, the ultraviolet light source was irradiated with light at an exposure dose of 200 mJ/cm 2 (365 nm) in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki, and no special optical filter was used.

The thin film irradiated with ultraviolet rays was developed by immersing it in a developing solution of a pH 10.5 KOH solution for 80 seconds. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 10 minutes to prepare a color filter pattern. The film thickness of the self-luminous color pattern prepared above was 3.0 μm.

1-1. Taper Angle measurement

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

If the taper angle is 0 to 90° or less, it is a pure taper, and if it exceeds 90°, it is a reverse taper.

1-2. Measurement of luminous intensity

The light-converted area was measured through a 365nm Tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT) on the pattern part formed in a 20mm x 20mm square pattern among each of the color filters prepared above, Examples 1 to 26 and In Comparative Examples 1 to 5, the light intensity in the 550 nm region was measured using a Spectrum meter (manufactured by Ocean Optics).

It can be determined that the higher the measured light intensity is, the more excellent self-luminescence properties are exhibited, and the results of the emission intensity measurement are shown in Table 2 below.

In addition, hard bake was performed at a temperature of 230°C for 60 minutes, and the luminescence intensity before hard bake and the intensity after hard bake were measured, and the level at which the luminous efficiency was maintained was checked, and the results are shown in Table 2 below. It was expressed as the luminous intensity retention rate.

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

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

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

More specifically, the self-luminous photosensitive resin compositions of Comparative Examples 1 to 3 containing only an acetophenone-based compound as a photoinitiator had excellent luminescence intensity and luminescence intensity retention, but the curing was not completely performed, resulting in a problem that reverse taper occurred.

In addition, the self-luminous photosensitive resin composition of Comparative Examples 4 and 5 containing a biimidazole-based compound and a triazine-based compound had a high degree of curing and did not generate reverse taper, but the luminous intensity and luminous intensity retention of the quantum dots were poor during the POB process. Showed.

Therefore, it can be seen that the self-luminous photosensitive resin composition of the present invention containing at least one selected from the group consisting of an acylphosphine-based compound and an oxime-based compound as a photopolymerization initiator does not generate reverse taper and exhibits excellent luminescence properties. there was.

Claims (14)

A self-luminous photosensitive resin composition containing quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,
The photopolymerization initiator includes at least one selected from the group consisting of acylphosphine compounds and oxime compounds,
In the color filter manufactured using the self-luminous photosensitive resin composition, the taper angle forms a pure taper, the luminous intensity in the 550 nm region is 42606 or more, and after heating at 230°C for 60 minutes A self-luminous photosensitive resin composition characterized in that the luminous intensity retention rate is 39.8% or more. The self-luminous photosensitive resin composition of claim 1, wherein the quantum dot particles include at least one selected from the group consisting of red quantum dot particles, green quantum dot particles, and blue quantum dot particles. The self-luminous photosensitive resin composition according to claim 1, wherein the acylphosphine-based compound includes at least one selected from the group consisting of a monoacylphosphine-based compound and a bisacylphosphine-based compound. The self-luminous photosensitive resin composition according to claim 3, wherein the monoacylphosphine-based compound comprises a compound represented by the following formula (1).
[Formula 1]

R ₁ and R ₂ are each 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 with or without a substituent, or a substituent It is a C5 to C30 aryloxy group containing or not including,
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 with or without a substituent 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-luminous photosensitive resin composition according to claim 3, wherein the bisacylphosphine-based compound comprises a compound represented by the following formula (2).
[Formula 2]

The R ₄ is 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, including or not including a substituent, or a substituent group. It is a C5 to C30 aryloxy group,
Each of R ₅ , identically or differently, 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 5 to carbon atoms with or without a substituent. Is an aryloxy group of 30,
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-luminous photosensitive resin composition according to claim 1, wherein the oxime-based compound contains at least one selected from the group consisting of a florene group, a carbazole group, and a diphenyl sulfide group in the structure. The self-luminous photosensitive resin composition of claim 1, wherein the oxime-based compound comprises at least one selected from the group consisting of the following Chemical Formulas 3 to 21.
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

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

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