KR102539870B1 - Self emission type photosensitive resin composition, color filter comprising color conversion layer using the same and display device - Google Patents

Abstract

(상기 화학식 1에서,
R₁ 및 R₂는 각각 독립적으로, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 6 내지 20의 헤테로 고리기, 및 치환 또는 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 20의 알킬기로 이루어진 군으로부터 선택되고,
R₃ 내지 R₆는 각각 독립적으로 하기 화학식 2 또는 화학식 3으로 표시되는 치환기를 포함하되, 화학식 3으로 표시되는 치환기를 적어도 하나 이상 포함된다)
[화학식 2]

(상기 화학식 2에서,
X₁ 내지 X₅는 각각 독립적으로, 수소원자, 할로겐 원자, 탄소수 1 내지 10인 직쇄 또는 분지쇄 알킬기, 탄소수 1 내지 10인 할로알킬기, 히드록시기, 탄소수 1 내지 10인 알콕시기, 시아닌기, 탄소수 1 내지 10의 에스터기 및 아민기에서 선택되는 치환기이고,
Y는 산소 원자 또는 황 원자이다)
[화학식 3]

(상기 화학식 3에서,
X₆ 내지 X₉는 각각 독립적으로, 수소원자, 할로겐 원자, 탄소수 1 내지 10인 직쇄 또는 분지쇄 알킬기, 탄소수 1 내지 10인 할로알킬기, 히드록시기, 탄소수 1 내지 10인 알콕시기, 시아닌기, 탄소수 1 내지 10의 에스터기 및 아민기에서 선택되는 치환기이고,
Y는 산소 원자 또는 황 원자이다).The present invention has the advantage of being able to form a color conversion layer with excellent fluorescence efficiency by containing a fluorescent dye containing a perylenebisimide-based compound represented by Formula 1 below, and also a color filter and an image display device including the same. It relates to a self-luminous photosensitive resin composition capable of high color reproduction, a color filter and an image display device including a color conversion layer using the same.
[Formula 1]

(In Formula 1 above,
R ₁ and R ₂ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 20 carbon atoms, and a substituted or unsubstituted straight or branched chain having 1 carbon atom It is selected from the group consisting of to 20 alkyl groups,
R ₃ to R ₆ each independently include a substituent represented by Formula 2 or Formula 3, and include at least one substituent represented by Formula 3)
[Formula 2]

(In Formula 2 above,
X ₁ to X ₅ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom. It is a substituent selected from ester groups and amine groups of 10 to 10,
Y is an oxygen atom or a sulfur atom)
[Formula 3]

(In Formula 3,
X ₆ to X ₉ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom; It is a substituent selected from ester groups and amine groups of 10 to 10,
Y is an oxygen atom or a sulfur atom).

Description

Self-luminous photosensitive resin composition, color filter and image display device including a color conversion layer using the same

The present invention relates to a self-luminous photosensitive resin composition having excellent color conversion characteristics and fluorescence efficiency, a color filter including a color conversion layer using the same, and an image display device.

Recently, the display industry has undergone a rapid change from CRT to flat panel displays represented by PDP, OLED, and LCD. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding. However, since the LCD does not have its own light emitting device, a separate backlight unit is essential.

Pigment or dye-based colored color filters used for color implementation in conventional liquid crystal display devices use the characteristics of light absorption and transmission in a specific area for the transmitted backlight source, so the transmission efficiency of the backlight source to be irradiated is rapidly reduced. have a problem

A cold cathode fluorescent lamp (CCFL) was used as a light source for a general backlight unit. However, a backlight unit using CCFL consumes a considerable amount of power because power is always applied to the CCFL, a color reproduction rate of about 70% compared to a CRT, and environmental pollution problems due to the addition of mercury are pointed out as disadvantages. As an alternative product to solve the above problems, research on a backlight unit using a light emitting diode (LED) is being actively conducted.

In the case of using LED as a backlight unit, more vivid picture quality can be provided to consumers by exceeding 100% of the NTSC (National Television System Committee) color gamut specification.

