TW201732017A - Self-light-emitting photosensitive resin composition, and color filter and display device comprising the same - Google Patents

Abstract

This invention relates to a self-light-emitting photosensitive resin composition, including quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator including at least one selected from the group consisting of an acylphosphine-based compound and an oxime-based compound, and a solvent, and to a color filter and a display device including the same. The self-light-emitting photosensitive resin composition generates no reverse taper and can exhibit superior emission properties.

Description

Self-luminous photosensitive resin composition, color filter, and display device including color filter

FIELD OF THE INVENTION The present invention relates to a self-luminous photosensitive resin composition and to a color filter and a display device including the same. More specifically, the present invention relates to a self-luminous photosensitive resin composition comprising quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, and light including at least one selected from the group consisting of a mercaptophosphine-based compound and a lanthanoid compound. A polymerization initiator, and a solvent, and relates to a color filter and a display device including the color filter.

BACKGROUND OF THE INVENTION The range of applications of color filters widely used in imaging devices, liquid crystal displays (LCDs) and the like is increasing significantly.

The color filter is configured to include: a black matrix layer formed on the transparent substrate in a predetermined pattern to block light for a boundary between pixels (each having a size of several tens to several hundreds of micrometers); and a pixel portion, wherein The fixed order sets three colors (usually red, green, and blue) to form individual pixels that are sequentially layered.

The color filter is mainly manufactured by repeating the following series of processes for respective colors: a colored photosensitive resin composition containing each of red, green, and blue pigments is uniformly coated on a substrate having a black matrix pattern by spin coating, Heat drying (which may be referred to as "prebaking") to form a coating that is subsequently exposed and developed, and optionally thermal curing (which may be referred to as "post-baking"), to form individual pixels. The black matrix pattern is usually formed of a black photosensitive resin composition.

The pigment dispersion method, which is a method of manufacturing a color filter, enables formation of a colored film by repeating a series of processes including coloring agents, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators, epoxy resins, A photosensitive resin composition of a solvent and other additives is coated with a transparent substrate having a black matrix; exposing a pattern to be formed; removing a non-exposed portion using a solvent; and performing thermal curing. This method is very useful in the manufacture of LCDs for mobile phones, notebook computers, monitors, televisions, and the like.

Recently, a photosensitive resin composition for a color filter using a pigment dispersion method, which has various advantages, is required to have improved properties such as a wide color gamut, high brightness and high contrast, and excellent pattern characteristics.

Color reproduction is achieved by passing light from the source through the color filter. However, in the process, some of the light is absorbed by the color filter, thereby reducing the light efficiency, making it difficult to obtain a complete color reproduction due to the pigment properties of the color filter.

In order to solve such a problem, a method of manufacturing a color filter using a quantum dot photosensitive resin composition has been devised. When quantum dots are used, the emission waveform can be narrowed, high color reproduction performance (which is difficult to achieve in the presence of a pigment) can be ensured, and high luminance can be obtained. However, the light efficiency may be lowered in the hard baking process, and therefore, the composition for the same needs further development.

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in consideration of the above problems encountered in the prior art, and the present invention is intended to provide a self-luminous photosensitive resin composition which does not lower the light efficiency and which does not deteriorate the photosensitive property.

Further, the present invention is intended to provide a color filter and a display device which are manufactured using a self-luminous photosensitive resin composition.

The present invention provides a self-luminous photosensitive resin composition comprising quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises a compound selected from the group consisting of a mercaptophosphine compound and a lanthanoid compound. At least one of the groups.

Further, the present invention provides a color filter manufactured using a self-luminous photosensitive resin composition.

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

According to the present invention, the self-luminous photosensitive resin composition enables self-emission of light, thus preventing reduction in light efficiency during the hard baking process, thereby achieving excellent light efficiency.

Moreover, according to the present invention, the self-luminous photosensitive resin composition has high color reproduction performance and a wide viewing angle and does not cause reverse taper.

Moreover, according to the present invention, the self-luminous photosensitive resin composition has high sensitivity, and therefore, an excellent fine pattern can be formed.

Moreover, according to the present invention, the color filter and the display device manufactured using the self-luminous photosensitive resin composition of the present invention can exhibit very high brightness.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a detailed description of the present invention will be given.

The present invention provides a self-luminous photosensitive resin composition comprising quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises a compound selected from the group consisting of a mercaptophosphine compound and a lanthanoid compound. At least one of the groups.

A typical display device (including a color filter formed of a photosensitive resin composition) develops color by passing white light through a color filter. However, during this process, some of the light is absorbed by the color filter, undesirably reducing the light efficiency.

In order to solve the above problems, in the present invention, the self-luminous photosensitive resin composition includes quantum dot particles for realizing light self-emission of a light source to reduce loss of light, thereby obtaining excellent light efficiency.

Moreover, when a pattern is formed using a conventional self-luminous photosensitive resin composition, an undesired inverted taper may be formed.

