KR20170112591A - Luminescence color filter, Liquid crystal pannel containing the same and Liquid crystal display containing the same - Google Patents

Abstract

The present invention relates to a novel luminescent color filter, a liquid crystal, and a liquid crystal display including the same. More specifically, the present invention relates to a color compensation extruded optical film capable of introducing a specific organic phosphor and a specific resin, And a method for producing the same.

Description

[0001] The present invention relates to a luminescent color filter, a liquid crystal panel including the luminescence color filter, and a liquid crystal display including the luminescence color filter,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting color filter, a liquid crystal panel, and a liquid crystal display including the same, wherein a specific organic fluorescent material is introduced.

A liquid crystal display device, which is one of the most widely used flat panel display devices, includes two substrates having a pixel electrode, a common electrode, and the like, and a liquid crystal layer interposed therebetween. The lower substrate has a plurality of gate wirings and data wirings defining a pixel region on the upper surface, and thin film transistors are provided at the intersections of the two wirings and connected to the pixel electrodes of the pixel regions. The upper substrate has a color filter layer including a patterned absorptive color filter corresponding to the pixel region, and the color filter layer is composed of an R (red) filter, a G (green) filter, and a B (blue) filter.

In addition, a liquid crystal display (LCD) is a non-active light emitting display, and a separate backlight device is required to display the image, and the RGB color is used for color image display.

In general, a liquid crystal display (LCD) is a method of forming a white light by applying a yellow light emitting material to the surface of a blue LED (light emitting diode), passing the color light through a backlight unit and a liquid crystal panel, A compensation film is introduced into the backlight unit to implement white light, and a method of separating RGB by a color filter is used.

In order to improve the RGB color reproducibility of the LCD, various inorganic materials such as CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe , HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HggZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe GaN, GaP, GaP, GaP, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPb, GaPb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, GaN, Group III-V compound quantum dots such as SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, Compound system amount Technology for solving the problem of low color reproducibility of RGB implementations of conventional LCD by introducing Group IV compound quantum dots such as Si, Ge, SiC and SiGe has been developed. However, these inorganic quantum dots have recently been attracting attention as environmental pollutants, and it is necessary to minimize the use of cadmium (Cd), which is one of typical environmental pollutants that pollute water quality and soil.

Therefore, it is urgent to develop a color filter capable of ensuring high color reproducibility while introducing new materials replacing existing inorganic quantum dots.

U.S. Published Patent Application No. 2012-0113672 (2012.05.10) Korea Patent No. 10-1110071 (Jan. 19, 2012)

Accordingly, the present inventors have made efforts to develop a color filter incorporating a new material capable of replacing existing non-luminous dyes, pigments, and inorganic luminous materials. As a result, they have found that a monomolecular form having excellent heat resistance, light resistance, Organic phosphors have been developed and it has been found that the introduction of an appropriate amount of organic phosphors to the green light emitting device and / or the red light emitting device of the color filter can reduce the optical loss and improve the color gamut of the color filter. That is, the present invention provides a light emitting color filter, a liquid crystal panel incorporating the same, and a liquid crystal display including the same, using a specific organic fluorescent material.

According to an aspect of the present invention, there is provided a color filter for converting a blue light passing through a liquid crystal into red and green, the color filter comprising a green organic phosphor and / or a red organic phosphor, Wherein the green light emitting filter includes a green organic phosphor having a PL wavelength of 500 to 570 nm in a monomolecular form, the red light emitting filter includes a red light emitting filter, A red organic phosphor having a PL wavelength in a monomolecular form of 580 to 680 nm; Or the green organic phosphor and the red organic phosphor.

In one preferred embodiment of the present invention, the green organic phosphor may include at least one selected from the group consisting of a perylene-based organic phosphor represented by the following formula (1) and a perylene-based organic phosphor represented by the following formula (2).

[Chemical Formula 1]

Wherein each of R ¹ , R ² , R ³ and R ⁴ independently represents a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, -CN or -COOR ⁵ And R ⁵ is a straight-chain alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms.

(2)

또는 -CN이며, 상기 R⁵ 및 R⁶ 각각은 독립적으로 수소원자, C1 ~ C5의 직쇄형 알킬기 또는 C3 ~ C5의 분쇄형 알킬기이다. Wherein each of R ² and R ⁴ is independently a hydrogen atom, a halogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, R ¹ and R ³ are each independently a straight-chain alkyl group having ¹ to 5 carbon atoms, A branched alkyl group, a C5-C6 cycloalkyl group,

Or -CN, and each of R ⁵ and R ⁶ is independently a hydrogen atom, a C 1 to C 5 linear alkyl group, or a C 3 to C 5 branched alkyl group.

In one preferred embodiment of the present invention, each of R ¹ and R ⁴ of the perylene-based organic phosphor represented by Formula 1 is -CN, each of R ² and R ³ is -COOR ⁵ , and R ⁵ is C 3 to C 5 Lt; / RTI >

이며, 상기 R⁵ 및 R⁶ 각각은 독립적으로 C3 ~ C5의 분쇄형 알킬기일 수 있다.In one preferred embodiment of the present invention, R ² and R ⁴ in the perylene-based organic phosphor represented by Formula 2 are each a hydrogen atom or a fluorine atom, R ¹ and R ³ are each independently a C 5 -C 6 cycloalkyl group,

And each of R ⁵ and R ⁶ may independently be a C3 to C5 branched alkyl group.

In one preferred embodiment of the present invention, the red organic phosphor may be at least one selected from among perylene-based organic phosphors represented by the following general formula (3).

(3)

또는 -CN이며, R², R³, R⁵ 및 R⁶ 각각은 독립적으로 수소원자, C1 ~ C5의 알콕시기, C5 ~ C10의 사이클릭알콕시기,

,

또는

이고, 다만 R³와 R⁶이 수소원자인 경우 R²와 R⁵는 수소원자가 아니며, 상기 R⁷ 및 R⁸은 각각 독립적으로 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기 또는 C1 ~ C3의 알콕시기이며, R⁹ 및 R¹⁰은 각각 독립적으로 수소원자, -SO₃H, -COOH, -CH₂COOH, -CH₂CH₂COOH, - CH₂CH₂CH₂COOH, -NR¹¹R¹², -CH₂NR¹¹R¹² 또는 -CH₂ CH₂NR¹¹R¹² 이며, 상기 R¹¹ 및 R¹²는 각각 독립적으로 수소원자 또는 C1~C3의 직쇄형 알킬기이다.In Formula 3, R ¹ and R ⁴ are each independently a hydrogen atom, a straight chain alkyl group of C 1 to C 5, a branched alkyl group of C 3 to C 5, a cycloalkyl group of C 5 to C 6,

Or -CN, and each of R ² , R ³ , R ⁵ and R ⁶ independently represents a hydrogen atom, a C 1 to C 5 alkoxy group, a C 5 to C 10 cyclic alkoxy group,

,

or

Lt; ³ > and R < ⁶ > When it is a hydrogen atom R ² and R ⁵ are not hydrogen atoms, the R ⁷ and R ⁸ are each independently a hydrogen atom, an alkoxy group of C1 ~ C5 straight alkyl, C3 ~ C5 grinding alkyl group or C1 ~ C3 a, R ⁹ and R ¹⁰ each independently represents a hydrogen atom, -SO ₃ H, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH, -NR ¹¹ R ¹² , -CH ₂ NR ¹¹ R ¹² or -CH ₂ CH ₂ NR ¹¹ R ¹² And R ¹¹ and R ¹² are each independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms.

