KR20170111554A - Color compensating and extruding optical film having excellent light-stability and Preparing method thereof - Google Patents

Abstract

The present invention relates to a novel color-compensated extrusion optical film and a method of manufacturing the same, and more particularly, to a color-compensated extrusion optical film capable of being manufactured by an extrusion method by introducing a specific organic phosphor and a specific resin, And a method for manufacturing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a color compensating extrusion optical film excellent in light stability and a manufacturing method thereof,

The present invention relates to a color-compensated extruded optical film into which a specific organic fluorescent material is introduced, and a method of manufacturing the extruded optical film.

Quantum dots are nanoscale semiconductor materials that exhibit a quantum confinement effect. The quantum dots generate stronger light in a narrow wavelength band than ordinary phosphors.

The luminescence of quantum dots is generated by the transfer of electrons excited from the conduction band to the valence band. In the case of the same material, the wavelength exhibits characteristics depending on the particle size. As the size of the quantum dots decreases, the light of a short wavelength is emitted, so that light of a desired wavelength range can be obtained by controlling the size.

The quantum dot emits when excitation wavelength is arbitrarily selected. Therefore, when there are various kinds of quantum dots, the quantum dot excites to one wavelength, and various colors of light can be observed at a time. Even if the quantum dots are made of the same material, the color of the emitted light may vary depending on the particle size. Due to such characteristics, quantum dots are attracting attention as next generation high brightness light emitting diodes (LEDs), bio sensors, lasers, and solar cell nano materials.

Currently, the production method that is commonly used to form quantum dots is nonhydrolytic synthesis. According to this method, a nucleus is formed (nuclraization) by thermal decomposition reaction by rapid injection of a metalorganic compound at room temperature as a precursor or precursor into a high-temperature solvent, and then nuclei are grown by applying a temperature to grow quantum dots Manufacturing. The quantum dots mainly synthesized by this method contain cadmium (Cd) such as cadmium selenium (CdSe) or cadmium tellurium (CdTe). However, considering the current trend of pursuing the green industry due to heightened environmental awareness, it is necessary to minimize the use of cadmium (Cd) which is one of the typical environmental pollutants that pollute water quality and soil.

Therefore, it is considered to manufacture quantum dots as a semiconductor material which does not contain cadmium as an alternative for replacing existing CdSe quantum dots or CdTe quantum dots. Indium phosphide (InP) quantum dots are one of them.

Particularly, the indium phosphide (InP) has a bulk band gap of 1.49 eV, and the InP quantum dot can emit light in a visible light region, and thus can be used for manufacturing a high-luminance light emitting diode device and the like. However, since Group 13 and Group 16 are generally difficult to synthesize, it is not only difficult to mass-produce indium phosphide quantum dots but also has a disadvantage in that the uniformity of the particle size is ensured and the quantum yield (QY) is lower than that of the conventional CdSe .

Therefore, there is a growing demand for the development of new fluorescent materials that do not use cadmium.

In addition, QDEF (3M ^@ beauty) adopts a method of coating inorganic quantum dots (QDs) by using a binder, and quantum dots are oxidized to deteriorate characteristics, so it is necessary to use an expensive gas barrier film . The quantum dot, which is the address material of the color reproduction compensation film, is generally an inorganic material, so a high-temperature extrusion process may be possible. However, it is very difficult to disperse the polymer because the specific gravity is 4 to 6 times higher than that of the binder polymer. There is a problem that the characteristic deterioration is large and the use thereof is practically impossible.

In addition, conventional organic phosphors have poor thermal stability, and thus there is a problem that optical stability and color reproducibility are greatly reduced when an optical film is produced through an extrusion process.

U.S. Published Patent Application No. 2012-0113672 (2012.05.10)

The present inventors have made efforts to produce a new material capable of replacing quantum dots of existing inorganic materials. As a result, they have found that when an organic fluorescent material having a stable thermal property is introduced into an optical film, (Mono) or a multilayer (multi-layer) structure can be produced on the extruded sheet. The extruded optical film can be produced by extruding the extruded optical film having a barrier property, Thereby completing the present invention. That is, the present invention provides a color-compensated extrusion optical film produced through an extrusion process using a specific organic phosphor and a method of manufacturing the same.

In order to solve the above problems, the present invention provides a color-compensated extruded optical film comprising a green organic phosphor having a PL wavelength of 500 to 570 nm and a red organic phosphor having a PL wavelength of 580 to 680 nm An organic fluorescent material comprising at least one organic fluorescent material; And a transparent resin.

In one preferred embodiment of the present invention, the green organic phosphor may include an organic phosphor represented by the following general formula (1).

[Chemical Formula 1]

또는

이며, R³은 C1 ~ C4의 직쇄형 알킬기 또는 C3 ~ C6의 분쇄형 알킬기이고, n은 0 ~ 3이다.In the formula 1, wherein R ¹ is a straight-chain alkyl group or branched alkyl group of C3 ~ C10 ~ C10 of the C3, A, B, C and D each independently represent a halogen atom or an -OR ^2, R ² is C3 ~ C10 straight-chain alkyl group, C3-C10 branched alkyl group, C5-C10 cycloalkyl group,

or

R ³ is a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and n is 0 to 3.

또는

이고, R³은 -CH₃, -CH₂CH₃, -C(CH₃)₃ 또는 -CH(CH₃)₂이며, n은 0 ~ 3일 수 있다.As a preferred embodiment of the present invention, R ¹ in the formula (1) is a straight-chain alkyl group of C 3 to C 5 or a branched alkyl group of C 3 to C 5, and each of A, B, C and D is independently a halogen atom or -OR ² And R ² is

or

And R ³ is -CH ₃ , -CH ₂ CH ₃ , -C (CH ₃ ) ₃ or -CH (CH ₃ ) ₂ , and n may be 0 to 3.

이고, n은 0이며, B 및 C는 -F 또는 -Cl일 수 있다.In one preferred embodiment of the present invention, A and D in Formula 1 are -OR ² , and R ² is

, N is 0, and B and C may be -F or -Cl.

In one preferred embodiment of the present invention, the green organic phosphor may include an organic phosphor represented by the following general formula (2).

(2)

이다.In Formula 2, R ¹ , R ^2, R ³ and R ⁴ are each independently selected from the olefin group of C1 ~ C5 alkyl group, C2 ~ C5 of, a cycloalkyl group of C5 ~ C6, a styrene group, a phenyl group, a phenol group or a benzyl group, R ⁵ is a phenyl group, ( alkoxy of C1 ~ C3) (a trialkyl) phenyl group or a phenol group of C1 ~ C3 of dialkyl) group, a phenyl group, a (C1 ~ C3 (dialkylamino of C1 ~ C3), R ⁶ and R ⁷ are each independently - Each of R ⁸ and R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

to be.

일 수 있다.In one preferred embodiment of the present invention, R ¹ , R ² , R ³ and R ⁴ are each a C1 to C3 alkyl group or a phenyl group, R ⁵ is a phenyl group, a 4-methoxy-2,6-dimethylphenyl group, a 4-methoxy- An ethoxy-2,6-dimethylphenyl group, a 4-ethoxy-2,6-diethylphenyl group, a 2,4,6-trimethylphenyl group or a 2,4,6-triethylphenyl group, R ⁶ and R ⁷ is -F or an alkyl group of C1 ~ C2, R ⁸ and R ⁹ is a hydrogen atom or

Lt; / RTI >

In one preferred embodiment of the present invention, the green organic phosphor and the red organic phosphor may have a specific gravity of 1.0 to 2.0 g / cm 3 and a pyrolysis temperature of 250 ° C or higher.