In order to solve the above problem, in the present invention, the self-luminous photosensitive resin composition includes a photopolymerization initiator containing at least one selected from the group consisting of a mercaptophosphine-based compound and a lanthanoid-based compound, thereby preventing generation of a reverse tapered shape and The sensitivity is increased to form the final pixel pattern.

The respective components of the colored photosensitive resin composition according to the present invention are explained in detail below.

(A Quantum dot particle

"Quantum dots" refers to nano-sized semiconductor materials. Atoms form molecules and form small aggregates of molecules (called clusters) that result in nanoparticles. When such nanoparticles show semiconductor features, they are referred to as quantum dots.

When quantum dots reach an excited state due to the application of external energy, they release energy corresponding to their band gap, which is called self-emission.

The self-luminous photosensitive resin composition according to the present invention includes self-luminous quantum dot particles, and a color filter manufactured therefrom can emit light when irradiated with light.

A typical display device including a color filter develops color by passing white light through a color filter. During this process, some of the light is absorbed by the color filter, undesirably reducing the light efficiency.

However, when the color filter formed of the self-luminous photosensitive resin composition according to the present invention is included, the color filter can self-illuminate under irradiation of light from the light source, thus achieving higher light efficiency.

Moreover, since light having color is emitted, color reproduction performance becomes excellent, and light is emitted in all directions by luminescent light, thereby improving the viewing angle.

In the present invention, the kinds of the quantum dot particles are not particularly limited as long as they can emit light due to optical stimulation, and such quantum dot particles may include a compound selected from the group consisting of a Group II-VI semiconductor compound and a Group III-V semiconductor compound. At least one of the group consisting of a Group IV-VI semiconductor compound and a Group IV element or a compound including the same.

Specific examples of the Group II-VI semiconductor compound may include: binary compounds such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; ternary compounds such as CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe , CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

Specific examples of the Group III-V semiconductor compound may include: binary compounds such as GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

Specific examples of the Group IV-VI semiconductor compound may include: binary compounds such as SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; ternary compounds such as SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and quaternary compounds such as SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

Specific examples of the Group IV element or a compound thereof may include: elemental compounds such as Si, Ge, and mixtures thereof; and binary compounds such as SiC, SiGe, and mixtures thereof.

Moreover, the quantum dot particles may have a uniform single structure, a dual structure such as a core-shell structure and a gradient structure, or a mixed structure thereof.

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

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

For example, the shell may include, but is not limited to, at least one selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe.

The colored photosensitive resin composition for producing a typical color filter includes red, green, and blue colorants to achieve color reproduction. Therefore, the quantum dot particles can be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles, and in the present invention, include a group selected from red quantum dot particles, green quantum dot particles, and blue quantum dot particles. At least one of them.

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

The wet chemical process is performed in such a manner that a precursor substance is added to an organic solvent to grow particles, and an organic solvent is naturally disposed on the surface of the quantum dot crystal and used as a dispersing agent at the time of crystal growth, thereby adjusting crystal growth. This wet chemical process is easy and inexpensive to perform, as compared to a vapor deposition process such as MOCVD or MBE, to control the size growth of quantum dot particles.

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

If the amount of quantum dot particles is less than 3 wt%, the emission efficiency may become inconspicuous. On the other hand, if the amount thereof exceeds 80% by weight, the relative amounts of the other components may decrease, making it difficult to form a pixel pattern.

In the present invention, the solid weight of the self-luminous photosensitive resin composition means the total weight of the self-luminous photosensitive resin composition excluding the solvent.

(B) alkali soluble resin

In the present invention, the kind of the alkali-soluble resin is not particularly limited as long as the non-exposed portion of the photosensitive resin layer formed of the self-luminous photosensitive resin composition is made alkali-soluble to remove it and leave the exposed region.

The alkali-soluble resin may include a copolymer of a monomer having a carboxyl group and an additional monomer copolymerizable therewith.

Specific examples of the monomer having a carboxyl group may include an unsaturated carboxylic acid having at least one carboxyl group in its molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid.

Examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, a-chloroacrylic acid, and benzoacrylic acid.

Examples of the unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, citraconic acid, and methyl fumaric acid.

Examples of the unsaturated polycarboxylic acid may include an acid anhydride such as maleic anhydride, itaconic anhydride, and citraconic anhydride.

The unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, and specific examples thereof may include mono(2-propenyloxyethyl) succinate, mono(2-methylpropene oxime). Oxyethyl) succinate, mono(2-propenyl oxiranyl) phthalate and mono(2-methylpropenyloxyethyl) phthalate.

The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, and specific examples thereof may include w-carboxypolycaprolactone monoacrylate and w-carboxypolycaprolactone Methacrylate.

Among the above compounds, acrylic acid or methacrylic acid is preferably used because of its high copolymerization reactivity and high solubility in a developing solution.

These carboxyl group-containing monomers may be used singly or in combination of two or more.