또는 -CN이며, R², R³, R⁵ 및 R⁶ 각각은 독립적으로 수소원자,

,

또는

이고, 다만 R³와 R⁶이 수소원자인 경우 R²와 R⁵는 수소원자가 아니며, 상기 R⁷ 및 R⁸은 각각 독립적으로 C1 ~ C5의 직쇄형 알킬기 또는 C1 ~ C3의 알콕시기이며, R⁹ 및 R¹⁰은 각각 독립적으로 수소원자, -SO₃H, -COOH, -CH₂COOH, -CH₂CH₂COOH 또는 -CH₂CH₂CH₂COOH일 수 있다.In one preferred embodiment of the present invention, R ¹ and R ⁴ of the perylene-based organic phosphor represented by Formula 3 are each independently a C 5 -C 6 cycloalkyl group,

Or -CN, and each of R ² , R ³ , R ^5, and R ⁶ is independently a hydrogen atom,

,

or

Lt; ³ > and R < ⁶ > When it is a hydrogen atom R ² and R ⁵ are not hydrogen atoms, R ⁷ and R ⁸ are each independently a straight-chain alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R ⁹ and R ¹⁰ are each independently a hydrogen atom, -SO ₃ H, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ COOH.

In another preferred embodiment of the present invention, the green organic phosphor and / or the red organic phosphor may have a specific gravity of 1.0 to 2.0 g / cm 3 and a pyrolysis temperature of 270 ° C or higher.

In another preferred embodiment of the present invention, in the light emitting color filter of the present invention, the green light emitting filter may include 5 to 50 wt% of the green organic phosphor.

In another preferred embodiment of the present invention, the red light emitting filter of the present invention may comprise 10 to 50% by weight of the red organic phosphor.

The red light emitting filter may include the red organic phosphor and the green organic phosphor in a weight ratio of 1: 0.20 to 1: 1.

In another preferred embodiment of the present invention, a photosensitive thin film having a thickness of 2 占 퐉 and containing 10% by weight of the green organic phosphor is measured for color deviation based on NTSC (National Television System Committee) color coordinates under a blue light source, the deviation range of the x-coordinate may be 0.0001 to 0.008, and the y-coordinate deviation range may be 0.0003 to 0.0010.

As another preferred embodiment of the present invention, the red-based organic phosphor; Or an organic fluorescent material containing the green organic fluorescent substance and the red organic fluorescent substance in an amount of 10% by weight based on NTSC color coordinates under a blue light source, The range is 0.0001 to 0.006, and the y coordinate deviation range is 0.0001 to 0.0008.

Another object of the present invention is to provide a liquid crystal panel including the above-described various types of emission color filters.

It is still another object of the present invention to provide a backlight unit that emits blue light and a liquid crystal display (LCD) including the liquid crystal panel.

The light emission color filter of the present invention not only improves the power efficiency of the liquid crystal display device by reducing the light loss as compared with the conventional color filter but also secures the light stability and improves the color reproduction ratio, It is possible to provide a liquid crystal display ensuring high color reproducibility using a filter.

Fig. 1 is a CIE 1931 coordinate system used for color coordinate measurement in Experimental Example 2. Fig.

The term "film" used in the present invention has a broad meaning including not only a film form commonly used in the art but also a sheet form.

The term " C1 ", "C2 ", etc. used in the present invention means a carbon number. For example," C1 to C5 alkyl "means an alkyl group having 1 to 5 carbon atoms.

로 표현된 화학식에서, R¹은 독립적으로 수소원자, 메틸기 또는 에틸기이며, a는 1 ~ 3이다"라고 치환기에 대해 표현되어 있을 때, a가 3인 경우, 복수의 R¹, 즉 R¹ 치환기가 3개가 있고, 이들 복수 개의 R¹들 각각은 서로 같거나 다른 것으로서, R¹들 각각은 모두 수소원자, 메틸기 또는 에틸기일 수 있으며, 또는 R¹들 각각은 다른 것으로서, R¹ 중 하나는 수소원자, 다른 하나는 메틸기 및 또 다른 하나는 에틸기일 수 있음을 의미하는 것이다. 그리고, 상기 내용은 본 발명에서 표현된 치환기를 해석하는 일례로서, 다른 형태의 유사 치환기도 동일한 방법으로 해석되어야 할 것이다.In the present invention,

Lt; RTI ID = 0.0 > R ¹ is independently a hydrogen atom, a methyl group or an ethyl group, a is 1 to 3, "when a is 3, there are a plurality of R ¹ , that is, R ¹ substituents, Each of R ¹ s may be the same or different and each of R ¹ s may all be a hydrogen atom, a methyl group or an ethyl group, or each of R ¹ s are different and one of R ¹ is Hydrogen atom, the other is a methyl group, and the other is an ethyl group. The above is an example of interpreting the substituent represented by the present invention, and other similar substituents should also be interpreted in the same way.

"로 표현된 화학식에서 "*"표시는 치환기가 연결되는 부위를 의미한다.Further, in the present invention,

Quot; in the chemical formula represented by "" means a site to which a substituent is connected.

Hereinafter, the present invention will be described in detail.

(Heat stability at 230 DEG C or higher), light resistance (light stability against UV and / or blue light backlight), and chemical resistance (solvent resistance) that can withstand the color filter manufacturing process are required for use as a colorant for a color filter of a liquid crystal panel. However, the known organic phosphors have poor heat resistance and can not be introduced into color filters for color filters.

Therefore, the present inventors have found that a green organic phosphor and / or a red-based organic phosphor having a low specific gravity and a high solubility in a solvent and having excellent dispersibility in a resin, and / Organic fluorescent material, and the present invention provides a light emitting color filter into which the organic fluorescent material is introduced.

The light-emitting color filter of the present invention is a color filter that converts blue light into red light and green light when blue light emitted from the backlight unit passes through the liquid crystal of the liquid crystal panel. The color filter includes a blue light transmission filter, a green light emission filter, And is provided in a pattern.

The green organic phosphor and / or the red organic phosphor used in the light emitting color filter of the present invention preferably has a specific gravity of 1.0 to 2.0 g / cm 3 and a thermal decomposition temperature (TD) of 250 ° C or higher, preferably 270 ° C or higher When the specific gravity of the organic phosphor is less than 1.0 g / cm < 3 > or the specific gravity exceeds 2.0 g / cm < 3 >, dispersibility in the resin decreases and workability is deteriorated. There is a problem that the organic phosphor in the filter is not uniformly dispersed and the optical characteristics are deteriorated.

If the thermal decomposition temperature of the green organic phosphor and / or the red organic phosphor is less than 270 캜, inherent optical characteristics may be lost due to the deformation and decomposition of the organic phosphor due to the characteristics of color filters performed at high temperatures. There is a problem that the structure of the organic phosphor is broken and the light stability is greatly deteriorated.

In the present invention, the green light emitting filter includes a green organic phosphor having a PL wavelength of 500 to 570 nm in a monomolecular form satisfying the above characteristics, preferably a perylene-based organic phosphor represented by the following formula (1) And one or two species selected from among the perylene-based organic phosphors to be displayed.

 [Chemical Formula 1]

Wherein each of R ¹ , R ² , R ³ and R ⁴ independently represents a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, -CN or -COOR ⁵ , Preferably each of R ¹ and R ⁴ is a straight-chain alkyl group of C 1 to C 5 or -CN, each of R ² and R ³ is -COOR ⁵ , more preferably R ¹ and R ⁴ are -CN, R ² and R ³ are -COOR ⁵ .

R ⁵ in the formula (1) is a straight-chain alkyl group of C 1 to C ⁵ or a branched alkyl group of C 3 to C 5, preferably a branched alkyl group of C 3 to C 5, more preferably an isopropyl group or a methylpropyl group.