As another preferred embodiment of the present invention, the color-compensated extrusion optical film of the present invention may contain 100 to 2,500 ppm of the green-based organic phosphor and / or 10 to 1,000 ppm of the red-based organic phosphor.

In one preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention may contain the green-based organic phosphor and the red-based organic phosphor in a weight ratio of 1: 0.05 to 0.8.

As a preferred embodiment of the present invention, in the color-compensated extrusion optical film of the present invention, the transparent resin may be a polycarbonate resin, a polyethylene terephthalate resin, polymethyl methacrylate (PMMA) And may include at least one selected from polymethyl methacrylate (co-PMMA), acrylonitrile-butadiene-styrene (ABS) resin and PS (polystyrene) resin.

In one preferred embodiment of the present invention, the polycarbonate resin may have a MI (melting index) of 1 to 40 and a glass transition temperature (Tg) of 130 ° C to 160 ° C.

In one preferred embodiment of the present invention, the polyethylene terephthalate resin may be a polyethylene terephthalate resin having an intrinsic viscosity (IV) of 0.5 to 1.0 dl / g.

In one preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention may have an average thickness of 10 to 1,000 μm.

In one preferred embodiment of the present invention, the color-compensated extrusion optical film of the present invention has a single-layer structure of an organic phosphor layer including a green organic phosphor and a red organic phosphor; Or a multi-layer structure in which a plurality of organic phosphor layers of the single-layer structure are stacked.

As a preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention is a multi-layered structure in which a green organic fluorescent substance layer containing a green organic fluorescent substance and a red organic fluorescent substance layer containing a red organic fluorescent substance are alternately laminated Green organic phosphor layer may be a multilayer structure in which red organic fluorescent layers are randomly laminated.

As a preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention may have a light diffusion pattern or a condensed pattern formed on the upper surface of the uppermost organic fluorescent layer of the color-compensated extruded optical film have.

In one preferred embodiment of the present invention, the color-compensated extrusion optical film of the present invention may further comprise a skin layer on one or both sides.

In one preferred embodiment of the present invention, the surface of the skin layer of the color-compensated extrusion optical film of the present invention may have a light diffusion pattern or a light condensing pattern formed thereon.

In one preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention has a deviation range of x-coordinate of 0.0001 to 0.0020 when measuring color deviation based on NTSC (National Television System Committee) color coordinates under a blue light source , and the y coordinate deviation range may be 0.0002 to 0.0022.

As a preferred embodiment of the present invention, the color compensated extruded optical film of the present invention has a temperature (T _d ) at which a weight loss of 5% is lost when a temperature at which a weight loss of 5% is measured using a thermogravimetric analyzer It may be 300 ° C or higher.

Another object of the present invention is to provide a method of producing various types of color-compensated extruded optical films as described above, wherein a green organic phosphor having a PL wavelength of 500 to 570 nm in a monomolecular form, a PL wavelength of 580 to 680 nm A first step of preparing a master batch by mixing a red organic phosphor and a transparent resin; A second step of putting the master batch in an extruder and then melting it; 3) extruding the molten master batch into a continuous phase; And 4) a step of calendaring and quenching the continuous extrudate to produce a film. The color-compensated extruded optical film can be produced by a process comprising:

In one preferred embodiment of the present invention, the above-described various types of color-compensated extrusion optical films have a green-based master batch containing green-based organic phosphors having a PL wavelength of 500 to 570 nm and a transparent resin, A green system organic phosphor having a PL wavelength of 580 to 680 nm and a transparent resin; The green system master batch and the red system master batch are put into an extruder and then melted; Three steps of extruding or co-extruding the molten green masterbatch and the red base masterbatch into a continuous phase; And 4) a step of calendaring and quenching the continuous extrudate to produce a film.

In one preferred embodiment of the present invention, the green organic phosphor of the first stage may be an organic phosphor represented by Formula 1, and the red organic phosphor may be an organic phosphor represented by Formula 2. [

In one preferred embodiment of the present invention, the master batch for the skin layer is further prepared in step 1, the master batch for the skin layer is further injected into the extruder in step 2, and co-extruded with the organic phosphor batch in step 3, A film may also be produced.

As a preferred embodiment of the present invention, the melting of the two steps may be performed at a temperature of 250 ° C to 320 ° C.

As a preferred embodiment of the present invention, the calendering of the four steps may be performed using a calender roll at a temperature of 100 ° C to 140 ° C.

As a preferred embodiment of the present invention, the step 4 may further include a step of stretching the film after calendering and quenching, and then thermally fixing the film.

As a preferred embodiment of the present invention, the method of producing a color-compensated extruded optical film of the present invention may further comprise a fifth step of forming a surface structure on the surface of the four-step film.

As a preferred embodiment of the present invention, the surface structure formation may be performed by a roll-to-roll printing method or an imprinting method.

As a preferred embodiment of the present invention, in the case of the multilayer film of the four-step film in the method of producing a color-compensated extruded optical film of the present invention, the extruder of the two- Lt; / RTI >

Still another object of the present invention relates to a light emitting diode (LED) display comprising the above-described various types of color-compensated extrusion optical films.

It is another object of the present invention to provide a light emitting diode (LED) illumination device comprising the above-described various types of color-compensated extrusion optical films.

Still another object of the present invention relates to a backlight unit (BLU) or a liquid crystal display (LCD) including the above-described various types of color-compensated extrusion optical films.

Since the color-compensated extruded optical film of the present invention uses an organic phosphor excellent in thermal stability, an optical film can be produced through an extrusion process, and there is no problem of durability being oxidized like a quantum dot , Since the organic fluorescent material having a low specific gravity is used, the dispersibility in the resin is excellent, the optical uniformity and the optical stability of the optical film are excellent, and the optical film can be produced through the extrusion method other than the coating method. The castle is very good. The color-compensated extruded optical film of the present invention can be used in various fields such as an LED lighting device, an LED display device, and a liquid crystal display device.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a color-compensated extruded optical film of a single-layer structure according to one embodiment of the present invention. Fig.
2A and 2B are schematic views of a multi-layered color-compensated extrusion optical film as a preferred embodiment of the present invention.
FIGS. 3A to 3C are schematic views of a color-compensated extrusion optical film in which a green organic phosphor layer and a red organic phosphor layer are formed in a multilayer structure, according to a preferred embodiment of the present invention.
4 is a schematic view of a structure including a skin layer (skin film) as a preferred embodiment of the present invention.
5 is a graph showing PL intensity change measurement of Example 1 performed in Experimental Example 2. FIG.
FIG. 6 is a graph of the rate of change in luminance according to Example 1 performed in Experimental Example 2. FIG.
FIG. 7 is a graph of the rate of change in luminance measured in Example 1, Comparative Example 1, and Comparative Example 2 measured in Example 2. FIG.

The term "film" used in the present invention is meant to encompass not only film forms commonly used in the art, but also sheets.

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.

