KR102028439B1 - Self emission type photosensitive resin composition, and color filter comprising thereof and display device comprising of the same - Google Patents

Abstract

The present invention relates to a self-luminous photosensitive resin composition, a color filter including the same, and an image display device, and more particularly, a long-chain carboxyl group is introduced into an acrylate side chain in a molecular structure, and a highly reactive (meth) acrylate group is formed at the terminal. The present invention relates to an alkali-soluble resin, a quantum dot, a photopolymerizable compound, a self-luminous photosensitive resin composition comprising a photopolymerization initiator, a color filter and an image display device including the same.
The alkali-soluble resin can more effectively protect the quantum dots to effectively prevent the emission efficiency of the quantum dots after the hard bake process to provide a high quality color filter with excellent brightness characteristics.

Description

Self-emitting photosensitive resin composition, and color filter and image display device comprising the same

The present invention relates to a self-luminous photosensitive resin composition, a color filter and an image display device including the same, which can effectively prevent the emission efficiency of the quantum dot after the hard bake process.

The color filter is a thin film type optical component that extracts three colors of red, green, blue, and white color from white light, and enables the pixel unit to have a pixel size of about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate for shielding the boundary between each pixel, and a plurality of colors (typically, red (R) and green (G) to form each pixel. And a pixel portion in which three primary colors of blue (B) are arranged in a predetermined order. In general, color filters can be produced by coating three or more colors on a transparent substrate by a dyeing method, electrodeposition method, printing method, pigment dispersion method, etc. Recently, the pigment dispersion method using a pigment dispersion type photosensitive resin is mainly used in the mainstream. Achieve.

The pigment dispersion method, which is one of methods for implementing a color filter, coats a photosensitive resin composition including alkali colorant, alkali soluble resin, photopolymerization monomer, photopolymerization initiator, epoxy resin, solvent, and other additives on a transparent substrate provided with a black matrix. After exposing the pattern of the form to be formed, it is a method of forming a colored thin film by repeating a series of processes of removing the non-exposed areas with a solvent and thermally curing, and is active in manufacturing LCDs of mobile phones, laptops, monitors, and TVs. Is being applied. In recent years, even in the photosensitive resin composition for color filters using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also high color reproduction rate and high performance such as high brightness and high contrast ratio are required.

However, color reproduction is realized by the light emitted from the light source passing through the color filter. In this process, some of the light is absorbed by the color filter, and thus the light efficiency is lowered. There are fundamental limitations.

As a solution to this problem, there is a color filter manufacturing method using a quantum dot photosensitive resin composition.

Korean Patent Publication No. 2007-0094679 discloses that color reproducibility can be improved by having a color filter layer formed of quantum dots, and Korean Patent Publication No. 2009-0036373 discloses a light emitting layer made of a quantum dot phosphor. It is proposed that the display quality can be improved by improving the luminous efficiency by replacing with.

Thus, when the quantum dot is used as the light emitting material of the color filter, the light emission waveform can be narrowed, and the pigment has a high color rendering ability that cannot be realized by the pigment, and has excellent luminance characteristics. However, due to the low stability of the quantum dots during the hard bake process performed in the color filter manufacturing, crystals are generated on the surface, thereby causing a problem in that the luminous efficiency of the quantum dots is greatly decreased.

Republic of Korea Patent Publication No. 2007-0094679 Republic of Korea Patent Publication No. 2009-0036373

Accordingly, the present inventors have conducted various studies to suppress the decrease in the efficiency of the quantum dots. As a result, the present inventors introduced a long-chain carboxyl group into the acrylate side chain and an alkali-soluble resin designed by introducing a highly reactive (meth) acrylate group into the terminal. As a result, the present invention was completed by confirming that the quantum dot can be more effectively protected.

Accordingly, it is an object of the present invention to provide a color filter that can effectively prevent the light emission efficiency of the quantum dots.

Further, another object of the present invention is to provide an image display apparatus having the above-described color filter and having high luminance characteristics.

In order to achieve the above object, the present invention provides a self-luminous photosensitive resin composition comprising a quantum dot, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

At this time, the alkali-soluble resin is characterized in that it comprises a repeating unit represented by the following formula (1).

[Formula 1]

(In Formula 1, R ₁ to R ₄ are as described in the specification)

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

The present invention also provides an image display device having the color filter.

When the pixel pixel of the color filter is formed using the quantum dot photosensitive resin composition including the alkali-soluble resin of the present invention, a high quality color filter having excellent luminance characteristics by eliminating the luminous efficiency degradation and poor photosensitive characteristics of the quantum dots generated after the hard bake process Can be provided.

 The present invention provides a self-luminous photosensitive resin composition that can be used for a color filter of an image display device.

<Self-luminous photosensitive resin composition>

In the case of quantum dots used to replace pigments and dyes in the color filter, the color is generated by the self-luminous emission, wherein the spontaneous instability of the quantum dots reduces the efficiency of spontaneously emitted light, in particular, the hard bake process for manufacturing color filters Occurs seriously in Accordingly, the present invention provides a self-luminous photosensitive resin composition having a specific functional group and an alkali-soluble resin having a controlled chain length so as to surround and protect the surface of the quantum dot to effectively suppress the decrease in light efficiency.

Alkali soluble resin

Alkali-soluble resin makes the non-exposed part of the photosensitive resin layer alkali-soluble, and can remove it, and serves to remain an exposure area | region. In addition to performing the above-described role, the alkali-soluble resin according to the present invention serves as a protecting group so that the quantum dot particles are uniformly dispersed in the composition and do not cause defects on the surface of the quantum dot during the coating process.