Examples of the additional monomer copolymerizable with the monomer having a carboxyl group may include an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid such as methyl (meth) acrylate or ethyl (meth) acrylate. , (butyl) (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate;

An unsaturated carboxylic acid ester compound having an alicyclic substituent such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, or (meth)acrylic acid ring Heptyl ester, cyclooctyl (meth)acrylate, menthyl (meth)acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (methyl) Acrylate, cyclooctenyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, decyl (meth) acrylate, adamantyl (methyl ) acrylate, norbornene (meth)acrylate and nonenyl (meth) acrylate;

An unsaturated carboxylic acid ester having a thermosetting substituent such as 3-((meth)acryloxymethyl)oxetane, 3-((meth)acryloxymethyl)-3-B Oxycyclobutane, 3-((meth)acryloxymethyl)-2-methyloxetane and 3-((meth)acryloxymethyl)-2-tri Fluoromethyl oxetane;

a glycol mono-saturated carboxylic acid ester compound such as an oligoethylene glycol monoalkyl (meth) acrylate;

An unsaturated carboxylic acid ester compound having an aromatic ring substituent such as benzyl (meth) acrylate and phenoxy (meth) acrylate;

An aromatic vinyl compound such as styrene, a-methylstyrene and vinyltoluene;

a vinyl carboxylate compound such as vinyl acetate and vinyl propionate, and an acrylonitrile compound such as (meth)acrylonitrile and a-chloroacrylonitrile;

An aliphatic polycyclic compound having an epoxy group and an unsaturated bond, such as a glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl Methyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3-(methacryloxymethyl) oxetane, 3-(methacryloxymethyl) )-3-ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2- Trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2- Phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2, 4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxyethyl) Oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxycyclohexane Butane 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3- (methacryloxyethyl)-2,2,4-trifluorooxetane, 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxa Cyclobutane, 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl) -2-methyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoro Ethyloxetane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(acryloxymethyl)-2,2-difluorooxetane Alkanes, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxa Cyclobutane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3-B Oxetane, 2-ethyl-3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(Propyloxyethyl)-2-pentafluoroethyloxetane, 3-(acryloxyethyl)-2-phenyloxetane, 2,2-difluoro 3-(Allyloxyethyl)oxetane, 3-(acryloxyethyl)-2,2,4-trifluorooxetane, 3-(acryloxy) -2,2,4,4-tetrafluorooxetane, epoxidized bicyclodecyl (meth) acrylate, 3,4-epoxytricyclodec-8-yl (meth) acrylate Ester, 3,4-epoxytricyclodec-8-yl (meth) acrylate, epoxidized dicyclopentanyloxyethyl (meth)acrylate, 2-(3) , 4-epoxytricyclic fluoren-9-oxy)ethyl (meth) acrylate, 2-(3,4-epoxytricyclodecan-8-oxy)ethyl (meth) acrylate, And epoxidized dicyclopentanyloxyhexyl (meth)acrylate;

Epoxide compounds, such as dicyclopentane, tricyclodecane, norbornane, isodecane, bicyclooctane, cyclodecane, dicycloundecane, tricycloundecane, dicyclododecane And tricyclododecane; and

Dicarbonyl ruthenium imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-ammonium imino-3-arm醯iminobenzoate, N-succinimide-4-maleimine butyrate, N-succinimide-6-maleimide caproate, N Amber imino-3-maleimide propionate and N-(9-acrydinyl) maleimide.

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

The alkali-soluble resin may have an acid value of 30 to 150 (mg KOH/g). When the acid value falls within the above range, the solubility in the developing solution can be increased, and therefore, the non-exposed portion of the solution can be easily obtained and the sensitivity can be increased. Therefore, the exposed portion can be left at the time of development, thereby improving the film residual ratio.

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

Further, the alkali-soluble resin may have a weight average molecular weight of from 3,000 to 100,000, as calculated by gel permeation chromatography (GPC, using tetrahydrofuran as a dissolution solvent), based on polystyrene.

When the molecular weight falls within the above range, the hardness of the coating film is increased, and thus a high film remaining ratio can be produced. Further, the solubility of the non-exposed portion in the developing solution is high, and the resolution is increased.

In the present invention, the amount of the alkali-soluble resin is from 5 wt% to 80 wt%, preferably from 10 wt% to 70 wt%, based on the total solid weight of the self-luminous photosensitive resin composition.

When the amount of the alkali-soluble resin falls within the range of 5 wt% to 80 wt%, the solubility in the developing solution is sufficiently high, and therefore, it is difficult to leave a non-pixel portion on the substrate in the developing process. Further, in the developing process, it is difficult to reduce the size of the film corresponding to the exposed portion of the pixel portion, and thus the non-pixel portion is effectively removed.

(C) Photopolymerizable compound

In the self-luminous photosensitive resin composition according to the present invention, the photopolymerizable compound must be polymerizable by the action of the photopolymerization initiator (D) which will be described later. It may include, but is not limited to, a monofunctional photopolymerizable compound, a difunctional photopolymerizable compound, or a trifunctional photopolymerizable compound.

Specific examples of the monofunctional monomer may include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone, and commercially available products thereof may include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Wiskott 158 (Osaka Organic Chemical Industrial).