The conventional organic phosphors have poor heat resistance and can not be used for commercialization of extruded optical films through an extrusion process. However, the present invention has been made in view of the fact that by introducing specific organic phosphors having excellent heat resistance among monomolecular organic phosphors, As an invention enabling the production of a compensatory optical film, the color-compensated extruded optical film of the present invention comprises: an organic fluorescent material comprising at least one selected from a green organic fluorescent material and a red organic fluorescent material in a monomolecular form; And a transparent resin.

The color-compensated extruded optical film 1 (hereinafter referred to as an extruded optical film) of the present invention comprises a green-based organic phosphor 10 and a red-based organic fluorescent substance 20, as shown schematically in FIG. Structure.

Further, the color-compensated extrusion optical film of the present invention may have a multi-layer structure in which the single-layered organic phosphors (organic phosphor layers 1a to 1e) are stacked in two or more layers as schematically shown in FIGS. 2A to 2C. In the case of a multi-layer structure, the adhesive layer may not be formed between the laminated film and the film, and the film and the film may be bonded through the adhesive layer. Preferably, the film and the film are co- (Or bonded) directly to each other without any adhesive between them, which is advantageous in terms of ensuring a high luminance.

The color-compensated extrusion optical film of the present invention comprises a green organic phosphor layer 1 including a green organic phosphor and a red organic phosphor layer 2 including a red organic phosphor as schematically shown in FIGS. 3A through 3B , 2 ') may be alternately laminated or randomly laminated.

In addition, the color-compensated extruded optical film of the present invention may have a structure for light diffusion or condensation on the surface of the uppermost organic phosphor layer in the light traveling direction.

The color-compensated extrusion optical film of the present invention may be in the form of a skin layer on one or both sides of the organic phosphor layer as shown schematically in FIG. 4, Structure may be formed.

At this time, the pattern formed on the organic phosphor layer and / or the skin layer may be a pattern that diffuses or condenses light such as a prism pattern, a semicircle pattern, a wave pattern, a lenticular pattern, a microlens pattern, a polygonal pattern, And may be formed in various patterns.

The extruded optical film (or the organic fluorescent layer) preferably has an average thickness of 10 to 1,000 占 퐉, preferably 20 to 500 占 퐉, more preferably 50 to 400 占 퐉.

Among the components of the extruded optical film of the present invention, the transparent resin is preferably a material having excellent compatibility with the organic fluorescent substance and excellent transparency. For example, a polycarbonate (PC) resin, a polyethylene terephthalate (PMMA), co-polymethyl methacrylate (co-PMMA), ABS (acrylonitrile-butadiene-styrene) resin and PS (polystyrene) , And preferably one or two or more selected from a polycarbonate resin, a polyethylene terephthalate resin and a polymethyl methacrylate resin can be used.

The PC resin is an amorphous resin having a high glass transition temperature (Tg), so that a color-compensated extruded optical film having high reliability can be produced without stretching the extruded film, and a PC Preferably a PC resin having a MI (melting index) of 1 to 40 and a glass transition temperature (Tg) of 130 to 160 ° C, more preferably an MI of 4 to 35, and a glass transition PC resin with a temperature of 140 ° C to 160 ° C is recommended. At this time, if the MI of the PC resin exceeds 40, extrusion workability deteriorates, which is not only disadvantageous in terms of mass production, but also has a problem that the high temperature storage stability of the color compensated extruded optical film (WHTS) falls.

When a PET resin is used as the transparent resin, it is necessary to stretch the film to an extruded film. The PET resin used in the present invention may be a conventional PET resin. Preferably, the PET resin has an intrinsic viscosity (IV) It is preferable to use a PET resin having an intrinsic viscosity (IV) of 0.65 to 0.80 dl / g, more preferably a PET resin having a viscosity of 1.0 dl / g. If the intrinsic viscosity of the PET resin is less than 0.5 dl / g, the extrusion workability tends to deteriorate, which may be disadvantageous in terms of mass productivity. If the intrinsic viscosity exceeds 1.0 dl / g, The PET resin having an intrinsic viscosity within the above range may be used.

[Organic fluorescent material]

Hereinafter, the organic fluorescent substance applied to the extruded optical film of the present invention will be specifically described.

The organic phosphor used in the extrusion optical film of the present invention is an organic phosphor having a wavelength of 500 nm to 680 nm in the form of PL (monolayer) monolayer, preferably a green organic phosphor having a PL wavelength of 500 to 570 nm, 580 to 680 nm may be used alone or in combination of two or more.

When two or more of the green organic phosphor and the red organic phosphor are used in the extrusion optical film (or the organic fluorescent layer), the content of the green organic phosphor in the extruded optical film (or organic fluorescent layer) is preferably 100 to 2,500 ppm, Preferably 100 to 1,200 ppm, more preferably 100 to 900 ppm, and still more preferably 200 to 850 ppm. It is preferable that the content of the red organic phosphor in the extrusion optical film is 10 to 1,050 ppm, preferably 10 to 450 ppm, more preferably 10 to 300 ppm, and still more preferably 15 to 150 ppm. Good on the control surface.

It is also preferable to mix the green organic phosphor and the red organic phosphor at a weight ratio of 1: 0.01 to 0.8, preferably 1: 0.05 to 0.4, more preferably 1: 0.05 to 0.2. In this case, when the weight ratio of the red organic phosphor is less than 0.01 weight ratio or more than 0.8 weight ratio, the x coordinate range is 0.20 to 0.50 and the y coordinate range is 0.15 to 0.40 on the NTSC color coordinate of FIG. 3, This can be difficult.

The organic phosphor preferably has a specific gravity of 1.0 to 2.0 g / cm 3 and a thermal decomposition temperature (TD) of 250 or more, preferably 270 ° C or more, more preferably 300 ° C or more, When the specific gravity of the organic fluorescent substance is less than 1.0 g / cm 3 or the specific gravity exceeds 2.0 g / cm 3, the dispersibility in the transparent resin is decreased and the workability is deteriorated. The organic fluorescent substance in the extruded optical film is not uniformly dispersed, There may be a problem.

If the pyrolysis temperature of the organic phosphor is less than 250 ° C, the optical film may lose its inherent optical characteristics because it is deformed and decomposed during extrusion due to the characteristics of an extrusion process performed at a high temperature. There is a problem that the structure of the organic phosphor is broken and the light stability is greatly deteriorated. As the green organic phosphor having a PL wavelength of 500 to 570 nm satisfying such characteristics, the green organic phosphor may be a mixture of one or more selected from the perylene-based organic phosphors represented by the following formula (1).

[Chemical Formula 1]

R ¹ in the above formula (1) is a straight-chain alkyl group of C 3 to C 10 or a branched alkyl group of C 3 to C 10, preferably R ¹ is a straight-chain alkyl group of C 3 to C 5 or a branched alkyl group of C 3 to C 5, Is a C3 to C5 branched alkyl group.

Each of A, B, C and D is independently a halogen atom or -OR ² , preferably A, B, C and D are all or -OR ² , or A and D are -OR ² , And B and C may be a halogen atom.

또는

이며, 바람직하게는 R²는

또는

이고, 더욱 바람직하게는 R²는

이다. And R ² is a straight-chain alkyl group of C 3 to C 10, a branched alkyl group of C 3 to C 10, a cycloalkyl group of C 5 to C 10,

or

, Preferably R < ^{2 >} is

or

, More preferably R < ^{2 >} is

to be.