Such alkali-soluble resin has a long chain carboxyl group and a (meth) acrylate group in molecular structure, Preferably it is represented by following General formula (1).

(In Formula 1,

R ₁ is hydrogen or a methyl group,

R ₂ is a C1-C30 alkyl group, a C1-C30 alkyloxy group, or a C1-C30 alkyloxycarbonylaminoalkyl group, wherein the alkyl group, alkyloxy group or alkyloxycarbonylaminoalkyl group is C1-C20 alkyl group , C1-C20 alkoxy group, C1-C20 aralkyl group, C6-C20 aryl group, C1-C20 acyloxy group, C1-C20 acyl group, C1-C20 alkoxycarbonyl group, C6-C20 aryl Carbonyl group, C1-C20 dialkylamino group, C1-C20 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfuryl group, C1-C20 alkylthio group, Trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, or morpholinocarbonyl group,

R ₃ is represented by -R ₅ -R ₆ -COOH, wherein R ₅ is -OC (= 0)-, R ₆ is C1-C30 alkylene, C2-C30 alkenylene, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N- (R ₁₄ R ₁₅ )- , -RC (= 0) -NR ₁₆ -C (= 0) R _17- , -R ₁₈ -C (= 0) -N (R ₁₉ ) (C (= 0))-R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OCR _25- , -CH = CH-OC (= O) -N ( R ₂₆ ) (R ₂₇ ) —, an arylene group of C ₆ to C 30, a hetero arylene group of C ₅ to C 30, and a cycloalkylene group of C ₆ to C ₃₀ , wherein R ₇ to R ₂₇ have or are different from each other, and each independently , Hydrogen, C1-C30 alkylene, C6-C30 arylene group, or C6-C30 cycloalkylene group,

In this case, R ₆ is C1 to C20 alkyl group, C1 to C20 alkoxy group, C1 to C20 aralkyl group, C6 to C20 aryl group, C1 to C20 acyloxy group, C1 to C20 acyl group, C1 to C20 Alkoxycarbonyl group, C6-C20 arylcarbonyl group, C1-C20 dialkylamino group, C1-C20 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfu May be substituted with a aryl group, a C1-C20 alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, or morpholinocarbonyl group,

R ₄ is a C1-C20 alkyl (meth) acrylate group)

Preferably, R ₂ is a C1-C20 alkyl group, a C1-C20 alkyloxy group, or a C1-C20 alkyloxycarbonylaminoalkyl group. More preferably, R ₂ is particularly preferably a methyl group, an ethyl group, a propylene group, a butyl group, an ethyleneoxy group, a diethyleneoxy group, a triethyleneoxy group, an ethyloxycarbonylaminoethyl group, and these are functional groups of the trivalent form. And most preferably? H-.

Preferably, R ₆ is C1 to C20 alkylene, C2 to C20 alkenylene, C6 to C20 arylene group, or C6 to C20 cycloalkylene group, which may be substituted or unsubstituted with a carboxyl group.

More preferably, R ₆ is a methylene group, an ethylene group, a propylene group, isopropylene, pentylene, ethenylene, 2-methyl-ethenylene, dimethylpropylene group, butylene group, cyclohexylene group, 4-cyclohexene Especially preferred is a cylyl group, a bicyclo [4.4.0] decylene group, a bicyclo [2.2.1] -2-heptinylene group, a phenylene group, a carboxyphenylene or a naphthalenyl group.

It is preferable that R <_4> is a C1-C12 alkyl (meth) acrylate group, More preferably, it is an acrylate or methylacrylate group.

As used herein, an "alkyl group" includes straight or branched forms, for example methyl, ethyl, n-propyl, i-propylene, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl , n-octyl, n-decyl and the like, alkylene means a divalent form of alkyl.

As used herein, an "aryl group" includes phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, and the like, and arylene means a divalent form of aryl.

As used herein, a "cycloalkyl group" refers to cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, bornyl, norbornyl and norbornenyl and their condensed forms of dicyclopentyl, dicyclohexyl, dicycloheptyl , Diadamantyl, dibornyl, dinorbornyl or dinorbornenyl, and the like, cycloalkylene means a divalent form of cycloalkyl.