(2)

또는 -CN이며, 바람직하게는 C5 ~ C6의 사이클로알킬기,

또는 -CN이고, 더욱 바람직하게는

또는 -CN이다. In Formula 2, each of R ² and R ⁴ is independently a hydrogen atom or a halogen atom, preferably a hydrogen atom or a fluorine atom. Each of R ¹ and R ^{3 in the general} formula (2) is independently a straight chain alkyl group having ¹ to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms,

Or -CN, preferably a C5-C6 cycloalkyl group,

Or -CN, more preferably

Or -CN.

Each of R ⁵ and R ^{6 in} Formula (2) is independently a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, preferably a linear alkyl group having 2 to 4 carbon atoms or a A branched alkyl group, more preferably a C3 to C4 linear alkyl group or a C3 to C4 branched alkyl group.

In the present invention, when the green-based organic phosphor is used alone, the green light-emitting filter preferably contains 5 to 50% by weight, preferably 10 to 40% by weight, of the green- good. If the content of the green organic phosphor is less than 5% by weight, blue light is transmitted to reduce the effect of improving the color reproducibility with respect to the green light. If the content is more than 50% by weight, have.

In addition, the green light emission filter may further include, in addition to the green organic phosphor as the coloring agent, a general pigment and dye used in the related art, for example, C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58; C.I. solvent green 1, 4, 5, 7, 34, 35, etc. may be mixed with the green organic phosphor.

Further, the green emission filter may use a small amount of inorganic quantum dots used in the color filter. , For _{^{example, YBO 3: Ce 3 +,}} Tb 3 +; _{^{BaMgAl 10 O 17: Eu 2 +}} , Mn 2+; (Sr, Ca, Ba) (Al, Ga) 2 S 4: Eu 2+; ZnS: Cu, Al; _{Ca 8 Mg (SiO 4) 4} Cl 2: Eu 2 +, Mn 2 +; Ba ₂ SiO ₄ : Eu ²⁺ ; _{(Ba, Sr) 2 SiO 4} : Eu 2 +; _{Ba 2 (Mg, Zn) Si} 2 O 7: Eu 2 +; _{(Ba, Sr) Al 2 O} 4: Eu 2 +; May be added in small quantities.

A 2 μm thick photosensitive thin film containing 10% by weight of the green organic phosphor is subjected to color deviation measurement based on NTSC (National Television System Committee) color coordinates under a blue light source, 0.008, and the y coordinate deviation range may be 0.0003 to 0.0010. Preferably, the x coordinate deviation range is 0.0001 to 0.006, and the y coordinate deviation range is 0.0003 to 0.0008.

In the present invention, the red light emitting filter may include a red organic phosphor having a PL wavelength of 580 to 680 nm, a green organic phosphor having a PL wavelength of 500 to 570 nm, and a green organic phosphor having a PL wavelength of 580 to 680 nm, Based red phosphor and red-based organic phosphor.

The red organic phosphor having a PL wavelength of 580 to 680 nm may be a mixture of one or more selected from among perylene-based organic phosphors represented by the following formula (3).

 (3)

또는 -CN이며, 바람직하게는 C1 ~ C5의 알킬기 또는

이며, 더욱 바람직하게는

이다. In Formula 3, each of R ¹ and R ⁴ is independently a hydrogen atom, a straight-chain alkyl group of C 1 to C 5, a branched alkyl group of C 3 to C 5, a C 5 to C 6 cycloalkyl group,

Or -CN, preferably a C1-C5 alkyl group or

, And more preferably

to be.

,

또는

이고, 바람직하게는

,

또는

이며, 더욱 바람직하게는 R², R³, R⁵ 및 R⁶ 각각은 독립적으로

,

또는

이다. 다만, 상기 화학식 3의 R³와 R⁶이 수소원자인 경우 R²와 R⁵는 수소원자가 아니다. 이때, 상기 R⁷ 및 R⁸은 독립적으로 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 또는 C1 ~ C3의 알콕시기이고, 바람직하게는 C2 ~ C4의 직쇄형 알킬기, C3 ~ C4의 분쇄형 알킬기 또는 C1 ~ C3의 알콕시기, 더욱 바람직하게는 C3 ~ C4의 직쇄형 알킬기 또는 C1 ~ C2의 알콕시기이다.Each of R ² , R ³ , R ⁵ and R ^{6 in the general} formula (3) is independently a hydrogen atom, a C 1 to C 5 alkoxy group, a C 5 to C 10 cyclic alkoxy group,

,

or

, And preferably

,

or

, More preferably each of R ² , R ³ , R ⁵ and R ⁶ is independently

,

or

to be. However, when R < ³ > and R < ^{6 &} When it is a hydrogen atom R ² and R ⁵ are not hydrogen atoms. R ⁷ and R ⁸ are each independently a hydrogen atom, a straight-chain alkyl group of C 1 to C 5, a branched alkyl group of C 3 to C 5, or an alkoxy group of C 1 to C 3, preferably a linear alkyl group of C 2 to C 4, A C3 to C4 branched alkyl group or a C1 to C3 alkoxy group, more preferably a C3 to C4 linear alkyl group or a C1 to C2 alkoxy group.

Each of R ⁹ and R ^{10 in} Formula 3 is independently a hydrogen atom, -SO ₃ H, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH, -NR ¹¹ R ¹² , -CH ₂ NR ¹¹ R ¹² , or -CH ₂ CH ₂ NR ¹¹ R ¹² , preferably a hydrogen atom, -SO ₃ H, -COOH, -CH ₂ COOH or -CH ₂ NR ¹¹ R ¹² , and more preferably a hydrogen atom or a -SO ₃ H.

Each of R ¹¹ and R ¹² is independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms. Preferably, R ¹¹ and R ¹² are each independently A hydrogen atom or a methyl group.

In the present invention, when the red organic phosphor is used alone, the red light emitting filter preferably contains 10 to 50% by weight, preferably 15 to 45% by weight, of the red organic phosphor. If the content of the red organic phosphor is less than 10% by weight, the blue light is transmitted to reduce the color reproducibility improvement effect with respect to the red light. If the content exceeds 50% by weight, the luminance may be lowered due to the concentration light extinction effect .

The red light emitting filter may contain both the green organic phosphor and the red organic phosphor having excellent blue light absorbing ability. The red organic phosphor and the green organic phosphor may be mixed in a weight ratio of 1: 0.20 to 1: 1, preferably 1: 0.25 to 0.90 By weight, more preferably from 1: 0.30 to 0.80 by weight. When the weight ratio of the green organic phosphor is less than 0.20 weight ratio, it may be insufficient to exhibit the desired luminance improvement. When the weight ratio of the green organic phosphor is more than 1 weight ratio, the green light is expressed in the red pixel, have.

In addition, the red light emitting filter may further include, in addition to the red organic phosphor as a coloring agent, a general pigment and dye used in the related art, for example, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264; , 49, 125, 130, 218; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; And the like can be further mixed and used.

Furthermore, the red emission filter may use a small amount of inorganic quantum dots used in the color filter. , For ^{_{example, SrY 2 S 4: Eu 2}} +; (Ca, Sr) S: Eu ^< ^{2 + &gt};; SrS: Eu ^< ^{2 + &gt};; ^{_{Y 2 O 3: Eu 3+,}} Bi 3 +; YVO ₄ : Eu ^{3 +} , Bi ^{3 +,} Y ₂ O ₂ S: Eu ^{3 +} , and Bi ^{3 +} : Y ₂ O ₂ S: Eu ^{3 +} can be further used.