Accordingly, the same industry is trying to improve the light efficiency by changing the material and structure of the color filter and LCD panel to improve the efficiency of the backlight light source, but due to the limitation of the transmission characteristics of the coloring material, the color reproducibility and luminance characteristics are satisfied at the same time. Shiki has a problem that cannot go beyond a certain level.

Such a low color reproducibility problem can be solved through an increase in light efficiency. Therefore, a method of increasing the thickness of a color filter or introducing a color conversion layer (or light conversion layer) by stacking or adjacent to the color filter has been proposed.

1 is a schematic diagram showing the role of a color conversion layer in a display device. As shown in FIG. 1, the light source generated from the backlight 10 directly increases light efficiency through the color conversion layer 20 and the pixel unit 30. can

However, dyes or pigments are conventionally used as a composition of the color conversion layer 20, and it is difficult to expect light efficiency improvement only with these dyes and pigments, and rather, a problem of lowering luminance occurs. Accordingly, the use of a fluorescent material as a material of the color conversion layer 20 has been proposed.

In this regard, Korean Patent Publication No. 10-2017-0026245 discloses a novel perylene-based compound and a fluorescent dye containing the same, and the novel perylene-based compound has solubility in organic solvents, durability, and thermal stability. , it is described that the light emitting property shows an excellent effect, but this has a problem that does not reach the level of high color reproduction required recently.

In addition, Korean Patent Publication No. 10-2010-0056437 discloses (a) a process of forming a black matrix having a plurality of openings on a transparent substrate, and (b) at least two types of colors that transmit light in different wavelength regions. A step of forming the filter layers independently, comprising: forming a barrier rib by overlapping at least two color filter layers on a black matrix in which two different types of color filter layers are adjacent; (c) on at least one of the color filter layers; A color conversion layer having a high-definition pattern can be formed by including a step of forming a color conversion layer that absorbs light of a specific wavelength and outputs light having a wavelength different from the absorbed wavelength by using an inkjet method. and can use the film thickness of the black matrix as well as the film thickness of the color filter layer as the height of the barrier rib, thereby preventing the diffusion of ink more effectively. Since it further includes, the manufacturing process is complicated, and there is a problem in that it is difficult to thin a color filter and an image display device including the same.

Republic of Korea Patent Publication No. 10-2017-0026245 (2017.03.08.) Republic of Korea Patent Publication No. 10-2010-0056437 (2010.05.27.)

The present invention is to solve the above problems, and an object of the present invention is to provide a self-luminous photosensitive resin composition capable of high color reproduction with excellent fluorescence efficiency, a color filter and an image display device including a color conversion layer using the same. .

The self-luminous photosensitive resin composition of the present invention for achieving the above object is characterized by containing a fluorescent dye containing a perylenebisimide-based compound represented by Formula 1 below:

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 20 carbon atoms, and a substituted or unsubstituted straight or branched chain having 1 carbon atom It is selected from the group consisting of to 20 alkyl groups,

R ₃ to R ₆ are each independently a substituent represented by Formula 2 or Formula 3 below, including at least one substituent represented by Formula 3)

[Formula 2]

(In Formula 2 above,

X ₁ to X ₅ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom. It is a substituent selected from ester groups and amine groups of 10 to 10,

Y is an oxygen atom or a sulfur atom)

[Formula 3]

(In Formula 3,

X ₆ to X ₉ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom; It is a substituent selected from ester groups and amine groups of 10 to 10,

Y is an oxygen atom or a sulfur atom).

In addition, the color conversion layer according to the present invention is characterized by including a cured product of the above-described self-luminous photosensitive resin composition.

In addition, the color filter according to the present invention is characterized in that it includes the color conversion layer.

In addition, the image display device according to the present invention is characterized in that it includes the color filter.

The self-luminous photosensitive resin composition of the present invention has an advantage in that high color reproduction is possible due to excellent fluorescence efficiency.

The color conversion layer of the present invention has the same advantages as described above by including a cured product of the above-described self-luminous photosensitive resin composition.

The color filter of the present invention has the same advantages as described above by including the color conversion layer.

The image display device of the present invention has the same advantages as described above by including the color filter.

1 illustrates a color filter including a color conversion layer.

