KR101858085B1

KR101858085B1 - Photosensitive resin composition and color filter using same

Info

Publication number: KR101858085B1
Application number: KR1020160030361A
Authority: KR
Inventors: 김종기; 백호정; 권오범; 권지윤; 김민성; 박진성
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-03-14
Filing date: 2016-03-14
Publication date: 2018-06-28
Also published as: KR20170106791A

Abstract

(A) quantum dots; (B) a binder resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E) a thiol-based additive, and (F) a solvent, wherein the repeating unit represented by the formula (2) is contained in an amount of 30% by weight to 60% by weight based on the total amount of the binder resin, and A manufactured color filter is provided.
[Chemical Formula 1]

(2)

(Wherein each substituent is the same as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition and a color filter manufactured using the same.

Generally, a color filter applied to a display forms a desired pattern through an exposure process using a photoresist composition using a photosensitive resist composition, and forms a color filter through a patterning process in which an unexposed portion is dissolved and removed through a development process. The material for the color filter is alkali-soluble and requires high sensitivity, adhesion to the substrate, chemical resistance, and heat resistance. It is usual to use a pigment or a dye as a color material.

However, since the pigments are excellent in heat resistance and chemical resistance, they are not well dispersed in a solvent, and thus have poor color characteristics such as brightness. In the case of dyes, color characteristics are excellent, but durability is poor and heat resistance and chemical resistance are not excellent .

Accordingly, there is a continuing development of a novel self-luminous type photosensitive resin composition and a color filter material to which the present invention can overcome the technical limitations of a photosensitive resin composition using a pigment or a dye as a color material.

One embodiment is to provide a photosensitive resin composition capable of minimizing a decrease in the light conversion rate as the color filter process proceeds.

Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.

One embodiment includes (A) a quantum dot; (B) a binder resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E) thiol-based additives; And (F) a solvent, wherein the repeating unit represented by Formula 2 is contained in an amount of 30% by weight to 60% by weight based on the total amount of the binder resin.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ² is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

n1 is an integer of 0 to 5;

The repeating unit represented by the formula (2) may be contained in an amount of 30 wt% to 50 wt% with respect to the total amount of the binder resin.

The repeating unit represented by the formula (1) may be contained in an amount of 10% by weight to 30% by weight with respect to the total amount of the binder resin.

The binder resin may further include at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Chemical Formulas 3 to 5,

R ³ , R ⁵ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ⁴ , R ⁶ and R ⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ¹ and L ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,

n2 to n4 each independently represent an integer of 0 to 5;

The binder resin may have a weight average molecular weight of 3,000 g / mol to 10,000 g / mol.

The quantum dots may include a quantum dot, or a combination thereof having the maximum fluorescence wavelength (fluorescence λ _em) on the quantum dot, 580nm to 700nm with a maximum fluorescence wavelength (fluorescence λ _em) at 450nm to 580nm.

The thiol-based additive may include at least two functional groups represented by the following formula (6) at the terminal.

[Chemical Formula 6]

In Formula 6,

L ³ and L ⁴ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Lt; RTI ID = 0.0 > C2-C20heteroarylene < / RTI >

The thiol-based additive may be included in an amount of 1 wt% to 10 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further comprise (G) a diffusing agent.

The diffusing agent may comprise barium sulphate, calcium carbonate, titanium dioxide, zirconia or combinations thereof.

The diffusing agent may be included in an amount of 0.5 wt% to 10 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition preferably contains 1% by weight to 30% by weight of the quantum dot (A) in the total amount of the photosensitive resin composition; 1 to 20% by weight of the binder resin (B); 1 to 20% by weight of the (C) photopolymerizable monomer; 0.1 to 5% by weight of the photopolymerization initiator (D); 1% by weight to 10% by weight of the thiol-based additive (E) and the balance of the solvent (F).

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; A fluorine-based surfactant, or a combination thereof.

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

Other aspects of the present invention are included in the following detailed description.

The quantum dot-containing photosensitive resin composition according to one embodiment can minimize a decrease in the light conversion rate caused by the progress of the color filter manufacturing process such as coating, prebaking, exposure, development, and post-baking.