The photosensitive thin film having a thickness of 2 占 퐉 and comprising the red-based organic fluorescent material or the organic fluorescent material containing the green-based organic fluorescent substance and the red-based organic fluorescent substance in an amount of 10% by weight was subjected to color deviation measurement based on NTSC color coordinates under a blue light source And the y coordinate deviation range may be 0.0001 to 0.0008, preferably the x coordinate deviation range is 0.0001 to 0.005, and the y coordinate deviation range may be 0.0001 to 0.0006. Bar, can have very good light stability.

As described above, the combination of the light emitting color filter of the present invention including the green light emitting filter including the specific organic phosphor and the red light emitting filter, and the backlight unit emitting blue light, etc., is introduced into the color filter layer of the liquid crystal panel, Can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.

[Example]

Preparation Example 1: Preparation of Green Organic Phosphor represented by Formula 1-1

(1) Synthesis of Compound Represented by Formula 1-1a

9.2 g of perylene-3,9-dicarboxylic acid (27.03 mol) was added to 50 ml of isobutyl alcohol in DMF, and the mixture was stirred and reacted at 65 for 3 hours .

After completion of the reaction, the temperature was lowered, 500 ml of MeOH was added thereto, and the precipitated material was formed.

Next, after filtering, the precipitated substance obtained by filtering was washed with cold MeOH, and then dried in a vacuum oven to obtain a yellow solid substance (9.6 g, yield 78%). It was confirmed by ¹ H-NMR and ¹³ C NMR measurement that the compound was represented by the following formula 1-1a.

¹ H-NMR spectrum ( 300 MHz , CDCl ₃ ) :? (Ppm) = 8.19 (d, 2H), 7.96-91 (m, 4H), 7.39 (m, 4H), 4.03 m, 2H), 0.91 (d, 12H)

^{_{13 C NMR (CDCl 3, ppm}} ): 167.9, 139.1, 129.8, 128.8, 128.1, 127.1, 126.9, 125.3, 124.4, 122.8, 120.2, 70.8, 27.6, 19.4

 [Formula 1-1a]

In Formula 1-1a, each of R ¹ and R ⁴ is -COOCH ₂ CH (CH ₃ ) ₂ , and each of R ² and R ³ is a hydrogen atom.

(2) Synthesis of Compound Represented by Formula 1-1b

9.6 g of the compound represented by the formula 1-1a (21.22 mol), 7.85 g of N-bromosuccinimide (44 mol), and CH ₂ Cl ₂ were added, and the mixture was stirred at room temperature for 12 hours (Reaction terminated by TLC).

After completion of the reaction, the solution was removed with an evaporator, and a solid (yield: 88%) was obtained from the column.

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula 1-1b.

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.21 (d, 2H), 7.99 (d, 2H), 7.82 ~ 77 (m, 4H), 4.01 (d, 4H), 1.95 ( m, 2H), 0.90 (d, 12H)

¹³ C NMR ( CDCl ₃ , ppm): 167.7, 133.0, 129.7, 128.9, 128.1, 128.0, 127.9, 126.8, 126.1, 124.2, 120.0, 70.9, 27.7, 19.6

 [Formula 1-1b]

In Formula 1-1b, each of R ¹ and R ⁴ is -COOCH ₂ CH (CH ₃ ) ₂ , and each of R ² and R ³ is -Br.

(3) Synthesis of Compound Represented by Formula 1-1

12 g of the compound represented by the formula 1-1b (19.6 mol), 9 g of copper cyanide (98.3 mol), and sulfolane were added and stirred and reacted at 130 to 140 ° C for 25 hours.

After completion of the reaction, H ₂ O was added to form a precipitate, and the precipitate was filtered with diluted ammonia.

The filtered precipitate was then washed with distilled water and dried.

The dried material was extracted with toluene (Toulene) and then purified by silica gel column (trichloroethane / ethanol) to obtain an orange solid (yield: 61%).

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (2-2).

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.20 (d, 2H), 8.03 ~ 7.96 (m, 4H), 7.87 (d, 2H), 4.04 (d, 4H), 1.98 ( m, 2 H), 0.92 (d, 12 H)

^{_{13 C NMR (CDCl 3, ppm}} ): 167.9, 137.5, 130.4, 129.8, 127.4, 126.9, 125.7, 125.4, 125.3, 124.4, 117.1, 71.1, 27.9, 19.7

[Formula 1-1]

In Formula 1-1, each of R ¹ and R ⁴ is -COOCH ₂ CH (CH ₃ ) ₂ , and each of R ² and R ³ is -CN.

Preparation Example  1-2: Green system  Preparation of Organic Phosphor

10.0 g of perylene-3,4: 9,10-tetracarboxylic acid bisanhydride (25.49 mmol) was added and 400 ml of CH ₃ CN was added in a nitrogen atmosphere Respectively. Then 50 g of 1-bromo-2-methylpropane, 364.75 mmol), 32.5 g of 2-methyl-1-propanol, 438.43 mmol, 247.2 5 mmol) were added in this order, and the mixture was refluxed and reacted for 15 hours.

Next, the temperature was lowered and filtered, followed by silica gel column chromatography to obtain 15 g of an orange solid.

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (1-2).

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.12 (d, 4H), 7.97 (d, 4H), 4.11 (d, 8H), 2.10 (m, 4H), 1.05 ppm (d , 24H)

^{_{13 C NMR (CDCl 3, ppm}} ): δ (ppm) = 169.1, 132.5, 131.8, 130.1, 129.4, 128.9, 121.1, 70.8, 27.4, 19.1 ppm

 [Formula 1-2]

In Formula 1-2, each of R ¹ to R ⁴ is - COOCH ₂ CH (CH ₃ ) ₂ .

Preparation Example  2-1: Green system  Preparation of Organic Phosphor

(1) Synthesis of Compound Represented by Formula 2-1a

5.0 g of perylene-3,4: 9,10-tetracarboxylic acid bisanhydride (12.75 mmol) and 40 ml of H ₂ SO ₄ were mixed The mixture was stirred at room temperature (24-28 < 0 > C) for 12 hours.

Next, 130 mg of I ₂ (0.51 mmol) was added to the stirred mixture, and the mixture was stirred at 85 to 30 minutes, and 2.04 g of bromine (12.75 mmol) was slowly added thereto over 2 hours. After the addition, the mixture was stirred at 85 ° C for 12 hours, then cooled to 24 ° C to 25 ° C, and then slowly added with ice to form a precipitate.

Next, the precipitate obtained by filtering was dried at 120 캜 to obtain a crude product represented by the following Chemical Formula 2-1a.

[Formula 2-1a]

(2) Synthesis of a compound represented by the formula (2-1b)

In a three-necked flask, 7 g of the red solid (12.72 mmol) represented by the above formula (2-1a) was added and 150 ml of propionic acid was added in a nitrogen atmosphere, followed by stirring.

10.28 ml of isopropylaniline (76.35 mmol) was added to the stirred mixture, and the mixture was refluxed and reacted at 140 for 10 hours.

After the completion of the reaction, the temperature was lowered to 24 to 25 ° C, water was added to the reaction solution, and the precipitated precipitate was collected by filtration, and the precipitate was neutralized by washing.

Next, the washed precipitate was purified by a silica gel column (Silica gel Column, CH ₂ Cl ₂ / Hexane) to obtain an orange solid represented by the following Formula 2-1b.