(상기 화학식 1-a에서,
a,b 각각은 0 내지 30의 정수로서, a+b는 30이하이고,
R₁은 수소 또는 메틸기이고,
R₃는 -R₅-R₆-COOH로 표시되고, 이때 R₅는 -O-C(=O)-이고, R₆는 C1∼C30의 알킬렌, C2∼C30의 알케닐렌, -R₇-C(=O)-R₈-, -R₉-C(=O)-O-R₁₀-, -R₁₁-O-R₁₂-, -R₁₈-C(=O)-N(R₁₉)(C(=O))-R₂₀-, -R₂₁-C(=NR₂₂)(R₂₃)-, -CH=CH-O-C(=O)-R₂₄-, -CH=CH-O-C(=O)-N(R₂₆)(R₂₇)-, C6∼C30의 아릴렌, C5∼C30의 헤테로아릴렌, 또는 C6∼C30의 사이클로알킬렌이고, 이때 R₇ 내지 R₁₂, R₁₈ 내지 R₂₄, R₂₆ 및 R₂₇은 서로 같거나 다르며, 각각 독립적으로, C1∼C30의 알킬렌, C6∼C30의 아릴렌, 또는 C6∼C30의 사이클로알킬렌이고,
이때 상기 R₆의 알킬렌, 알케닐렌, 아릴렌, 사이클론알킬렌, 및 R₇ 내지 R₁₂, R₁₈ 내지 R₂₄, R₂₆ 및 R₂₇의 알킬렌, 알케닐렌, 아릴렌, 사이클론알킬렌은 C1∼C20의 알킬기, C1∼C20의 알콕시기, C7∼C20의 아랄킬기, C6∼C20의 아릴기, C1∼C20의 아실옥시기, C1∼C20의 아실기, C2∼C20의 알콕시카보닐기, C7∼C20의 아릴카보닐기, C2∼C20의 다이알킬아미노기, C1∼C20의 알킬아미노기, 할로겐원자, 시아노기, 푸릴기, 푸르푸릴기, 테트라하이드로푸릴기, 테트라하이드로푸르푸릴기, C1∼C20의 알킬티오기, 트라이메틸실릴기, 트라이플루오로메틸기, 카르복실기, 티에닐기, 몰포리노기, 또는 몰포리노카보닐기로 선택된 치환체로 각각 치환 가능하고,
R₄는 C1∼C20의 알킬(메타)아크릴레이트기이다).
바람직하기로, 상기 화학식 1의 반복 단위는 하기 화학식 2 내지 31의 화합물의 구조일 수 있으며, 이때 관능기를 하기 표 1에 정리하였다. Preferably, the repeating unit of Formula 1 may be a structure of a compound of Formula 1-a.
[Formula 1-a]

(In Formula 1-a,
a, b are each an integer of 0 to 30, a + b is 30 or less,
R ₁ is hydrogen or a methyl group,
R ₃ is represented by -R ₅ -R ₆ -COOH, wherein R ₅ is -OC (= 0)-, R ₆ is C1-C30 alkylene, C2-C30 alkenylene, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₈ -C (= O) -N (R ₁₉ ) (C (= O))-R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OC (= O)- N (R ₂₆ ) (R ₂₇ ) —, C ₆ to C 30 arylene, C ₅ to C 30 heteroarylene, or C ₆ to C 30 cycloalkylene, wherein R ₇ to R ₁₂ , R ₁₈ to R ₂₄ , R ₂₆ and R ₂₇ are the same as or different from each other, and each independently, C1 to C30 alkylene, C6 to C30 arylene, or C6 to C30 cycloalkylene,
Wherein R ₆ is alkylene, alkenylene, arylene, cycloalkylene, and R ₇ to R ₁₂ , R ₁₈ to R ₂₄ , R ₂₆ and R ₂₇ Alkylene, alkenylene, arylene and cyclonealkylene are C1-C20 alkyl group, C1-C20 alkoxy group, C7-C20 aralkyl group, C6-C20 aryl group, C1-C20 acyloxy group, C1-C20 C20 acyl group, C2-C20 alkoxycarbonyl group, C7-C20 arylcarbonyl group, C2-C20 dialkylamino group, C1-C20 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetra Or a substituent selected from a hydrofuryl group, tetrahydrofurfuryl group, C1-C20 alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, or morpholinocarbonyl group, respectively. ,
R ₄ is a C1-C20 alkyl (meth) acrylate group).
Preferably, the repeating unit of Formula 1 may be a structure of the compound of Formula 2 to 31, wherein the functional group is summarized in Table 1 below.

R ₁ R ₂ R ₃ : -R ₅ -R ₆ -COOH R ₄ R ₅ R ₆ Formula 2 CH ₃ CH O-C (= O) CH ₂ A ¹⁾ Formula 3 CH ₃ CH O-C (= O) CH ₂ MA ²⁾ Formula 4 CH ₃ CH O-C (= O) CH ₂ -CH ₂ A Formula 5 CH ₃ CH O-C (= O) CH ₂ -CH ₂ MA Formula 6 CH ₃ CH O-C (= O) CH-CH (CH ₃ ) A Formula 7 CH ₃ CH O-C (= O) CH-CH (CH ₃ ) MA Formula 8 CH ₃ CH O-C (= O) CH ₂ -CH ₂ -CH ₂ A Formula 9 CH ₃ CH O-C (= O) CH ₂ -CH ₂ -CH ₂ MA Formula 10 CH ₃ CH O-C (= O) CH ₂ -C (CH ₃ ) ₂ -CH ₂ A Formula 11 CH ₃ CH O-C (= O) CH ₂ -C (CH ₃ ) ₂ -CH ₂ MA Formula 12 CH ₃ CH O-C (= O) CH = CH A Formula 13 CH ₃ CH O-C (= O) CH = CH MA Formula 14 CH ₃ CH O-C (= O) CH = C (CH ₃ ) A Formula 15 CH ₃ CH O-C (= O) CH = C (CH ₃ ) MA Formula 16 CH ₃ CH O-C (= O)

(ortho)

(ortho) A Formula 17 CH ₃ CH O-C (= O)

(ortho) MA Formula 18 CH ₃ CH O-C (= O)

(ortho) A Formula 19 CH ₃ CH O-C (= O)

(ortho) MA Formula 20 CH ₃ CH O-C (= O)

(ortho) A Formula 21 CH ₃ CH O-C (= O)

(ortho) MA Formula 22 CH ₃ CH O-C (= O)

(ortho) A Formula 23 CH ₃ CH O-C (= O)