In the present invention, when a member is said to be located “on” another member, this includes not only a case in which a member is in direct contact with the other member, but also a case in which another member is interposed between the two members.

In the present invention, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

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

< self-luminous Photosensitive Resin Composition>

fluorescent dye

The self-luminous photosensitive resin composition according to one aspect of the present invention contains a fluorescent dye containing a perylenebisimide-based compound represented by the following formula (1), thereby having an advantage of forming a color conversion layer with excellent fluorescence efficiency, In addition, there is an advantage capable of high color reproduction of a color filter and an image display device including the same.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 20 carbon atoms, and a substituted or unsubstituted straight or branched chain having 1 carbon atom It is selected from the group consisting of 20 alkyl groups,

R ₃ to R ₆ are each independently a substituent represented by Formula 2 or Formula 3 below, including at least one substituent represented by Formula 3)

[Formula 2]

(In Formula 2 above,

X ₁ to X ₅ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom. It is a substituent selected from ester groups and amine groups of 10 to 10,

Y is an oxygen atom or a sulfur atom)

[Formula 3]

(In Formula 3,

X ₆ to X ₉ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom; It is a substituent selected from ester groups and amine groups of 10 to 10,

Y is an oxygen atom or a sulfur atom).

In the present specification, 'substituted or unsubstituted' means a halogen group, a nitrile group, a nitro group, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a thiol group, an alkylthiol group, an allylthio group, and a sulfoxyl group. One selected from the group consisting of an alkyl sulfoxy group, an aryl sulfoxy group, a silyl group, a boron group, an arylamine group, an aralkylamine group, an alkylamine group, an aryl group, an arylalkyl group, an arylalkenyl group, a heterocyclic group, and an acetylene group It means that it is substituted with the above substituents or does not have any substituents.

In the present specification, the halogen group may include, for example, -F, -Cl, -Br or -I.

In the present specification, the aryl group may include phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, or pyrenyl.

In the present specification, a heterocyclic group includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se, and S. For example, a thiophenyl group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, Acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquin Nolinyl group, indole group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, Dibenzofuranyl group; Benzosilol group; dibenzosilol group; A phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, and condensation structures thereof.

In the present specification, the alkyl group may be straight-chain or branched-chain, and for example, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl- butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl and the like.

In the present specification, the haloalkyl group refers to an alkyl group substituted with one or more halogen atoms selected from the group consisting of fluorine, chlorine, bromine and iodine.

As described above, when the fluorescent dye included in the self-luminous photosensitive resin composition of the present invention includes the perylenebisimide-based compound of the present invention including one or more substituents of Formula 3, even at high concentration through the steric hindrance effect of the substituents. Fluorescence can be increased, and solubility in solvents can also be improved. In addition, it exhibits excellent chemical, thermal, and optical stability, which has advantages in processing.

Specifically, the perylenebisimide-based compound represented by Chemical Formula 1 may be a compound represented by Chemical Formulas 4 to 12 below.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

As such, when the fluorescent dye included in the self-luminous photosensitive resin of the present invention includes the compounds of Chemical Formulas 4 to 12, there is an advantage in that fluorescence efficiency can be further improved.

Such compounds may be synthesized and used by conventional methods as described in the Examples.

According to one embodiment of the present invention, the perylenebisimide-based compound represented by Chemical Formula 1 is present in an amount of 0.01 to 70% by weight, preferably 0.01 to 40%, based on 100% by weight of the total solid content in the self-luminous photosensitive resin composition containing the compound. % by weight, more preferably 5 to 35% by weight. In this way, when the content of the perylenebisimide-based compound is included within the above-described range, the fluorescence efficiency can be further improved, and the productivity of the color conversion layer formed including the perylenebisimide-based compound can be improved, which is preferable.

The fluorescent dye included in the self-luminous photosensitive resin composition of the present invention may further include a fluorescent dye used in the art in addition to the perylenebisimide-based compound of Formula 1 described above.

The fluorescent dyes that may be further included are Solvent, Acid, Basic, Reactive, Direct, and dyes classified as Disperse or Vat. More specifically, dyes of the following color index (C.I.) numbers may be mentioned, but are not limited thereto.