[Formula 2-1b]

^{_{1 H NMR (CDCl 3, 400}} MHz ppm): δ = 9.58 (d, 2H, perylene-H), 9.03 (s, 2H, perylene-H), 8.82 (d, 2H, perylene-H), 7.52 (t , 2H, phenyl-H), 7.38 (d, 4H, phenyl-H), 2.78-2.71 (m, 4H, isopropyl-

¹³ C NMR ( CDCl ₃ , 100 MHz , ppm) :? = 163.34, 162.84, 145.92, 138.82, 133.61, 130.25, 128.03,124.56, 123.51, 123.19, 121.40, 29.62, 24.38, 24.35

(3) Synthesis of Compound Represented by Formula (2-1)

2 g of the orange solid (2.30 mmol) and 122 mg of 18-crown-6 (0.46 mmol) represented by the above formula 2-1b were placed in a three-necked flask and 35 ml of sulfone was added in a nitrogen atmosphere. And stirred and refluxed for 30 minutes. Next, 803 mg of KF (13.8 mmol) was added thereto, and the reaction was carried out for 1.5 hours.

After the completion of the reaction, the temperature was lowered, water was added, stirring was performed for 1 hour, and the resulting precipitate was separated by filtration. The precipitate was washed with water and vacuum dried.

Next, the dried material was purified by a silica gel column (Silica gel Column, Toluene / Ethyl acetate) to prepare a green organic phosphor which is an orange solid. The orange solid was confirmed to be a compound represented by the following formula (2-1).

^{1 H NMR (400 MHz, CDCl} 3): δ = 9.25 (dd, 2H, 8.82 (d, 2H), 8.64 (d, 2H), 7.52 (t, 2H), 7.36 (d, 4H,), 2.74 ( sep >, 4H), 1.19 (d, 24H)

[Formula 2-1]

이고, R⁵ 및 R⁶은 이소프로필기이며, R² 및 R⁴는 불소원자이다.In Formula (2-1), R ¹ and R ³ are

, R ⁵ and R ⁶ are isopropyl groups, and R ² and R ⁴ are fluorine atoms.

Preparation Example  2-2: Green system  Preparation of Organic Phosphor

In a nitrogen atmosphere, 1 g of 3,4,9,10-perylenetetracarboxydianhydride (2.55 mmol), 7.5 g of imidazole, and 2,6-diisopropylamine (2,6-diisopropylamine (10.6 mmol)) was refluxed at 190 DEG C for 24 hours. After completion of the reaction, the temperature was lowered to room temperature (24 to 25 DEG C).

Next, EtOH and 2M HCl were added thereto, followed by stirring for 3 hours, followed by filtering. The dark red material obtained by filtering was subjected to silica column chromatography to obtain 1.2 g (65%).

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (2-2).

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ = 8.65 (d, 4H), 8.45 (d, 4H), 7.5 (t, 2H), 7.35 (d, 4H), 2.76 (m, 4H), 1.18 (d, 24H).

¹³ C-NMR ( CDCl ₃ , ppm): δ 162.1, 144.3, 136.2, 132.3, 130.8, 130.4, 129.9, 127.1, 124.3, 123.7, 123.6, 29.5, 24.2 ppm

[Formula 2-2]

이고, R⁵ 및 R⁶은 이소프로필기이며, R² 및 R⁴는 수소원자이다.In Formula (2-2), R ¹ and R ³ are

, R ⁵ and R ⁶ are isopropyl groups, and R ² and R ⁴ are hydrogen atoms.

Preparation Example  3-1: < RTI ID = 0.0 > Red  Preparation of Organic Phosphor

(1) Synthesis of Compound Represented by Formula 3-1a

, 3.30 g of 3,4,9,10-perylenetetracarboxylic dianhydride (8.41 mmol), 20 mL of chlorosulfonic acid (300 mmol) and iodine , 2.20 mmol) were placed in a three-necked flask, and stirred and reacted at 65 ° C for 30 hours.

After completion of the reaction, the temperature was lowered, and then ice was slowly added to precipitate, which was filtered and dried to obtain a red solid (4.14 g, yield = 92%).

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula 3-1a.

^{1 H-NMR (d- DMSO,} ppm): δ = 8.75 (s, 4H).

¹³ C-NMR (d- DMSO , ppm) :? = 119.75, 125.29, 129.5, 134.88, 136.22, 158.16, 168.53

[Formula 3-1a]

(2) Synthesis of Compound Represented by Formula 3-1b

1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride (1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride, 0.019 mol), 16.67 g of 2,6-diisopropylaniline (0.094 mol) and 250 ml of propionic acid were placed in a three-necked flask, and the mixture was refluxed for 17 hours Followed by stirring to carry out the reaction.

Next, after the reaction was completed, the temperature was lowered to room temperature, and then the solid was filtered through a glass filter. The filtered solid was washed with a water / methanol (1: 3) ratio and dried in a vacuum oven (75 ° C) to obtain a red-orange solid (13.61 g).

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (3-1b).

^{1 H-NMR spectrum (250 MHz} , C 2 D 2 Cl 4): δ = 8.11 (s, 4H), 7.34 (t, 2H), 7.18 (d, 4H), 2.63 (h, 4H), 1.10 (d , 24H,)

¹³ C-NMR spectrum ( 62.5 MHz , C ₂ D ₂ Cl ₄ ): δ = 162.50, 145.82, 135.86, 133.61, 131.94, 130.25, 130.04, 129.14, 124.53, 124.2, 123.47, 29.52,

[Formula 3-1b]

(3) Synthesis of Compound Represented by Formula 3-1

(1.199 mmol) and K ₂ CO ₃ (5.995 mmol) were added to a three-necked flask, and the mixture was vacuum-poured into the flask. Nitrogen (n-methyl-2-pyrrolidone) .

Next, 564 mg of phenol (Phenol, 5.995 mmol) was added thereto, and the mixture was heated to 80 ° C and stirred at this temperature for 15 hours to complete the reaction.

Next, the reaction product was treated with water, water was taken with MgSO ₄ solution and dried using a rotary evaporator. The dried reaction product was then subjected to column chromatography to obtain a compound represented by the following formula (3-1).

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (3-1).

^{_{1 H-NMR (CDCl 3,}} 400MHz): δ (ppm) = 7.543 (t, 8H), 7.443 (t, 2H), 7.284 (m, 8H), 7.159 (t, 4H), 7.097 (d, 8H) , 2.953 (m, 4H), 1.617 (d, 24H)

[Formula 3-1]

이며, R⁷ 및 R⁸은 이소프로필기이고, R², R³, R⁵ 및 R⁶은 페녹시기이다.In the above formula (3-1), R ¹ and R ⁴ are

, R ⁷ and R ⁸ are isopropyl groups, and R ² , R ³ , R ⁵ and R ⁶ are phenoxy groups.

Preparation Example  3-2: Red  Preparation of Organic Phosphor

Compound of the formula 3-1b of the Preparation Example 3-1 In a nitrogen atmosphere (5.76mmol) 5g, 4- methoxyphenyl boronic acid (4-methoxyphenylboronic acid, 45.5mmol) 6.9g, Pd (PPh 3) 4 ( 166 mg) and Na ₂ CO ₃ (7.3 mmol) (1.8 g) were put in a three-necked flask, and then EtOH, benzene and water were added in this order, followed by stirring and reacting at 80 ° C for 8 hours. After completion of the reaction, a red solid (3.5 g) represented by the following Formula 3-2 was obtained through a silica column.