(ortho) MA Formula 24 CH ₃ CH O-C (= O)

(meta) A Formula 25 CH ₃ CH O-C (= O)

(meta) MA Formula 26 CH ₃ CH O-C (= O)

(para) A Formula 27 CH ₃ CH O-C (= O)

(para) MA Formula 28 CH ₃ CH O-C (= O)

(meta)
A Formula 29 CH ₃ CH O-C (= O)

(meta) MA Formula 30 CH ₃ CH O-C (= O)

(para) A Formula 31 CH ₃ CH O-C (= O)

(para) MA week)
1) A: acrylate, -CH ₂ -OC (= O) -CH = CH ₂
2) MA: Methylacrylate, -CH ₂ -OC (= O) -C (CH ₃ ) = CH ₂

In the present invention, the alkali-soluble resin may preferably be in the range of 3,000 to 100,000 in weight average molecular weight thereof in terms of polystyrene, and more preferably in the range of 5,000 to 50,000. If the weight average molecular weight of alkali-soluble resin exists in the range of 3,000-100,000, since the film | membrane decrease of an exposed part hardly arises at the time of image development, since it exists in the solubility of a non-exposed part, it may be preferable.

The acid value of the alkali-soluble resin of the present invention may be in the range of 30 to 150 mgKOH / g based on solids. If the acid value is less than 30mgKOH / g, solubility in the alkaline developer may be low and residues may remain on the substrate. If the acid value is more than 150mgKOH / g, the pattern may be more likely to break.

It is preferable that the molecular weight distribution of alkali-soluble resin is 1.0-6.0, and it is more preferable that it is 1.5-4.0. If the molecular weight distribution is 1.0 to 6.0, it may be preferable because of its developability.

Alkali-soluble resin according to the present invention may be a homopolymer containing a repeating unit of Formula 1 alone, or may be a copolymer with other unsaturated monomers. In this case, the copolymer may be an alternating copolymer, a random copolymer, or a block copolymer, and is not particularly limited in the present invention.

The copolymerizable unsaturated monomer may be (i) a carboxyl group-containing unsaturated monomer, and / or (ii) a glycidyl group-containing unsaturated monomer, and (iii) a monomer having other unsaturated bonds.

(i) The carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, or the like. Specifically, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, a-chloroacrylic acid, cinnamic acid, etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned. Moreover, the unsaturated polyhydric carboxylic acid may be the mono (meth) acrylate of a dicarboxy polymer in the both terminal, For example, (omega) -carboxypolycaprolactone monoacrylate, (omega) -carboxypolycaprolactone monomethacrylate, etc. may be used. Can be mentioned. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

(ii) Glycidyl group-containing unsaturated monomers include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acryl Acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, and the like, and more preferably glycidyl It may be (meth) acrylate, and these can be used individually or in combination of 2 types or more, respectively.

(iii) Monomers having other unsaturated bonds include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p Aromatic vinyl compounds such as methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether and indene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, tricyclodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth ) Acrylic, methoxytriethylene glycol (meth) acrylate, methoxy Propylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl Unsaturated carboxylic acid esters such as (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and the like; 2-aminoethyl acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3 Unsaturated carboxylic acid aminoalkyl ester compounds such as -aminopropyl (meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N -2-hydroxyethylacrylamide and N -2-hydroxyethyl methacrylamide; Maleimide, N - benzyl-maleimide, N - phenylmaleimide, N - unsaturated imide compounds such as cyclohexyl maleimide; Monomers, such as aliphatic conjugated dienes, such as 1, 3- butadiene, isoprene, and chloroprene, can be used.

The alkali-soluble resin is easy to disperse the quantum dots, but is used in the range of 5 to 80% by weight, preferably 10 to 70% by weight in the total self-luminous photosensitive resin in a solid content to maintain a high luminous efficiency during the process. . If the content is less than the above range, it is difficult to form a coating film. On the contrary, if the content exceeds the above range, the content of the other composition decreases, affecting the function as the color filter. Therefore, it is appropriately used within the above range.

The self-luminous photosensitive composition according to the present invention together with the alkali-soluble resin includes a quantum dot, a photopolymerizable compound, and a photopolymerization initiator. Each composition is explained in more detail below.

Quantum dots

Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are semiconducting. When a quantum dot reaches an excited state from the outside, the quantum dot emits energy according to a corresponding energy band gap.

The quantum dots used for the photosensitive resin composition of this invention are photoluminescence quantum dot particle | grains which can emit light by light irradiation.

The quantum dot according to the present invention is not particularly limited as long as it is a quantum dot capable of emitting light by stimulation by light, for example, a group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; And combinations thereof may be selected from the group. These can be used individually or in mixture of 2 or more types.

The II-VI semiconductor compound may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, and the group III-V semiconductor compound , A binary element selected from the group consisting of GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; And an elemental compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The group IV-VI semiconductor compound is a binary element selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and an elemental compound selected from the group consisting of a mixture thereof, and the group IV element or the compound comprising the same is Si, Ge, and a mixture thereof. An element compound selected from; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

In addition, the quantum dots are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.

In the dual structure of the core-shell, the material forming each core and shell may be made of the above-mentioned different semiconductor compounds. For example, the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

As the colored photosensitive resin composition used in the manufacture of a conventional color filter includes colorants of red, green, and blue for color implementation, the quantum dots of the present invention can be classified into quantum dots representing red, quantum dots representing green, and quantum dots representing blue. The quantum dot according to the present invention may be one selected from the above-mentioned red, green, blue, and combinations thereof.