Specific examples of the difunctional monomer may include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol Alcohol di(meth)acrylate, bisphenol A bis(acryloxyethyl)ether and 3-methylpentanediol di(meth)acrylate, and commercially available products thereof may include Aronix M- 210, M-1100, 1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Wiskott 260 (Osaka Organic Chemical Industrial) and AH-600, AT-600 or UA-306H (Kyoeisha Chemical).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound may include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy group Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol Methyl) acrylate, propoxylated dipentaerythritol hexa(meth) acrylate and dipentaerythritol hexa (meth) acrylate, and commercially available products thereof may include Aronix M-309, TO-1382 (Toagosei) And KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

Moreover, the dipentaerythritol (poly) acrylate having a hydroxyl group or a carboxyl group may include at least one selected from the group consisting of compounds of the following Chemical Formulas 22 and 23. [Chemical Formula 22] [Chemical Formula 23]

In Chemical Formulas 22 and 23, R ₆ to R ₁₀ are each independently an acrylate group or a methacrylate group,

R ₁₁ is hydrogen, propylene fluorenyl or methacryl fluorenyl,

R ₁₂ to R ₁₄ are each independently a hydroxyl group, a C1 to C4 alkyl group, an acrylate group, a methacrylate group or OR ₁₆ .

R ₁₅ is hydrogen, C1 to C4 alkyl, acrylate group, 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, and

R ₁₆ is a compound of the following Chemical Formula 24. [Chemical Formula 24]

In Chemical Formula 24, R ₁₇ and R ₁₈ are each independently an acrylate group or a methacrylate group, and

R ₁₉ is hydrogen, propylene fluorenyl, methacryl fluorenyl or -C(=O)CH ₂ CH ₂ C(=O)OH.

Among the examples of the photopolymerizable compound, a difunctional or higher polyfunctional monomer is preferably used. Particularly used are pentafunctional or higher polyfunctional monomers having a carboxyl group.

The use of a pentafunctional or higher photopolymerizable compound makes it easier to form a pixel pattern. In particular, when a pentafunctional or higher polyfunctional monomer having a carboxyl group is used, since the luminescent property is prevented from deteriorating due to agglomeration of the quantum dot particles, and photoreactivity is increased, a pixel pattern having high luminescent properties is formed.

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

When the amount of the photopolymerizable compound falls within the range of 5 wt% to 70 wt%, the pixel pattern can be easily formed by the light source, and therefore, the strength and smoothness of the pixel portion can be made good.

If the amount of the photopolymerizable compound is less than 5% by weight, photocurability may be lowered, making it difficult to form a pixel pattern. On the other hand, if the amount exceeds 70% by weight, the pattern may be peeled off, which is not desirable.

(D) Photopolymerization initiator

In the self-luminous photosensitive resin composition according to the present invention, the photopolymerization initiator may include at least one selected from the group consisting of a mercaptophosphine compound and a lanthanoid compound.

When the above compound is contained, when a pattern is formed, the occurrence of a reverse taper can be prevented.

The mercaptophosphine-based compound may include at least one selected from the group consisting of a monodecylphosphine-based compound and a bis-fluorenylphosphine-based compound.

The monothiol phosphine-based compound includes the compound of the following Chemical Formula 1. [Chemical Formula 1]

In Chemical Formula 1, R1 and R2 are each independently a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or C5 to C30 aryloxy group with or without a substituent,

R3 is a C4 to C20 alkyl group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or a C5 to C30 aryloxy group with or without a substituent, and

The substituent is a halogen atom, a C1 to C10 alkyl group or a C1 to C10 alkoxy group.

Examples of the compound of Chemical Formula 1 may include diphenyl (2,4,6-trimethylbenzimidyl)phosphine oxide (Irgacure TPO, manufactured by BASF Corporation) and ethyl (2,4,6-trimethyl) Benzhydrazinyl phenyl phosphite (Irgacure TPO-L, manufactured by BASF Corporation).

The bis-decylphosphine-based compound includes the compound of the following Chemical Formula 2. [Chemical Formula 2]

In Chemical Formula 2, R ₄ is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or with or without a C5 to C30 aryloxy group of a substituent,

R _{5 is the} same or different from each other, and is a C4 to C20 alkyl group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or a C5 to C30 group with or without a substituent. Aryloxy, and

The substituent is a halogen atom, a C1 to C10 alkyl group or a C1 to C10 alkoxy group.

The compound of Chemical Formula 2 may, for example, be phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide (Irgacure 819, manufactured by BASF Corporation).

The lanthanoid compound may be a compound having at least one selected from the group consisting of a mercapto group, a carbazolyl group, and a diphenyl sulfide.

The lanthanoid compound preferably includes at least one selected from the group consisting of the following Chemical Formulas 3 to 21. Moreover, a combination of two or more lanthanoid compounds thereof may be used. [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 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]

Further, the photopolymerization initiator may further include an acetophenone-based compound.

Examples of the acetophenone-based compound may include oligomers such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl) Phenylthio)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 2-hydroxyl -2-Methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

In order to increase the strength or contact hole characteristics, the photopolymerization initiator may further include a triazine compound or a biimidazole compound.