And R ³ is a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, preferably -CH ₃ , -CH ₂ CH ₃ , -C (CH ₃ ) ₃ or -CH (CH ₃ ) ₂ . In formula (1), n is 0 to 3.

In addition, as a red organic phosphor having a PL wavelength of 580 to 680 nm satisfying the above characteristics, one or more organic phosphor selected from organic phosphors represented by the following formula (2) may be used in combination.

 (2)

In Formula 2, R ¹ , R ² , R ³ and / or R ⁴ may each independently be a C 1 to C 5 alkyl group, a C 2 to C 5 olefin group, a C 5 to C 6 cycloalkyl group, a styrene group, a phenyl group, a phenol group or a benzyl group, R ¹ , R ² , R ³ and / or R ⁴ may each independently be a phenyl group or a C 1 to C 3 alkyl group, more preferably R ¹ , R ² , R ³ and / or R ⁴ may each independently be a phenyl group, a methyl group or an ethyl group.

The R ⁵ in Formula 2 may be a phenyl group, a (C1-C3 alkoxy) (C1-C3 dialkyl) phenyl group, a C1-C3 dialkylphenyl group, or a C1- preferably, the R ⁵ is a phenyl group, (alkoxy of C1 ~ C2) is (dialkylamino of C1 ~ C2) phenyl group or a phenyl group (trialkyl of C1 ~ C3), more preferably the R ⁵ is a phenyl group, 4- Ethoxy-2,6-dimethylphenyl group, 4-methoxy-2,6-diethylphenyl group, 4-ethoxy-2,6-dimethylphenyl group, , 4,6-trimethylphenyl group or 2,4,6-triethylphenyl group.

R ⁶ and / or R ⁷ in Formula 2 may each independently be -Br, -F, -Cl, -OH, a C 1 -C 5 alkyl group, a C 5 -C 6 cycloalkyl group, a phenyl group, or a naphthalene group, , R ⁶ and / or R ⁷ may each independently be -Br, -F, -Cl, a C 1 -C 3 alkyl group or a naphthalene group, more preferably R ⁶ and R ⁷ are -F or C 1 -C 2 Alkyl group.

이며, 바람직하게는 R⁸ 및 R⁹는 모두 수소원자 또는

이다.Each of R ⁸ and R ^{9 in} the above formula (2) is independently a hydrogen atom or

, And preferably R ⁸ and R ⁹ are both a hydrogen atom or

to be.

The extruded optical film (or the organic fluorescent layer) of the present invention may contain, in addition to the green and / or red organic fluorescent material and the transparent resin described above, beads; And other phosphors including at least one selected from polymer dots and dyes; And additives; , And the like.

The beads are additionally used to uniformly distribute light to improve color, and the beads may include at least one selected from monodisperse beads and polydisperse beads. The beads may be formed of at least one selected from silica, zirconia, titanium dioxide, polystyrene, polypropylene, polyethylene, polyurethane and polymethyl (meth) acrylate, preferably in a monodispersed form of silica, polystyrene and titanium dioxide One or more selected ones may be used, and monodisperse type beads containing silica of a transparent material may be more preferably used.

Among the other phosphors, the polymer dot may include at least one selected from a random copolymer represented by the following formula (3) and a random copolymer represented by the following formula (4).

(3)

을 포함하는 C2 ~ C4의 올레핀기이고, 여기서, R¹⁴는 메틸기 또는 에틸기이며, n은 0 ~ 3의 정수이며, R⁶ ~ R¹¹ 각각은 독립적으로 C1 ~ C12의 직쇄형알킬기, C4 ~ C12의 분쇄형알킬기 또는 C2 ~ C12의 올레핀기이며, R¹² ~ R¹³는 독립적으로 C1 ~ C5의 알킬기고, R¹⁵는 -OH, -OCH₃ 또는 -OCH₂CH₃이며, a, b, c, d는 중합체를 구성하는 단량체간의 몰비를 나타낸 것으로서, a, b, c, d의 몰비는 1 : 1 ~ 1.5 : 5 ~ 25 : 1 ~ 1.5이고, A 및 B는 독립적으로 페닐기, 페닐기, 바이페닐기, 안트라센기 및 나프탈렌기 중에서 선택된 1종 이상의 말단기이며, L은 공중합체의 중량평균분자량 1,000 ~ 50,000을 만족하는 유리수이다.Wherein R ¹ is a methyl group or an ethyl group, m is an integer of 0 to 3, R ² is a hydrogen atom, a methyl group or an ethyl group, R ³ is a C1 to C5 alkyl group, a C2 to C5 olefin group, A C5-C6 cycloalkyl group, a phenyl group or

Wherein R ¹⁴ is a methyl group or an ethyl group, n is an integer of 0 to 3, each of R ⁶ to R ¹¹ is independently a straight-chain alkyl group of C 1 to C 12, a straight chain alkyl group of C 4 to C 12 R ¹² to R ¹³ are each independently a C 1 to C 5 alkyl group, R ¹⁵ is -OH, -OCH ₃ or -OCH ₂ CH ₃ , and a, b, c and d is a molar ratio between the monomers constituting the polymer, wherein the molar ratio of a, b, c and d is 1: 1 to 1.5: 5 to 25: 1 to 1.5, A and B independently represent a phenyl group, An anthracene group and a naphthalene group, and L is a rational number satisfying a weight average molecular weight of the copolymer of 1,000 to 50,000.

을 포함하는 C2 ~ C4의 올레핀기이며, R¹⁴는 메틸기이고, n은 0 또는 1이고, R⁶ ~ R¹¹ 각각은 모두 동일하며, R⁶ ~ R¹¹은 C6 ~ C10의 직쇄형 알킬기 또는 C6 ~ C10의 분쇄형 알킬기이고, A 및 B는 페닐기인 것을 특징으로 할 수 있다.Preferably, R ¹ in the general formula (3) is a methyl group, m is an integer of 1 to 3, R ² is a hydrogen atom or a methyl group, R ³ is a C 1 to C 5 olefin or

, R ¹⁴ is a methyl group, n is 0 or 1, R ⁶ to R ¹¹ are all the same, R ⁶ to R ¹¹ are a straight-chain alkyl group of C6 to C10 or C6 To C10, and A and B are phenyl groups.

[Chemical Formula 4]

을 포함하는 C2 ~ C4의 올레핀기이고, 여기서, R⁸은 메틸기 또는 에틸기이며, n은 0 ~ 3의 정수이며, R⁶ 및 R⁷ 각각은 독립적으로 C1 ~ C12의 직쇄형 알킬기, C4 ~ C12의 분쇄형 알킬기 또는 C2 ~ C12의 올레핀기이고, a 및 b의 몰비는1 :5 ~ 15이고, A 및 B는 독립적으로 페닐기, 바이페닐기, 안트라센기 및 나프탈렌기 중에서 선택된 1종 이상의 말단기이며, L은 공중합체의 중량평균분자량 1,000 ~ 100,000을 만족하는 유리수이다.Wherein R ¹ is a hydrogen atom or an alkyl group having ¹ to 5 carbon atoms, R ² and R ³ are independently a hydrogen atom, a methyl group or an ethyl group, R ⁴ and R ⁵ are each independently a hydrogen atom, a C 1 to C 5 An alkyl group, a C2 to C5 olefin group, a C5 to C6 cycloalkyl group, a phenyl group or

Wherein R ⁸ is a methyl group or an ethyl group, n is an integer of 0 to 3, each of R ⁶ and R ⁷ is independently a straight-chain alkyl group of C 1 to C 12, a straight chain alkyl group of C 4 to C 12 And the molar ratio of a and b is 1: 5 to 15, and A and B are independently at least one end group selected from a phenyl group, a biphenyl group, an anthracene group and a naphthalene group , And L is a rational number satisfying the weight-average molecular weight of the copolymer of 1,000 to 100,000.