C.I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C.I. Acid Yellow 7, 23, 25, 42, 65, 76;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct Yellow 4, 28, 44, 86, 132;

C.I. Dispulse Yellow 54, 76;

C.I. Solvent Orange 41, 54, 56, 99;

C.I. Acid Orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct Orange 26;

C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 102;

C.I. Solvent Green 1, 5;

C.I. Acid Green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1st and more.

Common fluorescent dyes include 3-(2-benzothiazolyl)-7-diethylaminocoumarin (Coumarin 6), 3-(2-benzoimidazolyl)-7-diethylaminocoumarin (Coumarin 7), and Coumarin 135. Coumarin-type dyes, such as these, are mentioned. In addition, low molecular weight organic fluorescent dyes such as naphthalimide-based dyes such as Solvent Yellow 43 and Solvent Yellow 44 may be used, and polyphenylene, polyarylene, and polyfluorene may be used. A typical high-molecular fluorescent material can also be used.

In addition, the fluorescent dye is a quinacridone derivative such as diethylquinacridone (DQ); Cyanine pigments such as 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM-1, (I)), DCM-2 (II), and DCATLB (II) ; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene (IV), Lumogen F red perylene pigment, Nile red ( V) and the like. In addition, a xanthene pigment such as rhodamine B or rhodamine 6G or a pyridine pigment such as pyridine 1 may be used.

Depending on the case, you may use the mixture of 2 or more types of pigment|dye as a color conversion pigment|dye. The use of a pigment mixture is a means that can be used when the wavelength shift width is wide, such as when converting blue light to red light. The pigment mixture may be a mixture of the above-mentioned pigments or a mixture of dyes other than the above-mentioned dyes.

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include at least one selected from the group consisting of a photopolymerizable compound, a photopolymerization initiator, a binder resin, a solvent, and an additive, in addition to the above-described fluorescent dye.

binder resin

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include a binder resin.

The binder resin usually means that it has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium for a coloring material. The binder resin contained in the self-luminous photosensitive resin composition of the present invention acts as a binder resin for a coloring material (fluorescent dye, etc.) and is soluble in an alkaline developer used in the development step for preparing the color conversion layer. can be used without

Examples of the binder resin include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with this monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in a molecule such as unsaturated tricarboxylic acids. can be heard Here, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. As unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. An acid anhydride may be sufficient as an unsaturated polyhydric carboxylic acid, and maleic acid anhydride, itaconic acid anhydride, a citraconic acid anhydride, etc. are mentioned specifically. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example mono(2-methacryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate ), mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both terminals thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. Toxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds, such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Rate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers 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-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and polysiloxane having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain. and macromonomers having These monomers can be used individually or in mixture of 2 or more types, respectively.

In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton tend to lower the relative dielectric constant value, so they are preferably used. can

The binder resin of the present invention may have an acid value ranging from 20 to 200 (KOH mg/g). When the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, a pattern of the exposed portion remains during development, so that the film remaining ratio can be improved. The acid value here is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titrating using an aqueous potassium hydroxide solution.

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. Binder resins may be preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of the non-exposed part in the developing solution is excellent, and the resolution can be further improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin may be preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0, developability can be further improved.

According to one embodiment of the present invention, the binder resin may be included in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on 100% by weight of the total solid content in the self-luminous photosensitive resin composition containing the binder resin. As such, when the content of the binder resin is within the above range, the solubility in the developing solution is sufficient so that it is difficult to generate development residues on the substrate in the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development. Omission of the pixel part can be made good.

photopolymerization compound

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerizable compound.

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other multifunctional monomers.

The monofunctional monomer is, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpy Rolidone etc. are mentioned.

The bifunctional monomer is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

The polyfunctional monomer is, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate etc. are mentioned.

Among these, bifunctional or more multifunctional monomers may be preferably used, and these are not limited to those described above, and may be used individually or in combination of two or more.

According to one embodiment of the present invention, the photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on 100% by weight of the total solid content in the self-luminous photosensitive resin composition including the photopolymerizable compound. When the content of the photopolymerizable compound is within the above range, strength or smoothness of the pixel portion may be improved.

light polymerization initiator

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerization initiator.