The quantum dots may be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process.

The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal is grown, the organic solvent is naturally coordinated to the surface of the quantum dot crystal to act as a dispersant to control the growth of the crystal, so that the organic metal chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE, molecular) The growth of nanoparticles can be controlled through an easier and cheaper process than vapor deposition such as beam epitaxy.

The content of the quantum dot particles according to the present invention is not particularly limited. For example, the quantum dot particles may be included in an amount of 3 to 80% by weight, preferably 5 to 70% by weight, based on the total weight of the solid content of the self-luminous photosensitive resin composition. If the content is less than 3% by weight, the luminous efficiency may be insignificant. If the content is more than 80% by weight, the content of the relatively different composition may be insufficient, making it difficult to form the pixel pattern.

Photopolymerizable compound

The self-luminous photosensitive resin composition which concerns on this invention with such a quantum dot contains a photopolymerizable compound.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli Money, etc. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol (poly) acrylate having a hydroxy group or a carboxylic acid group, such as the following Chemical Formulas 32 and 33;

(In Chemical Formula 32,

R ₂₈ is an acrylate group or a methacrylate group,

R ₂₉ is hydrogen, acryloyl group or methacryloyl group.)

(In Chemical Formula 33,

R ₃₀ R ₃₃ are the same as or different from each other, and each is OH, C 1 to C 4, an alkyl group, an acrylate group, a methacrylate group, or —OR ₃₄ , and R ₃₀ At least one of R ₃₃ is an acrylate group or a methacrylate group,

이고, 이때 R₃₅ 및 R₃₆은 아크릴레이트기 또는 메타크릴레이트기이고, R₃₇은 수소, 아크릴로일기, 메타크릴로일기 또는 -C(=O)CH₂CH₂C(=O)OH이고, R ₃₄

Wherein R ₃₅ and R ₃₆ are an acrylate group or a methacrylate group, and R ₃₇ is hydrogen, acryloyl group, methacryloyl group or -C (= 0) CH ₂ CH ₂ C (= 0) OH ,

R ₃₃ is —C (═O) CH ₂ CH ₂ C (═O) OH.

As the photopolymerizable compound of the present invention, a bifunctional or higher polyfunctional monomer may be used among them, and more preferably, a carboxylic acid group-containing 5-functional photopolymerizable compound may be used.

When using a 5-functional or more photopolymerizable compound, formation of a pixel pattern is more excellent. In particular, in the case of the 5-functional photopolymerizable compound containing a carboxylic acid group, there is no deterioration in luminescence properties due to particle aggregation of the quantum dots, and excellent light reactivity can form a pixel pattern excellent in luminescence.

The content of the photopolymerizable compound is used in the range of 5 to 50% by weight, preferably 7 to 45% by weight based on 100% by weight of the self-luminous photosensitive resin composition. At this time, when the photopolymerizable compound is used in the above-described content range, the pixel pattern is easily formed with respect to the light source, so that the intensity or smoothness of the pixel portion is improved. If the content is less than the above range, the degree of photocuring caused by light is lowered, making it difficult to form the pixel pattern. On the contrary, if the content exceeds the above range, the pattern is separated.

Photopolymerization initiator

Although the photoinitiator contained in the self-luminous photosensitive resin composition of this invention is not restrict | limited, It is 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The self-luminous photosensitive resin composition containing the photoinitiator described above is highly sensitive, and the pixel pixels formed by using the composition have good strength and patternability of the pixel portion.

Although the photoinitiator contained in the self-luminous photosensitive resin composition of this invention is not restrict | limited, It is 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The self-luminous photosensitive resin composition containing the photoinitiator described above is highly sensitive, and the pixel pixels formed by using the composition have good strength and patternability of the pixel portion.

As a triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned. Moreover, the compound represented by following formula (7) is mentioned.

(In Formula 34,

R ₃₈ to R ₄₁ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a phenyl group unsubstituted or substituted with C1-C2 alkyl, a benzyl group unsubstituted or substituted with C1-C12 alkyl, or a C1-C12 alkyl group. Substituted or unsubstituted naphthyl group)

Specific examples of the compound represented by Formula 34 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3, for example). -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 'position And imidazole compounds substituted with a boalkoxy group. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include the following chemical formulas 35, 36, 37, and the like.

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, a benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di ( N, N' -dimethylamino) -benzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

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

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

Moreover, when a photoinitiator adjuvant is used together with a photoinitiator, since the self-luminous photosensitive resin composition containing these is more sensitive and productivity at the time of forming a color filter using this composition is preferable, it is preferable.

In addition, in the present invention, as the photopolymerization initiator that can be used in combination with the photopolymerization initiator, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and the like may be preferably used.

Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N -dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

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

The content of the photopolymerization initiator in the self-luminous photosensitive photosensitive resin composition of the present invention is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the solid component within 100% by weight of the total composition, and the amount of the photopolymerization initiation aid is On the basis of, it is usually 0.1 to 20% by weight, preferably 1 to 10% by weight.

When the usage-amount of the said photoinitiator exists in the said range, since the self-luminous photosensitive resin composition becomes highly sensitive and the intensity | strength of a pixel part and the smoothness in this pixel part surface tend to become favorable, it is preferable. Moreover, when the usage-amount of a photoinitiator is in the said range, since the sensitivity efficiency of a self-luminous photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

additive

In addition to the above components, the self-luminous photosensitive resin composition of the present invention may further include a UV stabilizer, a filler, another polymer compound, a curing agent, a dispersant, an adhesion promoter, an antioxidant, an anti-agglomerating agent, and the like as needed.