^{1 H-NMR (CDCl3, ppm} ): δ (ppm) = 8.72 (s, 2H), 8.21 (d, 2H), 8.05 (d, 2H), 7.52 (d, 4H), 7.47 (t, 2H), 2H), 7.31 (d, 4H), 7.04 (d, 4H), 3.89 (s,

^{13 C-NMR (CDCl3, ppm} ): δ (ppm) = 163.4, 163.3, 160.5, 145.4, 140.9, 135.8, 135.5, 134.2, 132.8, 130.4, 130.3, 129.9, 129.7, 129.5, 129.3, 128.2, 124.1, 122.4 , 121.6, 114.6, 55.7, 29.1, 24.5, 24.4

[Formula 3-2]

Preparation Example  3-3: 3- To 3  Displayed Red  Preparation of Organic Phosphor

In a nitrogen atmosphere, 5 g of the compound represented by the formula 3-1b of Preparation Example 3-1 (5.76 mmol), 8.28 g of 2,4-dimethoxyphenylboronic acid (45.5 mmol), Pd 166 mg of PPh ₃ ( ₄ ) (0.144 mmol) and 1.8 g of Na ₂ CO ₃ (7.3 mmol) were put in a three-necked flask, and then EtOH, benzene and water were added in this order, Followed by stirring and reaction.

After completion of the reaction, a red solid (3.9 g) represented by the following Formula 3-3 was obtained through a silica column.

^{_{1 H-NMR (CDCl 3,}} ppm): δ (ppm) = 8.67 (s, 2H), 8.28 (d, 2H), 8.10-8.08 (m, 2H), 7.43 (t, 2H), 7.31 (d, (S, 3H), 3.66 (s, 3H), 3.63 (s, 3H), 2.77-2.72 m, 4H), 1.19-1. 13 (m, 24H)

¹³ C-NMR ( CDCl ₃ , ppm) :? (Ppm) = 163.5, 163.3, 154.7, 154.7, 149.8, 149.6, 145.5, 145.5, 137.00, 136.95, 136.3, 135.8, 135.7, 134.1, 131.92, 131.87, 128.3, 128.2, 124.2, 121.93, 121.87, 116.4, 116.2, 114.4, 114.1, 113.3, 113.1, 56.5, 56.2, 56.1, 55.9, 29.3, 29.2, 24.18, 24.14, 24.11

[Formula 3-3]

Example of comparison preparation  1: Green system  Preparation of Organic Phosphor

After adding 0.59 ml of 2,4,6-trimethylbenzaldehyde (4 mmol) into a three-necked flask, the mixture was vacuumed, and then dried CH ₂ Cl ₂ was added thereto and stirred.

Next, 1.029 ml of 2,4-dimethyl-1H-pyrrole (10 mmol) was added thereto, and then trifluoroacetic acid (44 Ul) and dried CH ₂ Cl ₂ diluted and slowly added.

Next, this was stirred at 25 ° C for 3 hours, and then 2,3-dichloro-5,6-dicyano-1,4 -benzoquinone, 4 mmol), and the mixture was stirred at 25 ° C for 1 hour.

Next, 8.1 mL of triethylamine (NEt ₃ , 57.6 mmol) was added thereto, and then 8.6 mL of BF ₃ .Et ₂ O (68 mmol) was slowly added thereto, followed by stirring at 25 ° C for 5 hours to complete the reaction.

Next, the reaction product was treated with Na ₂ CO ₃ solution, and then water was dried with Na ₂ SO ₄ solution and dried using a rotary evaporator. The dried reaction product was then subjected to column chromatography to obtain a compound represented by the following formula (4).

^{_{1 H NMR (CDCl 3, 400MHz}} ): 6.967 (s, 2H), 5.983 (s, 2H), 2.579 (s, 6H), 2.355 (s, 3H), 2.114 (s, 6H), 1.402 (s, 6H )

[Chemical Formula 4]

In Formula 4, R ² , R ⁴ , R ^7, and R ¹⁰ are each a hydrogen atom, and R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹¹ are methyl groups.

Experimental Example  1: UV absorption wavelength of the organic phosphor and PL  Wavelength measurement experiment

(1) UV absorption wavelength measurement

0.01 g of each of the organic phosphors of the preparation examples and comparative preparation examples was taken, dissolved in 3 ml of toluene, put into a test tube, and the emission spectra were measured according to UV absorbance. The results are shown in Table 1 below.

UV absorbance The UV absorbance was measured using a UV spectrometer (VARIAN, CARY 100 Conc.).

(2) PL (photoluminescence) measurement

Each of the organic phosphors of the preparation examples and comparative preparation examples was subjected to PL measurement using DarsaPro5200OEM PL (PSI Trading Co.) and 500W ARC Xenon Lamp, and the results are shown in Table 1 below.

division UV absorption maximum wavelength
(nm) PL maximum wavelength
(nm) Preparation Example 1-1 475 530 Preparation Example 1-2 474 529 Preparation Example 2-1 510 550 Preparation Example 2-2 515 552 Preparation Example 3-1 574 610 Preparation Example 3-2 573 621 Preparation Example 3-3 563 625 Comparative Preparation Example 1 501 523

Example  1-1: Photosensitive resin and green Of the light-emitting thin film  Produce

(1) An acrylic binder (solids content: solvent = 40:60 by weight, MWCM) having a weight average molecular weight of 22,000 g / mol and 1% by weight of a green organic phosphor represented by Formula 1-1 prepared in Preparation Example 1-1, 5% by weight of dipentaerythritol hexa (metha) acrylate (Sigma Aldrich), 1% by weight of Irgacure OXE02 (BASF) as a photoinitiator, and 49% by weight of propylene glycol monomethyl ether acetate (Sigma Aldrich) To prepare a photosensitive resin.

(2) Next, the photosensitive resin was applied onto a glass substrate by spin coating. Next, pre-baking was performed on a hot plate at 90 DEG C for 1 minute and then cooling at 24 DEG C to 25 DEG C for 1 minute to form a thin film.

Subsequently, ultraviolet rays of 365 nm were irradiated at an exposure amount of 100 mJ / cm ² , and then the thin film was post-baked in a hot air drier at 230 캜 for 20 minutes to prepare a green light-emitting thin film having a thickness of 2 탆.

Example  1-2 ~ Example  1-4: Green Of the light-emitting thin film  Produce

A photosensitive resin and a green light-emitting thin film were prepared in the same manner as in Example 1-1 except that, in the production of a photosensitive resin, Preparation Example 1-2, Preparation Example 2-1 and Preparation The green-based organic phosphors prepared in Example 2-2 were used to prepare photosensitive resins, and green luminescent thin films were prepared using them, respectively, to conduct Examples 1-2 to 1-4.

Example  2-1: Photosensitive resin and red Of the light-emitting thin film  Produce

(1) An acrylic binder (solids content: solvent = 40: 60 weight ratio, manufactured by MI Chemical Industry Co., Ltd.) having a weight-average molecular weight of 22,000 g / mol and 1% by weight of the red organic phosphor represented by Formula 3-1 prepared in Preparation Example 3-1 5% by weight of dipentaerythritol hexa (metha) acrylate (Sigma Aldrich), 1% by weight of Irgacure OXE02 (BASF) as a photoinitiator, and 49% by weight of propylene glycol monomethyl ether acetate (Sigma Aldrich) To prepare a photosensitive resin.

(2) Next, the photosensitive resin was applied onto a glass substrate by spin coating. Next, pre-baking was performed on a hot plate at 90 DEG C for 1 minute and then cooling at 24 DEG C to 25 DEG C for 1 minute to form a thin film.

Subsequently, ultraviolet rays of 365 nm were irradiated at an exposure dose of 100 mJ / cm ² , and then the thin film was subjected to post-bake for 20 minutes in a hot air drier at 230 캜 to prepare a red light-emitting thin film having a thickness of 2 탆.

Example  2-2 ~ Example  2-3: Red Luminescent thin film  Produce

A photosensitive resin and a red light-emitting thin film were prepared in the same manner as in Example 2-1, except that, in the preparation of the photosensitive resin, in Preparation Examples 3-2 and 3-3 in place of the red- A red light-emitting organic thin film was prepared by using a red organic phosphor, and then the red light-emitting thin film was prepared using each of the red light-emitting organic phosphors.