1 to 4 are graphs showing the average molecular weight of the binder resin in the photosensitive resin composition according to Example 1 and Comparative Example 3 to Comparative Example 5, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (9-1) to (9-11) is contained in the main backbone of the resin.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (A) a quantum dot; (B) a binder resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E) a thiol-based additive, and (F) a solvent, and the repeating unit represented by the formula (2) is contained in an amount of 30% by weight to 60% by weight based on the total amount of the binder resin.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

n1 is an integer of 0 to 5;

In general, a photosensitive resin composition uses a pigment or a dye as a colorant, but there is a technical limitation in terms of color characteristics, heat resistance, and chemical resistance. Accordingly, it has been proposed to use quantum dots other than pigments or dyes as the colorant. When a quantum dot is used as a coloring agent, the effect of improving color reproducibility and improving luminance is greater than in the case of using a pigment or a dye.

However, the color filter process consists of several steps, sometimes in very severe conditions. Particularly, quantum dots are susceptible to oxygen, moisture, heat and the like, and as the time passes or the color filter process proceeds, the light conversion rate of green light or red light of blue light absorbed from BLU (back light unit) There is a problem that it is rapidly reduced.

The photosensitive resin composition according to one embodiment includes a binder resin containing the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) to minimize the degradation of the photoconversion rate as described above, Since the repeating unit represented by the general formula (2) is contained in an amount of 30% by weight to 60% by weight with respect to the total amount of the binder resin, the decrease in the light conversion rate of the quantum dot can be minimized.

Each component will be described in detail below.

(A) Qdot

The quantum dot can absorb light in a wavelength range of 360 nm to 780 nm, for example, a wavelength range of 400 nm to 780 nm, and emit fluorescence in a wavelength range of 450 nm to 700 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence? _Em ) at 450 nm to 700 nm.

Specifically, the quantum dot has a maximum fluorescence wavelength (fluorescence λ _em) quantum dot has a (e.g. green quantum dots), the maximum fluorescence wavelength (fluorescence λ _em) quantum dots (e. G. The red quantum dots) with at 580nm to 700nm from 450nm to 580nm or And combinations of these.

The green quantum dot may have an average particle diameter of 5 nm to 10 nm, and the red quantum dot may have an average particle diameter of 7 nm to 15 nm.

The quantum dot may have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 80 nm, for example, 40 nm to 60 nm. When the quantum dots have a half width of the above range, the color purity is high when used as a color filter material as the color purity is high.

The quantum dot may be an organic material or an inorganic material or a hybrid of an organic material and an inorganic material.

The quantum dot may comprise a core and a shell surrounding the core. The core and the shell may each independently comprise a core, a core / shell, a core / a first shell / a second shell, , Alloys, alloys / shells, and the like, but the present invention is not limited thereto.

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs and alloys thereof , But is not limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe and alloys thereof.

The structure of the quantum dot is not particularly limited, but in the case of quantum dots of the core / shell structure, the size (average particle size) of the entire quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 10 nm.

In order to improve the stability and dispersibility of the quantum dots, it is possible to stabilize quantum dots by substituting organic materials on the surface of the shell. The organic materials include thiol compounds, amine compounds, phosphine oxide compounds, acryl compounds, Si Compounds, and the like, but the present invention is not limited thereto.

In recent years, interest in the environment has greatly increased worldwide, and regulations on toxic substances have been strengthened. Therefore, instead of a luminescent material having a cadmium core, a quantum yield is lowered, but an environmentally friendly non-cadmium luminous material For example, InP / ZnS core / shell type quantum dots, InP / ZnSe / ZnS core / first shell / second shell type quantum dots However, it is not necessary to use a non-cadmium-based light emitting material.

For the dispersion stability of the quantum dot, the photosensitive resin composition according to one embodiment may further include a dispersant. The dispersant helps the quantum dots to be uniformly dispersed in the photosensitive resin composition, and both nonionic, anionic and cationic dispersants can be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxides Adducts, alkylamines, and the like, which may be used alone or in admixture of two or more. The dispersant may be used in an amount of 0.1% by weight to 100% by weight, for example, 10% by weight to 20% by weight, based on the solid content of the quantum dot.