The photopolymerization initiator may preferably contain an acetophenone-based compound. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1 -one oligomers and the like, preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and the like.

In addition, photopolymerization initiators other than the acetophenone type may be used in combination. Photopolymerization initiators other than the acetophenone type include active radical generators, sensitizers, acid generators, and the like that generate active radicals by irradiation with light.

Examples of the active radical generating agent include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, o-benzoylmethyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra (t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned. Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl). )-6-(4-methoxynaphthyl)-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 (trichloro Methyl) -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-(3,4dimethoxyphenyl)ethenyl]-1,3, 5-triazine etc. are mentioned. Examples of the active radical generating agent include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate. nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzointosylate, etc. are mentioned.

In addition, as an active radical generator, some of the above compounds generate an acid simultaneously with an active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

According to one embodiment of the present invention, the photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on solid content, based on 100% by weight of the total amount of the binder resin and the photopolymerizable compound. there is. When the content of the photopolymerization initiator is within the above range, the self-luminous photosensitive resin composition containing the photopolymerization initiator is highly sensitive, so that the strength of the color conversion layer formed using the composition and the smoothness on the surface of the color conversion layer are good. This is desirable because it tends to

The self-luminous photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid, if necessary. The photopolymerization initiation aid may be used in combination with a photopolymerization initiator, and may be used to promote polymerization of a photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation auxiliary include amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone-based compounds, but are not limited thereto.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethyl benzoate. Aminoethyl, 4-dimethylaminobenzoic acid, 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(di Ethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene etc. are mentioned.

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxy thioxanthone etc. are mentioned.

Even if these photoinitiator adjuvants are used individually or in combination of a plurality, there is no problem. Moreover, commercially available photopolymerization initiation aids can be used, and commercially available photopolymerization initiation aids include, for example, trade name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.].

When the photopolymerization initiator is further included, the amount used may be 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator included together. When it is within the above range, the sensitivity of the self-luminous photosensitive resin composition is further increased, and productivity of color conversion layers and color filters formed using this composition tends to be improved, so it is preferable.

solvent

The photopolymerization initiation aid according to an embodiment of the present invention may further include a solvent.

The type of the solvent is not particularly limited in the present invention, and organic solvents used in the art may be used without particular limitation. For example, 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 dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene Alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, Acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methyl Cyclic esters, such as esters, such as methyl toxypropionate, and (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C are preferable from the viewpoint of coating properties and drying properties, and more preferably, alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy and esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxyethyl propionate, 3- methoxypropionate and the like, but are not limited thereto, and these may be used alone or in combination of two or more.

The solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on 100% by weight of the entire self-luminous photosensitive resin composition including the solvent. When the content of the solvent is within the above range, coating properties may be improved when applied with a coating device such as a roll coater, a spin coater, a slit-and-spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet. there is.

additive

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include an additive.

The type of the additive may be selected according to the needs of the manufacturer, and in the present invention, the type is not particularly limited. For example, fillers, other high molecular compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, An inhibitor etc. are mentioned.

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

Specific examples of the other high molecular compounds 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. can

Examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. . MEGAFAC (manufactured by Dainipbon Ink Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Sol SOLSPERSE (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As said adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole and alkoxybenzophenone. Specifically as an aggregation inhibitor, sodium polyacrylate etc. are mentioned.

< color conversion layer >

A color conversion layer according to another aspect of the present invention includes a cured product of the above-described self-luminous photosensitive resin composition.

When the color conversion layer 20 of the present invention is applied to an image display device, since it emits light from the light source 10 of the image display device, it is possible to realize superior light efficiency and emit colored light. The color reproducibility is better, the viewing angle can be improved because light is emitted in all directions by photoluminescence, and chemical resistance and surface properties are excellent (see FIG. 1).

More specifically, in a conventional image display device including a color conversion layer, white light is transmitted through the color conversion layer to implement color. In this process, light efficiency may decrease because a part of the light is absorbed by the color conversion layer. However, in the case of including a color conversion layer made of the self-luminous photosensitive resin composition of the present invention, since the color conversion layer emits light by itself by light from a light source, more excellent light efficiency can be implemented.