Example  2-4: Red Luminescent thin film  Produce

A photosensitive resin and a red light emitting thin film were prepared in the same manner as in Example 2-1 except that 0.3 wt% of the green organic phosphor represented by Formula 1-1 was used in place of the red organic phosphor represented by Formula 3-1, And 0.7% by weight of the red organic phosphor represented by the general formula (3-1) were used to prepare a photosensitive resin, and a red light emitting thin film was prepared therefrom.

Example  2-5: Red Luminescent thin film  Produce

A photosensitive resin and a red light emitting thin film were prepared in the same manner as in Example 2-1 except that 0.1% by weight of the green organic phosphor represented by the formula (1-1) was used instead of the red organic phosphor represented by the formula (3-1) And 0.7% by weight of the red organic phosphor represented by the general formula (3-1) were used, and a mixture of 35% by weight of an acrylic binder, 5% by weight of dipentaerythritol hexa (meth) acrylate, 1% by weight of a photoinitiator, To prepare a photosensitive resin, and using this, a red light-emitting thin film was prepared.

Comparative Example  1: Green Luminescent thin film  Produce

A green light emitting thin film prepared in Comparative Example 1 was used instead of the green organic phosphor represented by Formula 1-1 in the production of a photosensitive resin by the same method as in Example 1-1, A green light-emitting thin film was prepared by using a photosensitive resin.

Comparative Example  2: Green thin film manufacturing

C.I. 37% by weight of an acrylic binder (solids content: solvent = 40:60 by weight, solvent amount: MWC) having 5% by weight of Pigment Green 58, 0.5% by weight of Solvent Yellow 21 and a weight average molecular weight of 22,000 g / mol, dipentaerythritol hexa 5% by weight of acrylate (Sigma Aldrich), 1% by weight of Irgacure OXE02 (BASF) as a photoinitiator, and 51.5% by weight of propylene glycol monomethyl ether acetate (Sigma Aldrich) were mixed to prepare a photosensitive resin.

Next, using this, a red thin film having a thickness of 2 탆 was prepared in the same manner as in Example 2-1.

Comparative Example  3: Preparation of red thin film

C.I. (Solid content: solvent = 40: 60 weight ratio, Mwon Woong Company) having 6 weight% of Pigment Red 254, 2 weight% of Acid Red 94 and a weight average molecular weight of 22,000 g / mol, 36 weight% of dipentaerythritol hexa 5% by weight of acrylate (Sigma Aldrich), 1% by weight of Irgacure OXE02 (BASF) as a photoinitiator and 50% by weight of propylene glycol monomethyl ether acetate (Sigma Aldrich) were mixed to prepare a photosensitive resin.

Next, using this, a red thin film having a thickness of 2 탆 was prepared in the same manner as in Example 2-1.

Comparative Example  4: Red Luminescent thin film  Produce

A photosensitive resin and a red light emitting thin film were prepared in the same manner as in Example 2-1 except that 1.0 wt% of the green organic phosphor represented by the formula (1-1) was used instead of the red organic phosphor represented by the formula (3-1) And 0.7% by weight of the red organic phosphor represented by the general formula (3-1) were used to prepare a photosensitive resin, and a red light emitting thin film was prepared therefrom.

division Filter color Green phosphor Red phosphor content
(weight%) Organic phosphor
Mixing ratio
(Red: green) Example 1-1 green (1-1) - 10 wt% - Examples 1-2 green 1-2 - 10 wt% - Example 1-3 green 2-1 - 10 wt% - Examples 1-4 green 2-2 - 10 wt% - Example 2-1 Red - 3-1 10 wt% - Example 2-2 Red - 3-2 10 wt% - Example 2-3 Red - 3-3 10 wt% - Examples 2-4 Red (1-1) 3-1 10 wt% 1: 0.43 Example 2-5 Red (1-1) 3-1 8 wt% 1: 0.14 Comparative Example 1 green Formula 4 - 10 wt% - Comparative Example 2 green C.I. Pigment Green 58 - 5 wt% - Comparative Example 3 Red C.I. Pigment Red 254 - 6 wt% - Comparative Example 4 Red (1-1) 3-1 17 wt% 1: 1.4

Experimental Example  2 : Of the light-emitting thin film  Property measurement

The color coordinates, luminance and light stability of the green light-emitting thin film and the red light-emitting thin film prepared in the above Examples and Comparative Examples were measured and the results are shown in Table 3 below. Table 4 shows the results of the color reproduction rate measurement.

(One) Color coordinates , Luminance measurement

Using a SR3 luminance meter manufactured by TOPCON, Japan, the blue light emitted from a light guide plate having a blue LED having a center wavelength of 450 nm is measured to obtain the color coordinates and luminance of the blue state. Then, the light emitting thin films prepared in the above Examples and Comparative Examples were mounted on a light guide plate, and then the entire surface of the thin film was divided into 12 points. The color coordinates and luminance of each point were measured to obtain average values to obtain red and green color coordinates.

 (2) Light stability  Measurement experiment

Each of the light emitting thin films prepared in the above Examples and Comparative Examples was mounted on a light guide plate equipped with a blue LED having a center wavelength of 450 nm, and color deviations (x, y) after driving at room temperature for 20 hours before driving were measured, The degree of change of x and y was evaluated, and CA-310 of KONICA MINOLTA, Japan was used.

(3) Color recall  Measurement experiment

The color coordinates and luminance of the red, green, and blue states are respectively measured, and the color recall ratio can be obtained based on the measured color coordinates and luminance. The area of the triangle can be calculated by connecting the color coordinates of each of R, G, B of the light emitted through the BLU including the blue LED. The color recall ratio is calculated by comparing the above area with the area of the NTSC (International TV Standards Committee) Can be calculated. That is, the color reproduction ratio is expressed as a ratio of the relative area when assuming that the color coordinate area of NTSC is 100. At this time, the SR3 luminometer of TOPCON Co., Ltd. was used as the measuring device used.

division Color coordinates Light stability Luminance
(nit) x y X Y Example 1-1 green 0.2705 0.6811 0.0003 0.0005 83.25 Examples 1-2 green 0.2732 0.6820 0.0003 0.0004 81.90 Example 1-3 green 0.2725 0.6789 0.0002 0.0003 82.33 Examples 1-4 green 0.2711 0.6793 0.0003 0.0004 82.04 Example 2-1 Red 0.6693 0.3233 0.0001 0.0001 25.67 Example 2-2 Red 0.6699 0.3241 0.0002 0.0001 26.02 Example 2-3 Red 0.6705 0.3242 0.0001 0.0001 25.83 Examples 2-4 Red 0.6690 0.3231 0.0002 0.0002 31.92 Example 2-5 Red 0.6695 0.3234 0.0001 0.0002 27.03 Comparative Example 1 green 0.3513 0.4756 0.0090 0.0240 23.70 Comparative Example 2 green 0.3131 0.6416 0.0002 0.0004 62.50 Comparative Example 3 Red 0.6304 0.3403 0.0002 0.0001 19.01 Comparative Example 4 Red 0.6025 0.3811 0.0003 0.0005 36.80

division Color recall (%) green Red Example 1-1 Example 2-1 90.5 Example 1-1 Example 2-2 90.6 Example 1-1 Examples 2-4 90.5 Example 1-3 Example 2-1 90.0 Example 1-3 Example 2-2 90.1 Example 1-3 Examples 2-4 90.0 Comparative Example 2 Comparative Example 3 72.8 Example 1-1 Comparative Example 4 75.4

The green light-emitting thin films of Examples 1-1 to 1-4 and the green light-emitting thin films of Examples 2-1 to 2-4 were excellent in light stability, The red light emitting thin film of 2-5 also showed excellent light stability.