The quantum dot may be included in an amount of 1% by weight to 30% by weight based on the total amount of the photosensitive resin composition according to one embodiment. When the quantum dots are included within the above ranges, it is possible to prevent the development of the light conversion characteristic inherent to the quantum dots and the decrease in the light conversion efficiency.

(B) binder resin

The binder resin includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and the repeating unit represented by the following formula (2) is contained in an amount of 30 wt% to 60 wt% . For example, the repeating unit represented by the following formula (2) may be contained in an amount of 30% by weight to 50% by weight based on the total amount of the binder resin.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

n1 is an integer of 0 to 5;

The binder resin can improve developability by including the repeating unit represented by the formula (1), and the heat resistance can be improved by including the repeating unit represented by the formula (2). In particular, since the repeating unit represented by the above-mentioned formula (2) is contained in the above range relative to the total amount of the binder resin, the heat resistance can be greatly improved and the thermal stability of the quantum dot after the post- Can be increased, and deterioration of the light conversion rate can be minimized.

The repeating unit represented by the formula (1) may be contained in an amount of 10% by weight to 30% by weight with respect to the total amount of the binder resin. Since the repeating unit represented by the above formula (1) is included in the above range relative to the total amount of the binder resin, excellent developability can be maintained even during the color filter process.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Chemical Formulas 3 to 5,

n2 to n4 each independently represent an integer of 0 to 5;

For example, when the binder resin further comprises at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (3), the repeating unit represented by the formula (4) and the repeating unit represented by the formula (5), the hydrophobic ligand The affinity and compatibility with the quantum dot surface-substituted with the quencher are excellent.

For example, the repeating unit represented by Formula 3 may be contained in an amount of 10% by weight to 40% by weight based on the total amount of the binder resin, and the repeating unit represented by Formula 4 is preferably 7% by weight to 15% %, And the repeating unit represented by the formula (5) may be included in an amount of 5 to 20 wt% based on the total amount of the binder resin. For example, when the binder resin includes both the repeating unit represented by the above-mentioned formula (3), the repeating unit represented by the above formula (4) and the repeating unit represented by the above formula (5), the repeating unit represented by the above formula And the repeating unit represented by the general formula (5) may be independently included in an amount of 5 to 20% by weight, for example, 5 to 15% by weight based on the total amount of the binder resin. In this case, the color filter fine pattern formation property and the pattern straightness are excellent.

The binder resin may have a 3,000 g / mol to about a 10,000 g / mol weight-average molecular weight (M _w). When the weight average molecular weight of the binder resin is within the above range, the binder resin is excellent in adhesion with a substrate, has good physical and chemical properties, and is particularly suitable from the viewpoint of coating properties.

The photosensitive resin composition according to one embodiment may further include a cadmium binder resin. In this case, the developability of the photosensitive resin composition is excellent, the sensitivity upon photocuring is excellent, and the fine pattern forming property is excellent.

The cadmium binder resin may include a repeating unit represented by the following general formula (9).

[Chemical Formula 9]

In the above formula (9)

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxy group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁷ R ¹⁸ , SiR ¹⁹ R ²⁰ (wherein R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Is any one of the linking groups represented by formulas (9-1) to (9-11)

[Formula 9-1]

[Formula 9-2]

[Formula 9-3]

[Formula 9-4]

[Formula 9-5]

(9-5)

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or a phenyl group.

[Formula 9-6]

[Formula 9-7]

[Chemical Formula 9-8]

[Formula 9-9]

[Chemical Formula 9-10]

[Formula 9-11]

Z ² is an acid anhydride residue,

t1 and t2 are each independently an integer of 0 to 4;

The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, pattern formation is good without residue during the production of the photosensitive organic film, no loss of film thickness during development, and good patterns can be obtained.

The cadmium-based binder resin may include a functional group represented by the following formula (10) in at least one of both terminals.

[Chemical formula 10]

In Formula 10,

Z ³ may be represented by the following general formulas (10-1) to (10-7).

[Formula 10-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group)

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.

[Formula 10-6]

[Formula 10-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

The binder resin may be contained in an amount of 1% by weight to 20% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(C) Photopolymerization Monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^®, ^® copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 15 wt% based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the pattern is formed with sufficient curing during exposure in the step of pattern formation, so that the reliability is excellent, and the heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern are also excellent.