Preferably, R ¹ in Formula 4 is a methyl group, R ² and R ³ are independently a hydrogen atom or a C 1 to C 2 alkyl group, R ⁴ and R ⁵ are independently a hydrogen atom or a C 1 to C 5 alkyl group , R ⁶ and R ⁷ are independently a straight chain alkyl group of C 6 to C 10 or a branched alkyl group of C 6 to C 10, and A and B are phenyl groups.

In addition, among the above-mentioned other phosphors, the dyes for optical films used in the related art may be used, and preferably at least one selected from Coumain, Green and Rhodamine (Red) .

The additive may include one or more selected from a light stabilizer, an ultraviolet absorber, an antistatic agent, a lubricant, a leveling improver, a defoamer, a polymerization promoter, an antioxidant, a flame retardant, an infrared absorbent, a surfactant and a surface modifier .

[Manufacturing method]

Hereinafter, a method for producing the above-described color-compensated extruded optical film of the present invention will be described.

The color-compensated extruded optical film of the present invention is prepared by mixing a green organic phosphor having a PL wavelength of 500 to 570 nm in a monomolecular form, a red organic phosphor having a PL wavelength of 580 to 680 nm in a monomolecular form, Stage 1; A second step of putting the master batch in an extruder and then melting it; 3) extruding the molten master batch into a continuous phase; And 4) a step of calendering and quenching the continuous extrudate to produce a film. The color-compensated extruded optical film can be produced by a process comprising:

Further, the color-compensated extrusion optical film of the present invention is a green-based master batch containing a green organic phosphor and a transparent resin having a PL wavelength of 500 to 570 nm in a monomolecular form, a red organic compound having a PL wavelength of 580 to 680 nm A green master batch including a phosphor and a transparent resin; The green system master batch and the red system master batch are put into an extruder and then melted; Three steps of extruding or co-extruding the molten green masterbatch and the red base masterbatch into a continuous phase; And 4) a step of calendaring and quenching the extrudate in a continuous phase to produce a film. The color-compensated extruded optical film may also be produced.

The kind of the organic phosphor used in the master batch production in the first step, its content, the kind of the transparent resin, and the like are the same as those described above. In addition, in the production of the master batch in the first step, the beads described above in addition to the organic fluorescent substance and the transparent resin; Other dyes including at least one selected from polymer dots and dyes; And at least one selected from the above additives may be further mixed to prepare a highly concentrated masterbatch.

When the additive is added, the additive may be added in an amount of 1 to 60 parts by weight, preferably 1 to 20 parts by weight based on 100 parts by weight of the transparent resin. And when it exceeds 60 parts by weight, the dispersibility of the organic phosphor may be deteriorated.

In addition, in the above-mentioned two manufacturing methods, the master batch for the skin layer may be further prepared in step 1, the master batch for the skin layer may be further introduced into the extruder in step 2, and co-extruded with the organic phosphor batch in step 3.

Step 2 is a step of melting the master batch to extrude the master batch. In this case, a general extruder may be used depending on the structure of the optical film to be manufactured, or an optical film having a multilayer structure may be manufactured using a co-extruder. The melting is preferably performed at a temperature of 250 ° C to 320 ° C, preferably 260 ° C to 320 ° C, wherein the melting temperature is less than 250 ° C, The mechanical properties of the resulting film may be uneven. If the temperature exceeds 320 ° C, thermal deformation of the polymer may occur, resulting in deterioration or carbonization, and loss of functionality due to modification and decomposition of the additive It is preferable to melt the master batch in the above-mentioned temperature range.

Step 4 is a calendering process for filming a continuous extruded or coextruded extrudate in Step 3, and the calendering can be calendared by a general method used in the art, Calendering can be performed while quenching the continuous extrudate using a calender roll at a temperature of ~ 140 ° C.

If the transparent resin used in the master batch is a PET resin, the step 4 may further include a step of stretching the calendered and quenched film and then thermally fixing it to secure reliability. In this case, the stretching method may be a general method used in the art. For example, the stretched film may be stretched by 2 to 6 times, preferably 3 to 5 times, in the MD and / or TD directions It is advantageous in terms of securing the reliability of the color-compensated extrusion optical film.

The method of producing a color-compensated extruded optical film of the present invention comprises the steps of: forming a surface structure on the surface of the film produced in step 4; Process. ≪ / RTI > At this time, the surface structure may be formed by a general method used in the art. For example, a roll-to-roll printing method or an imprinting method may be used to form the surface structure. A surface structure can be formed on one surface or both surfaces. The shape of the surface structure is not particularly limited. For example, a surface structure such as a prism pattern, a semicircular pattern, a wavy pattern, a lenticular pattern, a microlens pattern, a polygonal pattern, an embossed pattern, .

The color-compensated extruded optical film of the present invention thus manufactured can have an x-coordinate range of 0.20 to 0.50 and a y-coordinate range of 0.15 to 0.40 based on the NTSC (National Television System Committee) color coordinate of FIG. 3 under a blue light source.

Further, the color-compensated extrusion optical film of the present invention has a deviation range of x-coordinate of 0.0001 to 0.0020 and a y-axis of 0.0001 to 0.0020 when measuring color deviation, based on NTSC (National Television System Committee) color coordinates of FIG. 3 under a blue light source, The coordinate deviation range may be 0.0001 to 0.0022, preferably the x coordinate deviation range is 0.0002 to 0.0015, and the y coordinate deviation range is 0.0004 to 0.0020, whereby excellent optical stability can be ensured.

In addition, the color-compensated extruded optical film of the present invention can have color reproducibility of 90% or more, preferably 95% to 115%, and more preferably 98% to 112%.

In addition, the color-compensated extruded optical film of the present invention has a temperature (T _d ) at which a weight of 5% is lost when the temperature at which a weight loss of 5% is measured using a thermogravimetric analyzer (TGA) Lt; / RTI >

Further, the color-compensated extruded optical film of the present invention can have a luminance uniformity of 88% or more, preferably 90% to 95%, and the dispersibility of the organic phosphor is very high.

The organic fluorescent material of the present invention and the optical film produced using the organic fluorescent substance of the present invention may be prepared or combined with a prism film, a diffusion film, a light guide plate, a reflective polarizer, or the like to produce R, G, (LED) display device, a light emitting diode (LED) lighting device, and / or a liquid crystal display device (LCD).

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  1-1: Green system  Preparation of Organic Phosphor

 (1) Preparation of the compound represented by the formula (a)

Perylene-3,4,9,10-tetracarboxylic dianhydride (25.49 mmol, 10 g) and iodine (iodine, 4.33 mmol, 1.1 g) were placed in a three-necked flask, Chlorosulfonic acid (40 ml) was added in the atmosphere.