The UV stabilizer may be included in the photosensitive resin composition to ensure light resistance.

Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranirate derivatives, dibenzoylmethane derivatives, and the like.

Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2'-. Dihydroxy-4-methoxy benzophenone, 2, 4- dihydroxy benzophenone, etc. are mentioned.

Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 -Hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.

Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like Can be mentioned.

Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

The UV stabilizer may also be commercially available, such as TINUVIN PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN479, TINUVIN1577 , CHIMASSORB81 (above, Ciba Specialty Chemicals make, brand name), etc. are mentioned.

The UV stabilizer may have a maximum absorption region in a wavelength range of 350 nm or less (including j-rays). UV stabilizers having a maximum absorption region of 350 nm or more may weaken the irradiation intensity of i-rays. In view of the structure of the UV stabilizer, the benzophenone derivative and the triazine derivative have a good absorption region at 350 nm or less. Examples of commercially available products include TINUVIN 400, TINUVIN 1577, CHIMASSORB81, and the like as preferable examples.

Said UV stabilizer can be used individually by 1 type or in combination of 2 or more types, and can prevent the light resistance and yellowing of the photosensitive resin composition of this invention.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters and polyurethanes, and the like. Can be.

The curing agent is used to increase the core hardening and mechanical strength, and the curing agent includes an epoxy compound, a polyfunctional isocyanate compound, an oxetane compound, and the like.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic compounds. Aliphatic, cycloaliphatic or aromatic epoxy compounds, butadiene (co) polymer epoxides other than group-based epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane and cyclohexane dicarboxylic acid bis oxetane. have.

The curing agent may further include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example. As the carboxylic anhydrides, those commercially available as epoxy resin curing agents can be used. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), brand name (MH-700) ( New Japan Ewha Co., Ltd.) is mentioned. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

These dispersants can be used individually or in combination of 2 or more types, respectively, and can be contained normally in 0.01-15 weight% with respect to solid content in the photosensitive resin composition.

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto Propyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. These adhesion promoters can be used individually or in combination of 2 or more types, respectively, and can contain 0.01-10 weight% normally, Preferably it is 0.05-2 weight% with respect to solid content in the photosensitive resin composition.

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

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

solvent

The self-luminous photosensitive resin composition including the alkali-soluble resin can be prepared in a form dissolved or dispersed in a solvent for coating. The solvent according to the present invention is not particularly limited and may be an organic solvent commonly used in the art.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

Since the solvent may vary in viscosity depending on the coating method or apparatus, the content of the solvent is appropriately adjusted so that the concentration of the self-luminous photosensitive resin composition having the above-mentioned composition may be 5 to 90% by weight, preferably 20 to 80% by weight. .

The preparation of the self-luminous photosensitive resin composition including the composition described above is not particularly limited in the present invention, and a known method of mixing each composition in an appropriate ratio may be used.

<Color filter>

In addition, the present invention is preferably applicable to a color filter made of the self-luminous photosensitive resin composition.

The manufacture of the color filter comprises the steps of applying the self-luminous photosensitive resin composition according to the present invention on a substrate, selectively exposing a portion of the photosensitive resin composition, and removing the exposed or non-exposed areas of the photosensitive resin composition. It comprises a step.

The color filter obtained through such a step includes the pixel formed by exposing and developing the photosensitive resin composition mentioned above in a predetermined pattern.

When the color filter of the present invention is applied to an image display device, since the light is emitted by the light of the display device light source, it is possible to implement more excellent light efficiency. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.

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

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

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

The pattern layer formed of the photosensitive resin composition may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In the light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

In such a case, the emission light of the light source is not particularly limited when applied to the image display device, but a light source that emits blue light may be used in view of better color reproducibility.

According to another embodiment of the present invention, the pattern layer may include only the pattern layer of two colors of red pattern layer, green pattern layer, and blue pattern layer. In such a case, the pattern layer further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included can be used. For example, when including a red pattern layer and a green pattern layer, the light source which emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light as it is transmitted.

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

<Image display device>

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

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

The image display apparatus of the present invention may include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In such a case, the emission light of the light source is not particularly limited when applied to the image display device, but in view of better color reproducibility, a light source that emits blue light may be preferably used.

According to another embodiment of the present invention, the image display device of the present invention may include a color filter including only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer. In such a case, the color filter further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layer of two colors is provided, a light source that emits light having a wavelength representing the remaining colors not included can be used. For example, when including a red pattern layer and a green pattern layer, the light source which emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light as it is transmitted.

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

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Preparation Example 1 Synthesis of Photoluminescent Green Quantum Dot Particle A with CdSe / ZnS Coreshell Structure

CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 mL) were added to the reactor together with 1-octadecene (20 mL) and heated to 150 ° C. Reacted. Thereafter, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr to remove acetic acid produced by substitution of oleic acid with zinc.

Then, 310 ° C. heat was applied to obtain a clear mixture. After maintaining 310 ° C. for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. And S solution was injected rapidly into the reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions.

The resulting mixture was grown at 310 ° C. for 5 minutes and then stopped using an ice bath.