(D) Light curing Initiator

The photopolymerization initiator is an initiator generally used in a photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanone compound, a benzoin compound, a triazine compound, a oxime compound, Etc. may be used.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate, and the like.

Examples of the aminoketone-based compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1).

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.3 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator sufficiently undergoes curing during exposure in the pattern formation step, thereby obtaining excellent reliability, and is excellent in heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern, .

(E) Thiol system additive

In order to improve stability and dispersibility of the quantum dot, the photosensitive resin composition according to one embodiment further includes a thiol-based additive.

The thiol-based additive is substituted on the surface of the shell of the quantum dots to improve the dispersion stability of the quantum dots with respect to the solvent and stabilize the quantum dots.

The thiol-based additive may have 2 to 10, for example, 2 to 4 thiol (-SH) at the terminal thereof depending on its structure.

For example, the thiol-based additive may include at least two functional groups represented by the following formula (6) at the terminal.

[Chemical Formula 6]

In Formula 6,

For example, the thiol-based additive may be represented by the following general formula (7).

(7)

In Formula 7,

L ³ and L ⁴ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Lt; / RTI > is a C2 to C20 heteroarylene group,

n5 and n6 are each independently an integer of 0 or 1;

For example, in the above formulas (6) and (7), L ³ and L ⁴ each independently represents a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

Specific examples of the thiol-based additive include pentaerythritol tetrakis (3-mercaptopropionate) represented by the following formula (8a), trimethylolpropane tris (3-mercaptopropionate) represented by the following formula 3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate) represented by the following formula 8c, pentaerythritol tetrakis (mercaptoacetate) represented by the following formula 8c, trimethylolpropane tris (mercaptoacetate) (2-mercaptoacetate) represented by the following formula (8e), Glycol di-3-mercaptopropionate represented by the following formula (8e), and a combination thereof. One can be said.

[Chemical Formula 8a]

[Formula 8b]

[Chemical Formula 8c]

[Chemical Formula 8d]

[Chemical Formula 8e]

The thiol-based additive may be included in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 5 wt% based on the total amount of the photosensitive resin composition. If the amount of the thiol-based additive is less than 1% by weight, it is difficult to maintain the stability of each quantum dot in each process. If the amount of the thiol-based additive is more than 10% by weight, patternability of the photosensitive resin composition may be deteriorated, .

(F) Solvent

The solvent may be a solvent having compatibility with the quantum dot, and a material having compatibility with the thiol additive, the binder resin, the photopolymerizable monomer, and the photopolymerization initiator and not reacting with the photopolymerizable monomer.

Examples of the solvent having compatibility with the quantum dots include alkanes such as pentane, hexane, heptane and the like (R-H, R means a hydrocarbon group); Aromatic hydrocarbons such as toluene and xylene (Ar-H and Ar represent aromatic hydrocarbon groups); Ethers such as diisobutyl ether, dibutyl ether and ethylene glycol dimethyl ether (R-O-R, wherein R represents a hydrocarbon group); Alkyl halides such as chloroform, trichloromethane and the like (R-X, wherein R represents a hydrocarbon group); Cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like, but the present invention is not limited thereto.

Examples of the solvent having compatibility with the thiol-based additive, the binder resin, the photopolymerizable monomer and the photopolymerization initiator include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of 30% by weight to 80% by weight, for example, 30% by weight to 70% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the photosensitive organic film is excellent.

(G) Diffuser (or Diffuser Dispersion)

The photosensitive resin composition according to one embodiment may further include a diffusing agent. For example, the photosensitive resin composition according to one embodiment may further include a dispersant dispersion in which the dispersant is dispersed. As the dispersion liquid in which the diffusion agent is dispersed, any organic solvent such as PGMEA can be used without any particular limitation.

For example, the diffusing material may include barium sulfate (BaSO _4), calcium carbonate (CaCO _3), titanium dioxide (TiO _2), zirconia (ZrO _2), or a combination thereof.

The diffusing agent reflects light that is not absorbed by the light conversion material described above, and allows the light conversion material to absorb the reflected light again. That is, the diffusing agent may increase the amount of light absorbed by the photo-conversion material, thereby increasing the light conversion rate of the quantum dot in the photosensitive resin composition. That is, it is possible to prevent a decrease in the blue light conversion rate as the color filter process proceeds.