Next, the reaction was carried out by raising the temperature to 70 ° C and heating and stirring for 20 hours. After completion of the reaction, the temperature was slowly cooled to 24 ° C to 25 ° C, and then cold water was slowly added to the cooled reaction solution A precipitate was formed.

Next, the precipitate was filtered, washed with water, and then dried to obtain an orange solid represented by the following formula (a).

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

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

(A)

(2) Synthesis of Compound Represented by Formula b

(18.86 mmol, 10 g) was added to a three-necked flask and CH ₃ CN (0.06 M, 310 ml), 1-bromo-2-methylpropane 269.88 mmol, 30 ml), 2-methyl-1-propanol (324.39 mmol, 30 ml) and DBU (182.94 mmol, 27.3 ml) were added in this order and refluxed for 12 hours.

Next, after the completion of the reaction, the temperature was lowered to 24 to 25 DEG C, methanol was added thereto, stirred, and filtered to obtain a solid.

Next, after the solid was subjected to hot-air drying, the dried solid was subjected to silica column to obtain a yellow solid which was a compound represented by the following formula (b).

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.09 (s, 4H), 4.15 (m, 8H), 2.14 (m, 4H), 1.05 (d, 24H)

^{_{13 C NMR (CDCl 3, ppm}} ): 166.2, 131.6, 128.6, 128.2, 127.9, 127.6, 124.4, 74.4, 27.7, 19.4

[Formula b]

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

(12.65 mmol, 10 g) and K ₂ CO ₃ (126.5 mmol, 17.5 g) were placed in a three-necked flask, and NMP (0.06M, 210 ml) was added in a nitrogen atmosphere and stirred.

Next, phenol (126.5 mmol, 11 ml) was added and stirred and reacted at 140 캜 for about 30 hours. After the reaction was completed, the temperature was decreased from 24 ° C to 25 ° C, 1N HCl was added, and precipitates were formed.

The precipitate was filtered, washed with water, and then dried with hot air. The dried solid was subjected to silica column chromatography to obtain a yellowish orange solid (yield: 70%).

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

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.24 (s, 4H), 7.21 (m, 8H), 6.97 (m, 4H), 6.91 (m, 8H), 4.21 (d, 8H), 2.42 (m, 4H), 1.01 (d, 24H)

¹³ C NMR ( CDCl ₃ , ppm): 166.3, 157.4, 149.9, 131.7, 128.7, 126.9, 123.1, 122.7, 121.9, 117.7, 115.2, 75.4, 27.7, 19.4

 [Formula 1-1]

이고, n은 0이다.In Formula 1-1, R ¹ is an isobutyl group (isobutyl group), and an A, B, C and D is -OR ^2, R ² is

And n is zero.

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

The compound represented by Formula (b) was prepared in the same manner as in Preparation Example 1-1.

(12.65 mmol, 10 g) and K ₂ CO ₃ (126.5 mmol, 17.5 g) were placed in a three-necked flask, and NMP (0.06M, 210 ml) was added in a nitrogen atmosphere and stirred.

Then, 4-tetra-butylphenol (126.5 mmol, 19 g) was added thereto, and the mixture was stirred and reacted at 140 ° C for about 30 hours. After the reaction was completed, the temperature was decreased from 24 ° C to 25 ° C, 1N HCl was added, and precipitates were formed.

The precipitate was filtered, washed with water, and then dried with hot air. The dried solid was subjected to silica column chromatography to obtain an orange solid (yield: 68%) as a yellowish color.

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) = 8.25 (s, 4H), 7.25 (d, 8H), 6.84 (d, 8H), 4.21 (d, 8H), 2.43 (m, 4H), 1.34 (s, 36H), 1.O1 (d, 24H)

¹³ C NMR ( CDCl ₃ , ppm): 166.1, 153.9, 149.9, 143.1, 131.7, 126.9, 124.8, 123.2, 122.7, 117.1, 115.2, 74.4, 40.7, 31.4, 27.7, 19.4

 [Formula 1-2]

이다.Wherein R ¹ is an isobutyl group, A, B, C and D are -OR ² , and R ² is

to be.

Preparation Example  One- 3:  Indicated by 1-3 Green system  Preparation of Organic Phosphor

The compound represented by Formula (b) was prepared in the same manner as in Preparation Example 1-1.

(12.65 mmol, 10 g) and K ₂ CO ₃ (126.5 mmol, 17.5 g) were placed in a three-necked flask, and NMP (0.06M, 210 ml) was added in a nitrogen atmosphere and stirred.

Next, 2,4,6-trimethylphenol (126.5 mmol, 17.2 g) was added thereto, and stirred and reacted at 140 ° C for about 30 hours. After the reaction was completed, the temperature was decreased from 24 ° C to 25 ° C, 1N HCl was added, and precipitates were formed.

The precipitate was filtered, washed with water, and then dried with hot air. The dried solid was subjected to silica column chromatography to obtain an orange solid (yield 69%) as a yellowish color.

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

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.27 (s, 4H), 6.64 (s, 8H), 4.20 (d, 8H), 2.45 (m, 4H), 2.37 (s, 36H), 1.03 (d, 24H)

¹³ C NMR ( CDCl ₃ , ppm): 165.9, 149.9, 147.1, 131.7, 131.3, 127.6, 127.5, 126.9, 123.2, 122.7, 115.2, 74.4, 27.7, 24.9,

 [Formula 1-3]

이다.In Formula 1-3, R ¹ is isobutyl group, A, B, C and D are -OR ² , R ² is

to be.

Preparation Example  1-4: Green system  Preparation of Organic Phosphor

The compound represented by Formula (b) was prepared in the same manner as in Preparation Example 1-1.

(12.65 mmol, 10 g) and K ₂ CO ₃ (126.5 mmol, 17.5 g) were placed in a three-necked flask, and NMP (0.06M, 210 ml) was added in a nitrogen atmosphere and stirred.

Next, phenol (126.5 mmol, 11 ml) was added thereto, and the mixture was stirred and reacted at 90 캜 for about 30 hours. After the reaction was completed, the temperature was decreased from 24 ° C to 25 ° C, 1N HCl was added, and precipitates were formed.

The precipitate was filtered, washed with water, and then dried with hot air. The dried solid was subjected to silica column chromatography to obtain an orange solid (yield: 71%) as a yellowish color.

It was confirmed by ¹ H-NMR and ¹³ C NMR measurements that the compound was represented by the following formula (1-4).

^{1 H-NMR spectrum (300 MHz} , CDCl 3): δ (ppm) = 8.60 (s, 2H), 8.25 (s, 2H), 7.22 (m, 8H), 6.98 (t, 4H), 6.92 (d, 8H), 4.21 (d, 8H), 2.43 (m, 4H), 1.01 (d, 24H)

¹³ C NMR ( CDCl ₃ , ppm): 166.5, 157.0, 149.9, 131.7, 131.6, 128.6, 128.5, 127.9, 127.6, 125.7, 123.5, 121.9, 117.5, 115.2, 74.4, 27.7, 19.4

 [Formula 1-4]

이고, n은 0이며, B 및 C는 -Cl이다.In Formula 1-4, R ¹ is isobutyl group, A and D are -OR ² , and R ² is

, N is 0, and B and C are -Cl.