<Color filter>

A color filter according to another aspect of the present invention includes the above-described color conversion layer, and thus has excellent fluorescence efficiency, excellent chemical resistance, and excellent surface properties.

The color filter includes a substrate and a pattern layer 30 formed on top of the substrate in addition to the color conversion layer 20 described above. The substrate may be a color conversion layer itself, or a color conversion layer may be included in a display device It may be a site to be located, and is not particularly limited in the present invention (see FIG. 1).

The substrate may be glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the polymer substrate may include polyethersulfone (PES) or polycarbonate (PC), but is limited thereto. it is not going to be

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

The pattern layer formed of the self-luminous 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. When light is irradiated, 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 an image display device, but a light source emitting blue light may be used in terms of better color reproducibility.

The pattern layer may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer may further include a transparent pattern layer that does not contain quantum dot particles.

In the case of having only two color pattern layers, a light source emitting light of a wavelength representing the colors other than those not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, showing a blue color.

The color conversion layer including the substrate and the pattern layer as described above may further include barrier ribs formed between the respective patterns, and may further include a black matrix. In addition, a protective film formed on the upper portion of the pattern layer of the color conversion layer may be further included.

<Image display device>

An image display device according to another aspect of the present invention includes the above-described color filter, and thus has good surface characteristics and excellent chemical resistance and color reproducibility. The image display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for game machines, a display device for portable terminals such as mobile phones, and a display for digital cameras. device, a display device such as a display device for car navigation, and the like, and a color display device may be particularly suitable.

The image display device may include other components that may be included in a conventional image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention, but the present invention is not limited thereto. don't

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. However, it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" representing contents are based on weight unless otherwise specified.

synthesis example 1. Intermediate compounds ( INT ) synthesis of

[Scheme 1]

As shown in Scheme 1, 1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (0.11 mol) and 2,6-diisopropylaniline (0.44 mol) were added to 1 L of propionic acid, and the temperature was raised to A reaction solution was prepared by maintaining the reaction at 140° C. for 5 hours. The reaction solution was cooled to room temperature, the precipitate was filtered under reduced pressure, and the filtered filtrate was washed with methanol. The filtrate was dispersed in water, maintained for 30 minutes, filtered under reduced pressure, dispersed again in methanol, maintained for 30 minutes, and filtered under reduced pressure. After drying, an intermediate compound (INT) was obtained in a yield of 80.5%. The chemical reaction occurring during this process is shown in Scheme 1 above.

MS (Mass Spectrometric) was measured for the intermediate compound formed above using a MALDI-TOF measuring device. As a result, it was confirmed that the molecular weight was 848.16.

synthesis example 2. Example Synthesis of fluorescent dyes

synthesis example 2-1. Synthesis of Compounds of Formula 4

[Scheme 2]

Potassium carbonate (0.04 mol) was added to the solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in 1 in the above synthesis, and then the temperature was raised to 120 ° C. to prepare a reaction solution. A solution obtained by dissolving 4-chlorophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120° C. for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-(1,2,2-triphenylvinyl)phenol (0.16 mol) and potassium carbonate (0.16 mol) were added, and stirring was maintained for 4 hours. After that, it was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. After redissolving the filter material in methylene chloride (MC), silica was filtered to remove impurities, and recrystallization was performed with MeOH to obtain the compound of Formula 4 in a yield of 40.4%. The chemical reaction occurring during this process is shown in Scheme 2 above.

MS (Mass Spectrometric) was measured for the intermediate compound formed above using a MALDI-TOF measuring device. As a result, it was confirmed that the molecular weight was 1434.41.

synthesis example 2-2. Synthesis of Compounds of Formula 7

[Scheme 3]

After adding potassium carbonate (0.04 mol) to the solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Synthesis Example 1, the temperature was raised to 120° C. to prepare a reaction solution. A solution obtained by dissolving 4-(1,2,2-triphenylvinyl)phenol (0.32 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120° C. for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-fluorophenol (0.32 mol) and potassium carbonate (0.16 mol) were added, and stirring was maintained for 4 hours. The reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. After redissolving the filter material in methylene chloride (MC), silica was filtered to remove impurities, and recrystallization was performed with MeOH to obtain the compound of Formula 7 in a yield of 36.0%. The chemical reaction occurring during this process is shown in Scheme 3 above.