The diffusing agent may have an average particle diameter (D ₅₀ ) of 150 nm to 250 nm, and more specifically, 180 nm to 230 nm. When the average particle diameter of the diffusing agent is within the above range, it is possible to have a better light diffusing effect and increase the light conversion efficiency.

The dispersing agent, specifically, the dispersant solid content may be included in an amount of 0.5% by weight to 10% by weight, for example, 1% by weight to 8% by weight based on the total amount of the photosensitive resin composition. When the amount of the dispersing agent is less than 0.5% by weight based on the total amount of the photosensitive resin composition, it is difficult to expect an effect of preventing a decrease in the photoconversion rate upon use of the dispersing agent. When the amount exceeds 10% by weight, The pattern characteristic of the film is deteriorated, and as a result, the light conversion rate is lowered. That is, the dispersion liquid may include 2.5 wt% to 50 wt%, for example, 5 wt% to 40 wt% of the total amount of the photosensitive resin composition.

(H) Other additives

The photosensitive resin composition according to one embodiment includes malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; A fluorine-based surfactant, or a combination thereof.

For example, the photosensitive resin composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group or an epoxy group in order to improve adhesion with a substrate or the like.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesion and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray silicone (Note)社SH-28PA ^®, ^® -190 copper, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ® , and the like; Fluorinated surfactants commercially available under the names F-482, F-484, F-478 and F-554 of DIC Co., Ltd. can be used.

The fluorine-based surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the fluorosurfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wettability to the glass substrate is excellent.

In addition, a certain amount of other additives such as an antioxidant, a stabilizer and the like may be further added to the above photosensitive resin composition within a range that does not impair the physical properties.

Another embodiment provides a color filter manufactured using the above-described photosensitive resin composition. A method of manufacturing the color filter is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is applied onto a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method, applicator method or the like to a desired thickness, for example, 9 to 10 탆 After coating, the solvent is removed by heating at a temperature of about 100 캜 for 1 minute to 10 minutes to form a coating film.

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type is interposed therebetween and then an active line of 200 to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.

The exposure dose varies depending on the kind of each component of the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high pressure mercury lamp is used, the exposure dose is 500 mJ / cm ² (By a 365 nm sensor).

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

By using the above-described photosensitive resin composition, it is possible to minimize a decrease in the light conversion rate due to the application and coating film formation step, the exposure step, the development step, the post-treatment step, and the like.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

(Preparation of photosensitive resin composition)

Binder resin synthesis

Into a 1 L three-neck reaction flask equipped with a condenser, propylene glycol monomethyl ether acetate (PGMEA) was added and the temperature was increased to 85 ° C under a nitrogen atmosphere. Acrylic acid, benzyl methacrylate, cyclohexyl methacrylate, styrene and N-phenyl maleimide are added to the weighing flask in the following Table 1 Weigh the weight% and dissolve in PGMEA. At the same time, 1.8 g of a thermosetting initiator (V-601) and 0.6 g of a chain transfer agent, Mercaptoethanol (10% in PGMEA) are added together and dissolved sufficiently. Insert one end of the injection tube into the prepared metering flask, connect the other end of the tube to the syringe pump, and drop into the reaction flask for 3 hours. When the addition is completed, the reaction is further maintained for 5 hours and then the temperature is lowered to room temperature to synthesize the binder resin according to Synthetic Examples 1 to 8.

(Unit: wt%) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Acrylic acid 20 20 20 20 20 20 20 20 Benzyl methacrylate 10 40 0 0 25 50 10 10 Cyclohexyl methacrylate 10 0 10 5 25 10 50 10 Styrene 10 10 10 10 10 10 10 50 N-phenylmaleimide 50 30 60 65 20 10 10 10

Photosensitive resin composition synthesis

Example 1 to Example 3 and Comparative Example 1 to Comparative Example 6

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were prepared with the compositions shown in Table 2 below using the following components.

(1) The photopolymerization initiator is dissolved in PGMEA. Add a photopolymerizable monomer, a binder resin, a thiol-based additive, and a fluorine-based surfactant to dissolve them sufficiently. Thereafter, a diffusing agent (dispersant dispersion) is added and stirred until uniformly dispersed.