Examples of the triazine-based compound may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethane). 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene 1,1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1 , 3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

Examples of the biimidazole-based compound may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole and at 4,4',5, An imidazole compound in which the phenyl group at the 5' position is substituted with an alkoxycarbonyl group. In particular, 2,2' bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)-4 are used. , 4', 5, 5'-tetraphenylbiimidazole.

Any other photopolymerization initiator generally used in the art can also be used within the range not impairing the effects of the present invention.

Any other photopolymerization initiator may include a benzoin compound, a benzophenone compound, a thioxantone compound, and an anthraquinone compound, which may be used singly or in combination of two or more.

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

Examples of the benzophenone compound may include benzophenone, methyl phthalic acid benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, and 3 , 3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and 4,4'-di(N,N'-di Methylamino)-benzophenone.

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

Examples of the ruthenium compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10- Diethoxy hydrazine.

Further photopolymerization initiators may include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl 9, 10-phenanthrenequinone, hydrazine, methyl phenyl glyoxylate, titanocene compound, and the like.

In the present invention, when the photopolymerization initiator (D) is used together with the photopolymerization initiating adjuvant (D1), the sensitivity of the resulting colored photosensitive resin composition is further increased, so that productivity can be increased when the color filter is formed.

The photopolymerization initiating adjuvant may include an amine compound or a carboxylic acid compound.

Specific examples of the amine compound may include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-Dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, 2-ethylhexyl 4-dimethylamino benzoate, 2-dimethylamine Ethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (milaxone) and 4,4'-double (two Ethylamino)benzophenone. It is preferred to use an aromatic amine compound.

Specific examples of the carboxylic acid compound may include aromatic heteroacetic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N- Naphthylglycine and naphthyloxyacetic acid.

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

When the amount of the photopolymerization initiator falls within the range of 0.1 wt% to 20 wt%, the sensitivity of the self-luminous photosensitive resin composition increases, and therefore, the formation of a fine pixel pattern can be made good.

(E) solvent

In the self-luminous photosensitive resin composition according to the present invention, any solvent commonly used in the art may be used without particular limitation as long as it is effective in dissolving other components, and examples thereof may include ether, acetate, and aromatic. Hydrocarbons, ketones, alcohols and esters.

Examples of the ether may 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 Alcohol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetate may include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, acetic acid. 3-methoxybutyl ester, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, 3- Methyl methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, two Ethylene 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 monoacetic acid Ester, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate.

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

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

Examples of the alcohol may include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the ester may include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and g-butyrolactone.

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

The solvent is preferably an organic solvent having a boiling point of from 100 ° C to 200 ° C according to coating and drying properties, and examples of the organic solvent may include alkylene glycol alkyl ether acetate, ketone, and ester such as 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like. Preference is given to using propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and 3-methoxypropionic acid ester.

The amount of the solvent is 60 wt% to 90 wt%, preferably 70 wt% to 85 wt%, based on the total weight of the self-luminous photosensitive resin composition. When the amount of the solvent falls within the range of 60 wt% to 90 wt%, using a coater such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or a die coater), and a spray The coating performance can be improved when the ink is or the like.

(F) additive

An additive may be optionally added as needed, and it may include, for example, at least one selected from the group consisting of an additional polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, a UV absorber, and an anti-coagulant. .

In particular, it is preferred to use a surfactant.

Specific examples of the other polymer compound may include a curable resin such as an epoxy resin and a maleimide resin, and a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluorocarbon. Acrylates, polyesters and polyurethanes.

The curing agent is used to increase core curing properties and mechanical strength, and specific examples thereof may include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

In the curing agent, specific examples of the epoxy compound may include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and the like. Aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, bromide derivative of epoxy resin, aliphatic or alicyclic group other than epoxy resin and its brominated derivative Or aromatic epoxy compound, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, glycidyl (meth)acrylate (co)polymer and isocyanuric acid Glycidyl ester.

In the curing agent, specific examples of the oxetane compound may include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate Dioxetane and cyclohexanedicarboxylic acid dioxetane.

The curing agent may be used together with a curing assistant compound capable of ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound.

The curing assistant compound may include, for example, a polycarboxylic acid, a polycarboxylic acid anhydride, and an acid generator. The polycarboxylic acid anhydride may include those commercially available as an epoxy resin curing agent. Examples of commercially available products may include Adeka Hardener EH-700 (Adeka Industry), Rikacid HH (Shin-Nippon Rika), and MH-700 (Shin-Nippon Rika). These curing agents may be used singly or in combination of two or more.

The surfactant may be used to promote the formation of a film of the self-luminous photosensitive resin composition, and an organic terpene surfactant, a fluorine-based surfactant, an ester surfactant, a cationic surfactant, an anionic surfactant, or the like may be used. Nonionic surfactants and amphoteric surfactants.

Examples of the organoquinone surfactant may include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF-4445, TSF-4446 from GE Toshiba Silicones. Commercially available products such as TSF-4460 and TSF-4452.

Examples of the fluorine-based surfactant may include commercially available products such as Megaface F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Industry Co., Ltd.