Preparation Example  2: a compound represented by the formula (2-1) Red  Preparation of Organic Phosphor

(1) A three-necked flask was charged with 8-mesityl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora 3-3a, 4a-diaza- Mesityl-1,3,5,7-tetramethyl-4,4- difluoro-4-bora3-3a, 4a-diaza-s-indacene) (2.708mmol) was placed to 1g, added to CH ₂ Cl _2, and then stirring .

Next, 2.44 g of NIS (N-iodosuccinimide, 10.832 mmol) was added, followed by stirring at room temperature (about 25 ° C) for 6 hours. Next, the solvent was removed using a rotary evaporator, and the obtained material was subjected to a column to obtain a red solid represented by the following formula (c).

^{_{1 H NMR (CDCl 3, 400MHz}} ): δ (ppm) = 6.973 (s, 2H), 2.646 (s, 6H), 2.356 (s, 3H), 2.061 (s, 6H), 1.402 (s, 6H)

(C)

(2) To a three-necked flask were added 1 g of the red solid (1.615 mmol) prepared above, c) 1.018 g of thiophene bornic acid pinacol ester (4.845 mmol), K ₂ CO ₃ (16.15 mmol) and 186.6 mg of Pd (PPh ₃ ) ₄ (0.1615 mmol) were added, and the mixture was subjected to vacuum treatment, followed by nitrogen blowing. Next, a solvent (THF: H ₂ O = 9: 1 by volume) was added thereto, followed by overnight reflux at 85 ° C.

After completion of the reaction, the reaction mixture was cooled to room temperature (about 25 ° C) and the solvent was removed using a rotary evaporator. The resulting material was subjected to column chromatography to obtain a dark red solid represented by the following formula 4-1 .

^{_{1 H NMR (CDCl 3, 400MHz}} ): 7.35 (d, 2H), 7.08 (m, 2H), 6.96 (s, 2H), 6.87 (m, 2H), 2.61 (s, 6H), 2.33 (s, 3H ), 2.16 (s, 6 H), 1.40 (s, 6 H)

[Formula 2-1]

Example of comparison preparation  One

(1) Preparation of the compound represented by the formula (d)

In a three-necked flask, perylene-3,9-dicarboxylic acid (9.2 g, 27.03 mol) and isobutyl alcohol (50 ml) were added and stirred at 65 ° C for 3 hours, . After completion of the reaction, the temperature was lowered to 24 ° C to 25 ° C, and MeOH (500 ml) was added thereto. The resulting precipitate was filtered, and the precipitate was washed with cold MeOH.

Next, the washed material was dried in a vacuum oven to obtain a yellow solid (9.6 g, 78%), which was confirmed to be a compound represented by the following formula (d).

¹ H-NMR ( 300 MHz , CDCl ₃ ) :? (Ppm) = 8.19 (d, 2H), 7.96-91 (m, 4H), 7.39 (m, 4H) , ≪ / RTI > 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

[Chemical formula d]

(2) Preparation of the compound represented by the formula (e)

(9.6 g, 21.22 mol), N-bromosuccinimide (7.85 g, 44 mol) and CH ₂ Cl ₂ were added to a three-necked flask and stirred (TLC terminated) .

Next, after the completion of the reaction, the solution was removed with an evaporator, and a column was obtained to obtain a solid, which was confirmed to be a compound represented by the following formula (e).

^{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

(E)

(3) Preparation of the compound represented by the general formula (5)

(12 parts by weight), copper cyanide (9 parts by weight) and sulfolane (100 parts by weight) were placed in a three-necked flask and stirred at 130 ° C to 140 ° C for 25 hours, Lt; / RTI > Next, after the reaction was completed, distilled water (H ₂ O, 400 parts by weight) was slowly added thereto, and a precipitate was formed.

Next, the precipitate was obtained by filtering with diluted ammonia, which was then washed with distilled water and dried.

Next, Br containing 1.2% of the dried material was extracted with toluene (9 parts by weight) and then purified with a silica gel column (trichloroethane / ethanol) to obtain an orange solid (yield: 61%) represented by the formula 5 .

^{1 H-NMR (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 , ≪ / RTI > 2H), 0.92 (d, 12H)

^{_{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

[Chemical Formula 5]

Example of comparison preparation  2

(Perylene-3,4,9,10-tetracarboxylic dianhydride, 25.49 mmol, 10 g) was added to a three-necked flask and CH ₃ CN (0.06M, 424 ml) 2-methylpropane (364.75 mmol, 40 ml), 2-methyl-1-propanol, 438.43 mmol, 40 ml), DBU (247.25 mmol, 37 ml) were added in this order and refluxed for 12 hours.

Next, after the completion of the reaction, the temperature was lowered to 24 to 25 DEG C, methanol was added thereto, stirred, and filtered to obtain a solid.

Next, the solid was subjected to hot-air drying, and the dried solid was subjected to silica column to obtain an orange solid (yield: 93%) represented by the following formula (6).

^{1 H-NMR (300 MHz,} CDCl 3): δ (ppm) = 8.25 (d, 4H), 8.03 (d, 4H), 4.11 (d, 8H), 2.12 (m, 4H), 1.03 (d, 24H )

^{_{13 C NMR (CDCl 3, ppm}} ): 168.5, 133.0, 130.5, 130.3, 129.0, 128.8, 121.4, 71.5, 27.9, 19.4

[Chemical Formula 6]

Example of comparison preparation  3: 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 general formula (7).

^{_{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 )

(7)

In Formula 7, 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 wavelength
(nm) PL wavelength measurement
(nm) Preparation Example 1-1 506 539 Preparation Example 1-2 510 543 Preparation Example 1-3 507 540 Preparation Example 1-4 501 537 Preparation Example 2 577 630 Comparative Preparation Example 1 475 527 Comparative Preparation Example 2 476 528 Comparative Preparation Example 3 501 523

Example  One: Extrusion process  Production of film through

A green batch organic phosphor represented by Formula 1-1 prepared in Preparation Example 1-1 was compounded in a high concentration in a polycarbonate (PC) resin having an MI of 10 to prepare a master batch. At this time, the master batch was prepared so that the green organic phosphor of Preparation Example 1-1 in the master batch had a concentration of 3,500 ppm.

Next, the master batch and the PC resin (base resin) were fed into a 1: 9 weight ratio extruder of a twin screw extruder of 300 psi L / D 30 using a feeding device, ° C and extruded into a continuous phase so that the resin can be dispersed in a molten state, and then the extrudate is calendered and quenched in a calender roll at 130 ° C to obtain a color compensation film having a single layer structure having an average thickness of 300 μm Green organic phosphor content 350 ppm).

Example 2 ~ Example  4 and Comparative Example  1-2

Optical films were prepared in the same manner as in Example 1 except that the green phosphors of Preparation Example 1-1 were used instead of the green phosphors of Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 2, Using the green organic phosphor represented by Chemical Formulas 5 and 6, a color compensation film having a single layer structure having an average thickness of 300 占 퐉 was prepared.

Experimental Example  2: Measurement of physical properties of optical film

The PL intensity change, the luminance change rate, the light stability, the thermal decomposition analysis, the dispersibility (luminance uniformity), the mass productivity and the high temperature and high humidity stability of the films prepared in the above Examples and Comparative Examples were measured by the following methods, The results are shown in Table 2 below.