(2) The quantum dot powder and the dispersant are dissolved in ethylene glycol dimethyl ether and then mixed with the binder to prepare a quantum dot-binder mixture.

(The content of the dispersant is 15 wt% based on the solid content of the quantum dot)

(3) The solution of the above-mentioned (1) and the solution of the quantum dot-binder mixture of (2) were mixed and stirred thoroughly for 30 minutes and then filtered three times to remove impurities to prepare a photosensitive resin composition.

(A) Qdot

InP / ZnSe / ZnS quantum dots (fluorescence λ _em = 530 nm, FWHM = 40 nm to 60 nm, Green QD, Hansol Chemical Co.)

(B) Binder resin

(B-1) The binder resin according to Synthesis Example 1 ( _Mw = 4,500 g / mol)

(B-2) The binder resin according to Synthesis Example 2 ( _Mw = 5,000 g / mol)

(B-3) The binder resin according to Synthesis Example 3 ( _Mw = 4,000 g / mol)

(B-4) A binder resin according to Synthesis Example 4 ( _Mw = 4,000 g / mol)

(B-5) The binder resin according to Synthesis Example 5 ( _Mw = 8,000 g / mol)

(B-6) A binder resin according to Synthesis Example 6 (M _w = 8,000 g / mol)

(B-7) The binder resin according to Synthesis Example 7 (M _w = 9,000 g / mol)

(B-8) a binder resin according to the Synthesis Example _{8 (M w = 8,000g / mol} )

(B-9) SM-400H (SMS社; M w = 7,000 g / mol)

The weight average molecular weight of the binder resin was measured by gel permeation chromatography (GPC), and the results of GPC measurement of the binder resin according to Synthesis Example 1 and Synthesis Example 6 to Synthesis Example 8 in the binder resin are shown in FIGS. 1 to 4 .

(C) Photopolymerization Monomer

Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku)

(D) Light curing Initiator

Oxime initiator (PBG-304, Tronyl)

(E) Thiol system additive

Glycol di-3-mercaptopropionate ^{(THIOCURE ® GDMP, BRUNO BOCK社} )

(F) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(G) Diffuser Dispersion

Titanium dioxide dispersion (TiO ₂ solid content 20 wt% in PGMEA, average particle diameter: 200 nm, Aldrich)

(H) Other additives

Fluorine-based surfactant (F-554, DIC)

(Unit: wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) Photoconductive material 18 18 18 18 18 18 18 18 18 (B) binder resin (B-1) 3 - - - - - - - - (B-2) - 3 - - - - - - (B-3) - - 3 - - - - - - (B-4) - - - 3 - - - - - (B-5) - - - - 3 - - - - (B-6) - - - - - 3 - - - (B-7) - - - - - - 3 - - (B-8) - - - - - - - 3 - (B-9) - - - - - - - - 3 (C) a photopolymerizable monomer 2 2 2 2 2 2 2 2 2 (D) a photopolymerization initiator 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (E) Thiol-based additives 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (F) Solvent 53 53 53 53 53 53 53 53 53 (G) Diffusing agent dispersion 22 22 22 22 22 22 22 22 22 (H) Other additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Evaluation: blue by process Light conversion rate And Light retention rate evaluation

Each of the photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 6 was coated on a glass substrate with a thickness of 10 占 퐉 using a spin coater (Mikasa, Opticoat MS-A150, 150 rpm) After pre-baking (PRB) at 100 ° C for 2 minutes using a hot-plate, initial blue light conversion was measured.

After irradiating UV with an output power of 60 mJ / cm ² to 100 mJ / cm ² using an exposure machine (Ushio, ghi broadband), the blue light conversion rate in the exposure step was measured.

Subsequently, post-baking (POB) was conducted in convection clean oven (jongro Co., Ltd.) at 180 ° C for 30 minutes, and the blue light conversion rate was measured.