Then, precipitated with ethanol to separate the quantum dots using a centrifuge and the excess impurities are washed with chloroform and ethanol to stabilize the particles with oleic acid and have a particle size of 3 to 5 nm. Quantum dot Particles A having a CdSe (core) / ZnS (shell) structure were obtained.

Preparation Example 2 Synthesis of Alkali-Soluble Resin (D1)

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts AIBN, 23 parts 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.6 parts of methylstyrene, 46 parts of acrylic acid, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, after reducing the temperature of the reaction solution to room temperature and replacing the flask atmosphere with nitrogen from air, 0.2 parts of triethylamine, 0.1 part of 4-methoxy phenol and 23.3 parts of glycidyl methacrylate were added thereto, followed by reaction at 100 ° C. for 6 hours. It was.

Then, the temperature of the reaction solution was lowered to room temperature, and the solid acid value of the alkali-soluble resin thus synthesized was 100 mgKOH / g, and a resin (D1) having a weight average molecular weight (MW) of 6500 measured by GPC was obtained.

Production Example  3: alkali-soluble resin ( D2 ) Synthesis

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.5 parts of methylstyrene, 46 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, the reaction solution was cooled to room temperature, and the flask atmosphere was replaced with nitrogen from air, followed by 0.2 parts of triethylamine, 0.1 parts of 4-methoxy phenol, and 23.3 parts of propionic acid, followed by reaction at 100 ° C. for 6 hours.

Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C. for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 35 mgKOH / g, and a resin (D2) having a weight average molecular weight (MW) of 6300 measured by GPC was obtained.

Preparation Example 4 Synthesis of Alkali-Soluble Resin (D3)

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.5 parts of methylstyrene, 46 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, the temperature of the reaction solution was lowered to room temperature, the flask atmosphere was replaced with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 23.3 parts of acrylic acid were added, and the mixture was reacted at 100 ° C. for 6 hours.

Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C. for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 33 mgKOH / g, and a resin (D3) having a weight average molecular weight (MW) of 6350 measured by GPC was obtained.

Preparation Example 5 Synthesis of Alkali-Soluble Resin (D4)

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.5 parts of methylstyrene, 46 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, the temperature of the reaction solution was lowered to room temperature, the flask atmosphere was replaced with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 23.3 parts of acrylic acid were added, and the mixture was reacted at 100 ° C. for 6 hours.

Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C. for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 69 mgKOH / g, and a resin (D4) having a weight average molecular weight (MW) of 5580 measured by GPC was obtained.

Preparation Example 6 Synthesis of Alkali-Soluble Resin (D5)

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.5 parts of methylstyrene, 46 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, the temperature of the reaction solution was lowered to room temperature, the flask atmosphere was replaced with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 23.3 parts of acrylic acid were added, and the mixture was reacted at 100 ° C. for 6 hours.

Thereafter, the reaction solution was cooled to room temperature, 12.5 parts of glutaric anhydride was added thereto, and the mixture was reacted at 80 ° C. for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 70 mgKOH / g, and a resin (D5) having a weight average molecular weight (MW) of 5600 measured by GPC was obtained.

Preparation Example 7 Synthesis of Alkali-Soluble Resin (D6)

100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate in a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot and a nitrogen introduction tube. 1.5 parts of methylstyrene, 46 parts of glycidyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 4 hours.

Subsequently, the temperature of the reaction solution was lowered to room temperature, the flask atmosphere was replaced with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 23.3 parts of acrylic acid were added, and the mixture was reacted at 100 ° C. for 6 hours.

Thereafter, the temperature of the reaction solution was decreased to room temperature, 12.5 parts of phthalic anhydride was added thereto, and the mixture was reacted at 80 ° C. for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 75 mgKOH / g, and a resin (D6) having a weight average molecular weight (MW) of 6500 measured by GPC was obtained.

Molecular weight evaluation

About the measurement of the weight average molecular weight (Mw) of each manufactured alkali-soluble resin, it carried out on condition of the following using GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Solid content

About 1 g of the polymer solution was weighed into an aluminum cup, and about 3 g of acetone was added for dissolution, and then naturally dried at room temperature. Then, the resultant was dried under vacuum at 160 ° C. for 3 hours using a hot air dryer (trade name: PHH-101 manufactured by ESPEC Co., Ltd.), and then cooled in a desiccator and weighed. The solid content of the polymer solution was calculated from the weight loss amount.

Acid

3 g of a resin solution was precisely weighed and dissolved in acetone 90 g / water 10 g mixed solvent, and an automatic titration apparatus (0.15 KOH aqueous solution was used as a titration solution using thymol blue as an indicator, manufactured by Hiranuma Industries, Inc. 555), the acid value of the polymer solution was measured, and the acid value per 1 g of solid content was determined from the acid value of the solution and the solid content of the solution.

< Example  1-4 Comparative Examples 1-2: Self-luminescence  Production of Photosensitive Resin Composition>

After mixing each component as shown in following Table 2, it diluted with propylene glycol monomethyl ether acetate so that total solid content might be 20 weight%, and fully stirred, and obtained the self-luminous photosensitive resin composition.