Other commercially available products may include KP (ShinEtsu Chemical Industrial), POLYFLOW (Kyoeisha Chemical), EFTOP (Tochem Products), MEGAFAC (Dainippon Ink Chemical Industry), Flourad (Sumitomo 3M), Asahi guard, and Surflon (Asahi Glass), SOLSPERSE (Lubrisol), EFKA (EFKA Chemicals), PB 821 (Ajinomoto) and Disperbyk series (BYK-Chemi).

Examples of the cationic surfactant may include an amine salt or a quaternary ammonium salt such as octadecylamine hydrochloride and lauryltrimethylammonium chloride.

Examples of anionic surfactants may include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate and alkyl aryl sulfonates, for example Sodium dodecylbenzene sulfonate and sodium dodecyl naphthalene sulfonate.

Examples of the nonionic surfactant may include polyethylene glycol alkyl ether, polyethylene glycol aryl ether, polyethylene glycol alkyl aryl ether, other polyethylene glycol derivatives, oxyethylene/oxypropylene groups. Block copolymer, sorbitan fatty acid ester, polyethylene glycol sorbitan fatty acid ester, polyethylene glycol sorbitan fatty acid ester, glycerol fatty acid ester, polyethylene glycol fatty acid ester and polyethylene Glycolalkylamine.

The exemplified surfactants may be used singly or in combination of two or more.

The kind of the adhesion promoter is not particularly limited, and specific examples of useful adhesion promoters may include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-amine Propyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyl Trimethoxydecane, 3-isocyanatopropyltrimethoxydecane and 3-isocyanatopropyltriethoxydecane.

The adhesion promoters may be used singly or in combination of two or more. The adhesion promoter is contained in an amount of from 0.01% by weight to 10% by weight, preferably from 0.05% by weight to 2% by weight based on the total solids of the self-luminous photosensitive resin composition.

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

The kind of the UV absorber is not particularly limited, but specific examples thereof include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. Wait.

The kind of the anti-coagulant is not particularly limited, and it is, for example, sodium polyacrylate.

Further, the present invention proposes a color filter manufactured using the self-luminous photosensitive resin composition of the present invention.

When the color filter according to the present invention is applied to an image display device, it can emit light when irradiated with light of a light source of the display device, thus exhibiting high light efficiency.

Further, since light having color is emitted, higher color reproduction performance can be obtained, and light can be emitted in all directions by self-luminescence, thereby improving the viewing angle.

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

The substrate itself may be a color filter or may be a place where a color filter is placed on a display device without particular limitation.

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

The pattern layer is a layer including the self-luminous photosensitive resin composition according to the present invention, and can be formed by coating a self-luminous photosensitive resin composition, followed by exposure, development, and heat curing 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 containing blue quantum dot particles. When illuminated with light, the red pattern layer can emit red light, the green pattern layer can emit green light, and the blue pattern layer can emit blue light.

When the pattern layer is applied to an image display device, light emitted from the light source is not particularly limited, but a blue light source can be used in terms of higher color reproduction performance.

In another embodiment of the present invention, the pattern layer may include only the 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 this case, the pattern layer may further include a transparent pattern layer without quantum dot particles.

In the case where only a pattern layer of two colors is provided, a light source that emits light at a wavelength corresponding to the remaining color may be used. For example, in the case of including a red pattern layer and a green pattern layer, a blue light source can be used. As such, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer appears blue because the blue light passes therethrough.

The color filter including the substrate and the pattern layer may further include a barrier layer formed between the patterns, and may further include a black matrix. Moreover, a protective film formed on the pattern layer of the color filter may also be included.

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

The color filter according to the present invention can be applied not only to a typical 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 according to the present invention may include a color filter including a red pattern layer having red quantum dot particles, a green pattern layer having green quantum dot particles, and a blue pattern layer having blue quantum dot particles. In this case, the light emitted from the light source applied to the display device is not particularly limited, but a light source that emits blue light is preferably used in terms of higher color reproduction performance.

In 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 this case, the color filter may also include a transparent pattern layer without quantum dot particles.

In the case where only a pattern layer of two colors is provided, a light source that emits light at a wavelength corresponding to the remaining color may be used. For example, in the case of including a red pattern layer and a green pattern layer, a blue light source can be used. As such, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer appears blue because the blue light passes therethrough.

The display device of the present invention exhibits excellent light efficiency, and thus exhibits high luminance, high color reproduction performance, and wide viewing angle.

The invention is better understood by the following examples, which are set forth to illustrate the invention and are not to be construed as limiting the scope of the appended claims. The modifications and variations are intended to be included within the scope and spirit of the invention.

Preparation Example 1. Preparation of Quantum Dot Particles

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 then heated to 150 ° C and allowed to react.

Subsequently, in order to remove acetic acid formed by the combination of zinc and oleic acid, the above reaction product was allowed to stand in a vacuum of 100 mTorr for 20 minutes (minutes). Then, heating was carried out at 310 ° C to obtain a transparent mixture, and then the transparent mixture was kept at 310 ° C for 20 min. Se and S solutions (0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine) were introduced into a reactor containing a solution of Cd(OA) ₂ and Zn(OA) ₂ .