The green light emitting thin films of Comparative Examples 2 and 1-1 to 1-4 were compared with the green light emitting thin films of Examples 1-1 to 1-4, (100%), the relative luminance value was increased by 31 ~ 33%.

In addition, when the red light-emitting thin films of Comparative Example 3 and Examples 2-1 to 2-5 were compared, the red light-emitting thin films of Examples 2-1 to 2-5 showed relatively high luminance, and Comparative Example 3 (100%) and the relative luminance value increased by 35 ~ 68%.

In contrast, the green light-emitting film prepared by using the green organic phosphor represented by the general formula (4) of Comparative Preparation Example 1 showed poor light stability and low luminance. This indicates that the organic phosphor of Formula 4 has light resistance and heat resistance This is because it is weak.

In the case of Comparative Example 4 in which the red organic phosphor and the green organic phosphor are used in a weight ratio of 1: 1.4, there is a problem that the green light is emitted from the red pixel and the color coordinates are shifted to the green side to reduce the color region.

The results of the colorimetric determination of Table 4 show that the light emitting filter composed of the green and red light emitting thin films of the present invention exhibited a color reproduction ratio of 90% or more. However, the green light of Comparative Example 2 and the red of Comparative Example 3 In the case of the light-emitting filter and the light-emitting filter composed of the red of Example 1-1 and Comparative Example 4, the color reproduction was very low.

A green light emitting filter and a red light emitting filter using specific organic phosphors are manufactured and then applied to a light emitting color filter to manufacture a light emitting color filter having excellent light stability and capable of increasing a color gamut . When the light emitting color filter of the present invention is introduced as a color filter of a liquid crystal panel of a liquid crystal display provided with a backlight unit emitting blue light, it is possible to provide a liquid crystal display ensuring high color reproducibility by applying the color filter.

Claims (14)

1. A color filter for converting blue light passing through a liquid crystal into red and green,
Wherein the color filter is a color filter provided with a blue transmission filter, a green emission filter, and a red emission filter patterned,
Wherein the green light emitting filter includes a green organic phosphor having a PL wavelength of 500 to 570 nm in a monomolecular form,
Wherein the red light emitting filter is a red organic phosphor having a PL wavelength in a monomolecular form of 580 to 680 nm; Or the green organic phosphor and the red organic phosphor.
The light emitting color filter according to claim 1, wherein the green organic phosphor comprises at least one selected from the group consisting of a perylene-based organic phosphor represented by the following formula (1) and a perylene-based organic phosphor represented by the following formula (2).
[Chemical Formula 1]

Wherein each of R ¹ , R ² , R ³ and R ⁴ independently represents a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, -CN or -COOR ⁵ , R ⁵ is a straight-chain alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms,
(2)

Wherein each of R ² and R ⁴ is independently a hydrogen atom, a halogen atom or a straight-chain alkyl group having ¹ to 5 carbon atoms, R ¹ and R ³ are each independently a straight-chain alkyl group having 1 to 5 carbon atoms, A branched alkyl group of C5 to C6, a cycloalkyl group of C5 to C6,

Or -CN, and each of R ⁵ and R ⁶ is independently a hydrogen atom, a C 1 to C 5 linear alkyl group, or a C 3 to C 5 branched alkyl group.
The method of claim 2, wherein, R ¹ and R ⁴ each perylene organic phosphor represented by Formula 1 is -CN, R ² and R ³ each is -COOR ^5, wherein R ⁵ is of the type grinding C3 ~ C5 Alkyl group.
3. The phosphor according to claim 2, wherein R ² and R ⁴ in the perylene-based organic phosphor represented by Formula 2 are hydrogen atoms or fluorine atoms, and R ¹ and R ³ are each independently a C 5 -C 6 cycloalkyl group or

And each of R ⁵ and R ⁶ is independently a C3 to C5 branched alkyl group.
The light-emitting color filter according to claim 1, wherein the red-based organic fluorescent material comprises a perylene-based organic fluorescent material represented by the following formula (3):
(3)

In Formula 3, R ¹ and R ⁴ are each independently a hydrogen atom, a straight chain alkyl group of C 1 to C 5, a branched alkyl group of C 3 to C 5, a cycloalkyl group of C 5 to C 6,

Or -CN, and each of R ² , R ³ , R ⁵ and R ⁶ independently represents a hydrogen atom, a C 1 to C 5 alkoxy group, a C 5 to C 10 cyclic alkoxy group,

,

or

Lt; ³ > and R < ⁶ > When it is a hydrogen atom R ² and R ⁵ are not hydrogen atoms, the R ⁷ and R ⁸ are each independently a hydrogen atom, an alkoxy group of C1 ~ C5 straight alkyl, C3 ~ C5 grinding alkyl group or C1 ~ C3 a, R ⁹ and R ¹⁰ each independently represents a hydrogen atom, -SO ₃ H, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH, -NR ¹¹ R ¹² , -CH ₂ NR ¹¹ R ¹² or -CH ₂ CH ₂ NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are each independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms.
6. The phosphor according to claim 5, wherein R ¹ and R ⁴ of the perylene-based organic phosphor represented by Formula 3 are each independently a C 5 -C 6 cycloalkyl group,

Or -CN, and each of R ² , R ³ , R ^5, and R ⁶ is independently a hydrogen atom,

,

or

Lt; ³ > and R < ⁶ > When it is a hydrogen atom R ² and R ⁵ are not hydrogen atoms, R ⁷ and R ⁸ are each independently a straight-chain alkyl group having 1 to 5 carbon atoms or an alkoxy group having ¹ to ₃ carbon atoms, R ⁹ and R ¹⁰ are each independently a hydrogen atom, _{H, -COOH, -CH 2 COOH,} -CH 2 CH 2 COOH or -CH ₂ CH ₂ CH ₂ emission color filter characterized in that the COOH.
The luminescent color filter according to claim 1, wherein each of the green organic phosphor and the red organic phosphor has a specific gravity of 1.0 to 2.0 g / cm 3 and a pyrolysis temperature of 270 ° C or more.
The luminescent color filter according to claim 1, wherein the green light emitting filter comprises 5 to 50% by weight of the green organic phosphor.
The light-emitting color filter according to claim 1, wherein the red light emitting filter comprises 10 to 50% by weight of the red organic phosphor.
The light emitting color filter according to claim 1, wherein the red light emitting filter comprises the red organic phosphor and the green organic phosphor in a weight ratio of 1: 0.20 to 1: 1.
The organic electroluminescent device according to claim 1, wherein the photosensitive thin film having a thickness of 2 占 퐉 and comprising 10% by weight of the green-based organic fluorescent material is subjected to color difference measurement based on NTSC (National Television System Committee) color coordinates under a blue light source, A range of 0.0001 to 0.008, and a y coordinate deviation range of 0.0003 to 0.0010.
The organic electroluminescent device according to claim 1, wherein the photosensitive thin film having a thickness of 2 占 퐉 and containing 10% by weight of the red organic phosphor or the organic fluorescent material containing the green organic fluorescent material and the red organic fluorescent material is grown on a blue light source according to NTSC color coordinates Wherein a deviation range of the x coordinate is 0.0001 to 0.006 and a y coordinate deviation range is 0.0001 to 0.0008 when the color deviation is measured.
12. A pharmaceutical composition according to any one of claims 1 to 12 A liquid crystal panel comprising a light emitting color filter.
A backlight unit emitting blue light, and a liquid crystal panel according to claim 13.

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