Composition (% by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Quantum dot A 30 30 30 30 30 30 Photopolymerization
compound B-1 9 9 9 9 9 9 B-2 24 24 24 24 24 24 Photopolymerization initiator 5 5 5 5 5 5 Alkali solubility
Suzy D1 - - - - 32 - D2 - - - - - 32 D3 32 - - - - - D4 - 32 - - - - D5 - - 32 - - - D6 - - - 32 - -

week)

1) Quantum dot A: CdSe (core) / ZnS (shell) structure quantum dot A of Preparation Example 1

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

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

4) Photoinitiator: Irgaqure-907 (manufactured by BASF Corporation)

5) Alkali-soluble resin prepared in Preparation Example 2

6) Alkali-soluble resin prepared in Preparation Example 3

7) Alkali-soluble resin prepared in Preparation Example 4

8) Alkali-soluble resin prepared in Preparation Example 5

9) Alkali-soluble resin prepared in Preparation Example 6

10) Alkali-soluble resin prepared in Preparation Example 7

Experimental Example 1: Preparation and Evaluation of Color Filter

(1) color filter manufacturing

Color filters were prepared using the self-luminous photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2.

That is, each of the self-luminous photosensitive resin compositions was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a transmissive pattern of 20 mm x 20 mm square and a line / space pattern of 1 µm to 100 µm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 µm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an air atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern.

The film thickness of the self-luminous color pattern prepared above was 3.0 μm.

(2) emission intensity measurement

Of the color filters in which the self-luminous pixels were formed, the light-converted area was measured by a 365 nm tubular 4W UV irradiator (VL-4LC, VILBER LOURMAT) in the pattern portion formed with a 20 mm x 20 mm square pattern, and Examples 1 to 4 and comparison. Examples 1 and 2 measured the emission intensity in the 550 nm region using a spectrometer (manufactured by Ocean Optics).

It can be determined that the higher the measured emission intensity exhibits excellent self-luminous properties, and the results of the measurement of the emission intensity are shown in Table 3 below.

In this case, the color filter was subjected to a hard bake at 230 ° C. for 60 minutes to measure the emission intensity before and after the hard bake and to confirm the level at which the emission efficiency was maintained.

Luminous intensity Luminous intensity retention Example 1 4078382 49.1% Example 2 4556218 52.3% Example 3 4612452 53.1% Example 4 4423529 51.8% Comparative Example 1 3241656 41.7% Comparative Example 2 2542135 32.5%

Referring to Table 3, in the case of the color filter using the self-luminous photosensitive resin composition of Examples 1 to 4 according to the present invention it can be seen that the emission intensity retention is maintained very high even after the hard bake.

The self-luminous photosensitive resin composition according to the present invention can be introduced into the color filter of the image display device to maintain excellent color reproduction characteristics and luminance to realize high quality vivid image quality.

Claims (5)

A self-luminous photosensitive resin composition for color filter pixels, comprising: a color filter pixel self-luminous composition comprising a quantum dot, an alkali-soluble resin having a repeating unit represented by the following Chemical Formula 1-a in a molecular structure, a photopolymerizable compound, and a photopolymerization initiator:
[Formula 1-a]

(In Formula 1-a,
a, b are each an integer of 0 to 30, a + b is 30 or less,
R ₁ is hydrogen or a methyl group,
R ₃ is represented by -R ₅ -R ₆ -COOH, wherein R ₅ is -OC (= 0)-, R ₆ is C1-C30 alkylene, C2-C30 alkenylene, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₈ -C (= O) -N (R ₁₉ ) (C (= O))-R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OC (= O)- N (R ₂₆ ) (R ₂₇ ) —, C ₆ to C 30 arylene, C ₅ to C 30 heteroarylene, or C ₆ to C 30 cycloalkylene, wherein R ₇ to R ₁₂ , R ₁₈ to R ₂₄ , R ₂₆ and R ₂₇ are the same as or different from each other, and each independently, C1 to C30 alkylene, C6 to C30 arylene, or C6 to C30 cycloalkylene,
Wherein R ₆ is alkylene, alkenylene, arylene, cycloalkylene, and R ₇ to R ₁₂ , R ₁₈ to R ₂₄ , R ₂₆ and R ₂₇ Alkylene, alkenylene, arylene and cyclonealkylene are C1-C20 alkyl group, C1-C20 alkoxy group, C7-C20 aralkyl group, C6-C20 aryl group, C1-C20 acyloxy group, C1-C20 C20 acyl group, C2-C20 alkoxycarbonyl group, C7-C20 arylcarbonyl group, C2-C20 dialkylamino group, C1-C20 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetra Or a substituent selected from a hydrofuryl group, tetrahydrofurfuryl group, C1-C20 alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, or morpholinocarbonyl group, respectively. ,
R ₄ is a C1-C20 alkyl (meth) acrylate group). The method according to claim 1,
R ₃ is represented by -R ₅ -R ₆ -COOH, wherein R ₅ is -OC (= O)-, R ₆ is C1-C20 alkylene, C2-C20 alkenylene, C6-C20 aryl Ethylene or C 6 to C 20 cycloalkylene, which may be unsubstituted or substituted with a carboxyl group,
R <_4> is C1-C12 alkyl (meth) acrylate group, The self-luminous photosensitive resin composition for color filter pixels characterized by the above-mentioned. The method according to claim 1, wherein the self-luminous photosensitive resin composition for the color filter pixel is within 100% by weight of the total composition,
3 to 80 wt% of quantum dots,
5 to 80% by weight of alkali-soluble resin,
5 to 70 wt% of a photopolymerizable compound, and
0.1 to 20% by weight of a photopolymerization initiator, characterized in that the self-luminous photosensitive resin composition for color filter pixels. The color filter manufactured from the self-luminous photosensitive resin composition for color filter pixels of any one of Claims 1-3. An image display device comprising the color filter of claim 4.