The resulting mixture was grown at 310 ° C for 5 min and then allowed to stop with ice bath. Subsequently, after precipitation in ethanol, the quantum dots were separated using a centrifuge, and additional impurities were washed with chloroform and ethanol to produce oleic acid-stabilized green quantum dot particles having a CdSe (nuclear)/ZnS (shell) structure, in which CdSe In the (nuclear)/ZnS (shell) structure, particles having a total of core diameter and shell thickness of 3 nm to 5 nm are distributed.

Synthesis Example 1. Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. 45 parts by weight of N-benzyl maleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexyl The acid ester and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA") were placed in a flask and stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of the positive twelve Thiol and 24 parts by weight of PGMEA were placed in a flask and stirred to prepare a chain transfer agent dropping funnel.

395 parts by weight of PGMEA was placed in the flask, the atmosphere was replaced with a nitrogen atmosphere, and the temperature of the flask was raised to 90 ° C with stirring. Subsequently, the monomer and chain transfer agent were dropped from their respective dropping funnels. The respective instillation of the monomer and the chain transfer agent was carried out for 2 hours while maintaining the temperature at 90 ° C, and after 1 hour, the temperature was raised to 110 ° C for 3 hours, after which the gas inlet tube was introduced. To this, bubbling was started with a mixed gas using oxygen/nitrogen = 5/95 (v/v).

Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 0.8 parts by weight of triethylamine were placed. The flask was allowed to react at 110 ° C for 8 hours, after which the resulting reaction product was cooled to room temperature to produce an alkali solubility 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. Resin.

<Preparation of Self-luminous Photosensitive Resin Composition>

Examples 1 to 26 and Comparative Examples 1 to 5

The solids of the self-luminous photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were prepared using the components in the amounts shown in Table 1 below.

20 wt% of each solid was mixed with 80 wt% of propylene glycol monomethyl ether acetate solvent, and thus, the self-luminous photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were produced [Table 1] (Unit: wt %) Quantum dot: green quantum dot particle alkali-soluble resin having the CdSe (core)/ZnS (shell) structure of Preparation Example 1: alkali-soluble resin photopolymerizable compound C-1 of Synthesis Example 1: dipentaerythritol pentaacrylate succinic acid single Ester (five-functional photopolymerizable compound containing a carboxylic acid, TO-1382, manufactured by Toagosei Co., Ltd.) C-2: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) Photopolymerization initiator D-1: single Acylphosphine-based compound, Irgacure TPO (manufactured by BASF Corporation) D-2: monoacylphosphine-based compound, Irgacure TPO-L (manufactured by BASF Corporation) D-3: bisacylphosphine-based compound, Irgaqure-819 (by BASF Corporation) Manufactured) D-4: acetophenone-based compound, Irgaqure-907 (manufactured by BASF Corporation) D-5: acetophenone-based compound, Irgaqure-651 (manufactured by BASF Corporation) D-6: acetophenone-based compound, Irgaqure-184 (manufactured by BASF Corporation) D-7: lanthanide compound, Irgaure 0XE01 (manufactured by BASF Corporation) - [Chemical Formula 3] D-8: lanthanide compound, [Chemical Formula 8] D-9: lanthanide compound, [Chemical Formula 11] D-10: lanthanide compound, [Chemical Formula 16] D-11: a biimidazole compound, CZ-HABI (manufactured by the company Torny) D-12: a triazine compound, TAZ-101 (manufactured by Midori Chemical Co., Ltd.)

Test Example 1. Performance Test

Each of the self-luminous photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 was coated on a glass substrate by spin coating, and the glass substrate was placed on a hot plate and kept at 100 ° C for 3 minutes to form a film. . Subsequently, a test photomask having a square transmission pattern (having a size of 20 mm (width) × 20 mm (length)) and a line/space pattern of 1 mm to 100 mm was placed on the film, and then irradiated with UV light at a distance of 100 mm.

The UV light source was an ultrahigh pressure Hg lamp (USH-250D) manufactured by Ushio Electric Co., Ltd., and UV light was applied by air at an amount of 200 mJ/cm ² (365 nm) without using a special filter.

The film to which UV light was applied was immersed in a KOH developing aqueous solution having a pH of 10.5 for 80 s (seconds) for development. The film-coated glass substrate was washed with distilled water, dried with nitrogen, and heated at 150 ° C for 10 min in an oven, thereby producing a color filter pattern. The self-luminous color film has a thickness of 3.0 mm.

1-1. Determination of cone angle

The cone angle of each color filter was measured using a scanning electron microscope (SEM). The results are shown in Table 2 below.

The case where the taper angle is 0° to 90° is a forward taper, and the case where the taper angle exceeds 90° is a reverse taper.

1-2. Determination of light intensity

A square pattern portion having a size of 20 mm × 20 mm of each color filter was irradiated with light of a 365 nm tubular 4W UV lamp (VL-4LC, VILBER LOURMAT), and Example 1 was measured using a spectrometer (manufactured by Ocean Optics Co., Ltd.). The intensity of light emitted by the light-illuminated color filter of 26 and Comparative Examples 1 to 5 at a wavelength of 550 nm.