MS (Mass Spectrometric) was measured for the intermediate compound formed above using a MALDI-TOF measuring device. As a result, it was confirmed that the molecular weight was 1622.62.

synthesis example 2-3. Preparation of compounds of Formula 10

[Scheme 4]

After adding potassium carbonate (0.04 mol) to the solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Synthesis Example 1, the temperature was raised to 120° C. to prepare a reaction solution. A solution obtained by dissolving 4-tetrabutylphenol (0.40 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120° C. for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-(1,2,2-triphenylvinyl)phenol (0.04 mol) and potassium carbonate (0.16 mol) were added, and stirring was maintained for 4 hours. Thereafter, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. After redissolving the filter material in methylene chloride (MC), silica was filtered to remove impurities, and recrystallization was performed with MeOH to obtain the compound of Formula 10 in a yield of 50.4%.

MS (Mass Spectrometric) was measured for the intermediate compound formed above using a MALDI-TOF measuring device. As a result, it was confirmed that the molecular weight was 1500.72.

synthesis example 3. Synthesis of Binder Resin (A)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet pipe was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and 118.0 vinyltoluene were used. g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred and mixed to prepare, and as a chain transfer agent dropping tank, n-dodecanethiol 6 g and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Subsequently, dropping of the monomer and chain transfer agent was started from the loading lot. Dropping proceeded for 2 h while maintaining 90 ° C. After 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Then, a gas inlet pipe was introduced to cause bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas. Initiated. Then, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% relative to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added into the flask, and the reaction was continued at 110° C. for 8 hours to obtain a binder resin (A) having a solid acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

<GPC measurement conditions>

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio of the weight average molecular weight and the number average molecular weight obtained above was taken as molecular weight distribution (Mw/Mn).

Example and comparative example : self-luminous Preparation of photosensitive resin composition

Self-luminous photosensitive resin compositions of Examples and Comparative Examples were prepared according to the content and composition shown in Table 1 below.

Example comparative example One 2 3 4 5 One 2 3 fluorescent dye R1 8 - - 10 40 - - - R2 - 8 - - - - - - R3 - - 8 - - - - - R4 - - - - - 8 50 - R5 - - - - - - - 8 Binder Resin (A) 8.3 8.3 8.3 8.3 8.3 8.3 8.3 8.3 Photopolymerizable Compound (B) 8.45 8.45 8.45 8.45 8.45 8.45 8.45 8.45 photopolymerization initiator C-1 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 C-2 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Solvent (D) balance balance balance balance balance balance balance balance R1: Fluorescent dye of Synthesis Example 2-1
R2: Fluorescent dye of Synthesis Example 2-2
R3: Fluorescent dye of Synthesis Example 2-3
R4: Lumogen F Red
R5: Acid red 52
A: binder resin of Synthesis Example 3
B: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
C-1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one
(Irgacure 369; manufactured by Ciba Specialty Chemical)
C-2: 4,4'-di(N,N'-dimethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
D: propylene glycol monomethyl ether acetate

manufacturing example : color conversion layer manufacturing

A color conversion layer was prepared using the self-luminous photosensitive resin composition prepared in Examples and Comparative Examples. That is, each of the self-luminous photosensitive resin compositions was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, ultraviolet rays were irradiated onto the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure amount (365 nm) of 40 mJ/cm 2 in an air atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Electric Co., Ltd., and no special optical filter was used. The UV-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 using a spray developer for 60 seconds and then heated in a heating oven at 220° C. for 20 minutes to form a pattern. The film thickness of the color conversion layer pattern prepared above was 3.0 μm. The thickness of the color conversion layer may be variously controlled up to 500 μm.

Experimental example 1: Emission intensity evaluation

Using a quantum efficiency meter (QE-1000, manufactured by Otsuka Co., Ltd.) for each color conversion layer prepared in Preparation Example, the luminous PL of each coated substrate was measured, and the luminous intensity was described in Table 2 below.