For each of the pre-baking step, the exposure step and the post-baking step, the light conversion efficiency and the light retention ratio of blue light incident from the BLU were evaluated, and the results are shown in Table 3 below. Here, the blue light conversion rate was measured with a CAS 140 CT spectrometer. The bare glass was placed on a blue BLU covered with a diffusing film, and the reference was measured by a detector. Then, (Green / Blue) was measured by calculating the increase amount of the peak converted to green against the decrease amount of the blue light absorption peak by placing a monolayer coated with the photosensitive resin composition according to Comparative Example 6 on the substrate. Also, how much the light conversion rate in the initial PRB step is maintained in the POB step, that is, the light retention rate in the course from the PRB step to the POB step, is also measured. Since the POB process can be added up to a maximum of two times depending on the color (for example, when the green quantum dot-containing photosensitive resin composition is first patterned, a photosensitive resin composition containing a quantum dot other than green (for example, red) When patterning, the thermal history is simultaneously received in the POB process), and the blue light conversion rate was measured in the same manner every time the POB process was added.

(unit: %) fair Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Light conversion rate Immediately after exposure 29 29 30 28 31 31 29 27 32 Immediately after POB 21 20 20 19 20 21 20 18 21 Immediately after POB twice 19 18 18 17 18 18 18 16 19 Immediately after 3 POB 18 17 17 16 17 16 16 15 17 Light retention rate Immediately after POB 70 69 67 67 65 63 63 60 65 Immediately after 3 POB 60 59 57 55 55 50 51 48 53

As shown in Table 3, the photosensitive resin compositions according to Examples 1 to 3 had lower degradation in blue light conversion rate as the color filter process proceeded, as compared with the photosensitive resin compositions according to Comparative Examples 1 to 6, It can be confirmed that the light retention rate is high. From this, a binder resin comprising the repeating unit represented by the formula (1) and the repeating unit represented by the following formula (2), wherein the repeating unit represented by the formula (2) is contained in an amount of 30 wt% to 60 wt% It can be seen that the decrease in the blue light conversion factor by the color filter process is prevented, and the light retention ratio can be effectively increased.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims

(A) quantum dots;
(B) a binder resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2);
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator;
(E) a thiol-based additive and
(F) Solvent
Lt; / RTI >
Wherein the repeating unit represented by Formula 2 is contained in an amount of 30% by weight to 50% by weight based on the total amount of the binder resin.
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ² is a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
n1 is an integer of 0 to 5;

delete

The method according to claim 1,
Wherein the repeating unit represented by Formula 1 is contained in an amount of 10 to 30% by weight based on the total amount of the binder resin.

The method according to claim 1,
Wherein the binder resin further comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Chemical Formulas 3 to 5,
R ³ , R ⁵ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ⁴ , R ⁶ and R ⁸ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L ¹ and L ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group,
n2 to n4 each independently represent an integer of 0 to 5;

The method according to claim 1,
Wherein the binder resin has a weight average molecular weight of 3,000 g / mol to 10,000 g / mol.

The method according to claim 1,
The quantum dots are 450nm to 580nm at the maximum fluorescence wavelength (fluorescence λ _em) having a quantum dot, the quantum dot from 580nm to 700nm with a maximum fluorescence wavelength (fluorescence λ _em) or a photosensitive resin composition comprising a combination of the two.

The method according to claim 1,
Wherein the thiol-based additive comprises at least two functional groups represented by the following formula (6) at the terminals:
[Chemical Formula 6]

In Formula 6,
L ³ and L ⁴ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Lt; RTI ID = 0.0 > C2-C20heteroarylene < / RTI >

The method according to claim 1,
Wherein the thiol-based additive is contained in an amount of 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.

The method according to claim 1,
The photosensitive resin composition further comprises (G) a diffusing agent.

10. The method of claim 9,
Wherein the diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.

10. The method of claim 9,
Wherein the diffusing agent is contained in an amount of 0.5% by weight to 10% by weight based on the total amount of the photosensitive resin composition.

The method according to claim 1,
The above-mentioned photosensitive resin composition is characterized in that the total amount of the photosensitive resin composition
1 to 30% by weight of the quantum dot (A);
1 to 20% by weight of the binder resin (B);
1 to 20% by weight of the (C) photopolymerizable monomer;
0.1 to 5% by weight of the photopolymerization initiator (D);
1% to 10% by weight of the (E) thiol-based additive and
The above (F) solvent
.

The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; A fluorine-based surfactant, or a combination thereof.

A color filter produced by using the photosensitive resin composition of any one of claims 1 to 13.