The higher the measured light intensity, the higher the self-luminous property. The measurement results of the light intensity are shown in Table 2 below.

Further, hard baking was performed at 230 ° C for 60 minutes, and light intensity was measured before and after hard baking, and the level of the maintained emission efficiency was evaluated and recorded as light intensity retention. The results are shown in Table 2 below. [Table 2]

As is apparent from the results of Table 2, the self-luminous photosensitive resin compositions according to Examples 1 to 26 of the present invention did not produce a reverse taper, and the light intensity and light intensity were both kept high.

However, in the self-luminous photosensitive resin compositions of Comparative Examples 1 to 5 (containing no mercaptophosphine-based compound or an anthraquinone-based compound as a photopolymerization initiator), at least one of the above three evaluation items was poor.

More specifically, the self-luminous photosensitive resin compositions of Comparative Examples 1 to 3 (containing only the acetophenone-based compound as a photopolymerization initiator) exhibited high light intensity and light intensity retention, but inverted conical shape due to incomplete curing .

Further, the self-luminous photosensitive resin compositions of Comparative Examples 4 and 5 (including a biimidazole-based compound and a triazine-based compound) have high curing degree, and thus do not produce a reverse taper, but the light intensity and light intensity of the quantum dots during the POB process. Keep it very poor.

Therefore, the self-luminous photosensitive resin composition according to the present invention (including at least one selected from the group consisting of a mercaptophosphine compound and an anthracene compound is a photopolymerization initiator) does not cause reverse taper and exhibits excellent light-emitting characteristics.

While the preferred embodiment of the present invention has been disclosed for the purposes of illustration, it will be understood by those skilled in the art of.

Figure 1 shows a color filter without an inverted cone; and

Figure 2 shows a color filter with an inverted cone.

Claims (14)

A self-luminous photosensitive resin composition comprising quantum dot particles, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises a compound selected from the group consisting of a mercaptophosphine compound and a lanthanoid compound. At least one of the groups. The self-luminous photosensitive resin composition of 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-luminous photosensitive resin composition of claim 1, wherein the mercaptophosphine-based compound comprises at least one selected from the group consisting of a monodecylphosphine-based compound and a bis-fluorenylphosphine-based compound. The self-luminous photosensitive resin composition of claim 3, wherein the monodecylphosphine compound comprises a compound of the following Chemical Formula 1: [Chemical Formula 1] Wherein R ₁ and R ₂ are each independently a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or a band A C5 to C30 aryloxy group with or without a substituent, R ₃ is a C4 to C20 alkyl group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or with or There is no C5 to C30 aryloxy group of the substituent, and the substituent is a halogen atom, a C1 to C10 alkyl group or a C1 to C10 alkoxy group. The self-luminous photosensitive resin composition of claim 3, wherein the bis-fluorenylphosphine compound comprises a compound of the following chemical formula 2: [Chemical Formula 2] Wherein R ₄ is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C5 to C30 cycloalkyl group, a C5 to C30 aryl group with or without a substituent, or with or without a substituent. C5 to C30 aryl group, R ₅ the same or different, is a C4 to C20 alkyl, C5 to C30 cycloalkyl, C5 to C30 aryl with or without substituent groups, or with or without a C5 to C30 aryloxy group of the substituent, and the substituent is a halogen atom, a C1 to C10 alkyl group or a C1 to C10 alkoxy group. The self-luminous photosensitive resin composition of claim 1, wherein the lanthanoid compound comprises at least one selected from the group consisting of a mercapto group, a carbazolyl group, and a diphenyl sulfide group in its structure. The self-luminous photosensitive resin composition of claim 1, wherein the lanthanoid compound comprises at least one selected from the group consisting of the following Chemical Formulas 3 to 21, [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 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-luminous photosensitive resin composition of claim 1, wherein the photopolymerization initiator comprises two or more mercaptophosphine-based compounds. The self-luminous photosensitive resin composition of claim 1, wherein the photopolymerization initiator comprises two or more lanthanoid compounds. The self-luminous photosensitive resin composition of claim 1, wherein the photopolymerization initiator comprises both the mercaptophosphine compound and the anthracene compound. The self-luminous photosensitive resin composition of claim 1, wherein the photopolymerization initiator further comprises an acetophenone-based compound. The self-luminous photosensitive resin composition of claim 1, comprising: 3% by weight to 80% by weight of the quantum dot particles, and 5% by weight to 80% by weight of the alkali-soluble resin based on the total solid weight of the self-luminous photosensitive resin composition 5 wt% to 70 wt% of the photopolymerizable compound and 0.1 wt% to 20 wt% of the photopolymerization initiator, and it includes 60 wt% to 90 wt% based on the total weight of the self-luminous photosensitive resin composition The solvent. A color filter manufactured using the self-luminous photosensitive resin composition according to any one of claims 1 to 12. A display device comprising a color filter as in claim 13.