It can be judged that the higher the measured luminous intensity, the better the luminance characteristics.

Experimental example 2: Evaluation of heat resistance

After performing an additional heat treatment at 230 ° C. for 2 hours, each color conversion test prepared in the above Preparation Example was evaluated by measuring the color change value (ΔE*ab) before/after heat treatment. ΔE*ab is a value required by the following chromaticity formula based on the CIE 1976 (L*, a*, b*) space colorimetric system (The Japanese Society of Color Studies, Handbook of Color Science (Showa 60) P.266) . The evaluation criteria for heat resistance are as follows, and the results are shown in Table 2 below.

<Evaluation Criteria>

○: △E*ab: 3 or less

△: △E*ab: greater than 3 and less than or equal to 10

×: ΔE*ab: greater than 10

Luminous intensity (λmax:610) ΔE*ab Example 1 4100 ○ Example 2 3500 ○ Example 3 4123 ○ Example 4 4050 ○ Example 5 3900 ○ Comparative Example 1 2143 △ Comparative Example 2 540 × Comparative Example 3 200 ×

Referring to Table 2, in the case of Examples 1 to 5 satisfying all the conditions of the present invention, it was confirmed that the fluorescence efficiency was better than that of Comparative Examples 1 to 3 which did not satisfy the conditions of the present invention. As in Examples 4 and 5, it was confirmed that the fluorescence efficiency did not decrease even though the concentration of the dye was increased.

In addition, in the case of Examples 1 to 5 satisfying all the conditions of the present invention, it was confirmed that the heat resistance was better than that of Comparative Examples 1 to 3 which did not satisfy the conditions of the present invention.

10: light source
20: color conversion layer
30: pixel unit

Claims (9)

A self-luminous photosensitive resin composition comprising a fluorescent dye containing a perylenebisimide-based compound represented by the following formula (1):
[Formula 1]

(In Formula 1 above,
R ₁ and R ₂ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 6 to 20 carbon atoms, and a substituted or unsubstituted straight or branched chain having 1 to 20 carbon atoms It is selected from the group consisting of 20 alkyl groups,
R ₃ to R ₆ are each independently a substituent represented by Formula 2 or Formula 3 below, including at least one substituent represented by Formula 3)
[Formula 2]

(In Formula 2 above,
X ₁ to X ₅ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom. It is a substituent selected from ester groups and amine groups of 10 to 10,
Y is an oxygen atom or a sulfur atom)
[Formula 3]

(In Formula 3,
X ₆ to X ₉ are each independently a hydrogen atom, a halogen atom, a straight-chain or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a cyanine group, and 1 carbon atom; It is a substituent selected from ester groups and amine groups of 10 to 10,
Y is an oxygen atom or a sulfur atom). According to claim 1,
The self-luminous photosensitive resin composition further comprises at least one selected from the group consisting of a photopolymerizable compound, a photopolymerization initiator, a binder resin, a solvent, and an additive. According to claim 1,
The self-luminous photosensitive resin composition, characterized in that the perylenebisimide-based compound is included in an amount of 0.01 to 70% by weight based on 100% by weight of the total solid content in the self-luminous photosensitive resin composition containing the same. According to claim 2,
The self-luminous photosensitive resin composition, characterized in that the binder resin is included in 5 to 85% by weight based on 100% by weight of the total solid content of the self-luminous photosensitive resin containing the same. According to claim 2,
The photopolymerizable compound is a self-luminous photosensitive resin composition, characterized in that it is included in 5 to 50% by weight based on 100% by weight of the total solid content of the self-luminous photosensitive resin composition containing the same. According to claim 2,
The photopolymerization initiator is a self-luminous photosensitive resin composition, characterized in that it is included in 0.1 to 40% by weight based on solid content, based on 100% by weight of the total sum of the binder resin and the photopolymerizable compound. A color conversion layer comprising a cured product of the self-luminous photosensitive resin composition according to any one of claims 1 to 6. A color filter comprising the color conversion layer of claim 7 . An image display device comprising the color filter of claim 8.

Images