(One) PL  Experiment to measure the rate of change

The optical films of Production Examples and Comparative Production Examples were fixed on Blue LED BLU having a center wavelength of 450 nm and then the maximum PL peak intensity change amount after 0 hours and 120 hours was measured using CL-500A manufactured by KONICA MINOLTA Co., The results of PL intensity change measurement are shown in Fig.

 (2) Experiment to measure luminance change rate

The optical films of Production Examples and Comparative Production Examples were constituted by fixing a diffusion film and a prism reflective polarizing film on a blue LED BLU having a center wavelength of 450 nm and then fixing the entire screen area to 12 points by using an SR3 luminometer of Japan TOPCON Co., And the change rate of luminance of each point with time was measured.

At this time, the rate of change in luminance is the rate of change measured based on the luminance value at the initial measurement of 100%.

FIG. 6 shows the results of the measurement of the rate of change in luminance over time in Example 1, and FIG. 7 shows the results of measurement of the rate of change in luminance during 12 hours in Example 1, Comparative Example 1, and Comparative Example 2.

(3) Light stability  Measurement experiment

By measuring the color range that can be expressed by the liquid crystal display device with the TFT panel mounted on the BLU module, it is possible to measure the color coordinates and luminance of the red, green, and blue states, have. 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.

The color compensation films of Examples and Comparative Examples were mounted on a BLU module on which a TFT was mounted, and the color deviation (x, y) after driving at room temperature for 120 hours was measured to evaluate the degree of change of the color coordinates x and y. CA-310 of Konica Minolta, Japan was used.

(4) Thermal decomposition measurement experiment

The color compensating optical film was evaluated by measuring the temperature (T _d ) at which the weight loss was 5% while heating by using a thermogravimetric analysis (TGA).

(5) Measurement experiment of dispersibility (luminance uniformity)

The SR3 camera of TOPCON Co., Ltd. was used to measure the brightness of 9 points over the entire area of the backlight, and the difference between the maximum value and the minimum value was compared and evaluated.

(6) Mass production (workability) measurement experiment

The productivity was measured by integrating the handling from the preparation of the raw material to the final product and the complexity in the process yield process. The evaluation criteria were as follows: ⊚: very excellent, ◯: excellent, △: normal,

(7) High Temperature and Humidity Stability WHTS , Wet High Temperature Storage)

After assembling the BLU module in the same way as the optical stability measurement, the blue screen was driven for 500 hours in a chamber of relative humidity 60% and 75, and the uniformity of the whole screen and the stain phenomenon due to film deformation were qualitatively evaluated , Evaluation criteria were as follows:?: Very good,?: Good,?: Poor, and X: not used.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Organic phosphor (1-1) 1-2 1-3 Formula 1-4 Formula 5 6 PL maximum peak value 539 543 540 537 527 528 After 120 hours
PL maximum peak
Rate of change (%) 0.01% 0.3% 0.4% 0.04% 10% 8% Initial brightness (Nit) 225 226 228 227 226 228 After 12 hours, the luminance change rate 0.03% 0.2% 0.3% 0.05% 4% 3% Gwangan
Qualitative ΔX 0.0007 0.0008 0.0010 0.0004 0.0010 0.0019 Y 0.0003 0.0004 0.0007 0.0003 0.0052 0.0041 T _d 5 wt% 314 ° C 316 ° C 321 DEG C 311 ℃ 330 ℃ 312 ° C Dispersibility 92.5% 91.7% 92.4% 91.5% 89.8% 91.0% Mass production property ◎ ◎ ◎ ◎ ◎ ◎ WHTS ◎ ◎ ◎ ◎ △ △

As a result of the experiment of Table 2, it was confirmed that in the case of Embodiments 1 to 4, a low PL peak intensity change rate (see FIG. 5) and a brightness change rate (see FIG. 6). However, in the case of Comparative Example 1 and Comparative Example 2, the peak intensity change rate was large. Referring to FIG. 3, in Comparative Example 1 and Comparative Example 2, after 12 hours, the luminance was lowered, Respectively.

In Examples 1 to 3, it was confirmed that the range of color deviation (x, y) was 0.0020 or less for both the x-coordinate and the y-coordinate, and the light stability was excellent. On the other hand, in the case of Comparative Example 1 and Comparative Example 2, there was a problem that the y-coordinate is 0.0040 or more and color deviation is very large.

In addition, in Examples 1 to 4, the dispersibility, the mass productivity, and the high temperature and humidity stability were all excellent.

Manufacturing example  One : Color compensation Of extruded optical film  Produce

The green organic phosphor represented by Formula 1-1 prepared in Preparation Example 1-1 and the red organic phosphor represented by Formula 2-1 prepared in Preparation Example 2 were mixed with a polycarbonate (PC) resin having an MI of 10 The master batch was prepared by high concentration compounding. At this time, the masterbatch was prepared so that the green organic phosphor of Preparative Example 1-1 in the master batch had a concentration of 3,500 ppm and the concentration of the red organic phosphor of Preparation Example 2 was 280 ppm.

Next, the master batch and the PC resin (base resin) were fed into a 1: 9 weight ratio extruder of a twin screw extruder of 300 psi L / D 30 using a feeding device, And extruded into a continuous phase so that the resin can be dispersed in a molten state. The extrudate is then calendered and quenched on a 130 calender roll to obtain a color-compensated extruded optical film having a single layer structure with an average thickness of 300 占 퐉 Based organic phosphor of 350 ppm and red-based organic phosphor of 28 ppm).

Manufacturing example  2

The green-based organic phosphor represented by Formula 1-2 prepared in Preparative Example 1-2 was used instead of the green-based phosphor prepared in Preparative Example 1-1, except that the green- To prepare a color-compensated extruded optical film having a single-layer structure having an average thickness of 300 占 퐉.

Manufacturing example  3

A color-compensated extruded optical film was prepared in the same manner as in Example 1-1, except that the green-based organic phosphor represented by Formula 1-3 prepared in Preparation Example 1-3 was used instead of the green- To prepare a color-compensated extruded optical film having a single-layer structure having an average thickness of 300 占 퐉.

Manufacturing example  3

A color-compensated extruded optical film was prepared in the same manner as in Example 1-1, except that the green-based organic phosphor represented by Formula 1-4 prepared in Preparation Example 1-3 was used instead of the green- To prepare a color-compensated extruded optical film having a single-layer structure having an average thickness of 300 占 퐉.

Manufacturing example  4

A color-compensated extruded optical film was prepared in the same manner as in Example 1-1, except that the green-based organic phosphor represented by Formula 1-4 prepared in Preparation Example 1-4 was used instead of the green- To prepare a color-compensated extruded optical film having a single-layer structure having an average thickness of 300 占 퐉.

Manufacturing example  5

A color-compensated extruded optical film having a single-layer structure having an average thickness of 300 탆 was prepared using a polycarbonate resin having an MI of 30 instead of a polycarbonate resin having an MI of 10, in the same manner as in Example 1 .

Manufacturing example  6

The green organic phosphor represented by Formula 1-1 prepared in Preparation Example 1-1 and the red organic phosphor represented by Formula 2-1 prepared in Preparation Example 2 were mixed with polyethylene having an intrinsic viscosity (IV) of 0.8 dl / g Master batch was prepared by high concentration compounding in terephthalate (PET) resin. At this time, the masterbatch was prepared so that the green organic phosphor of preparation example 1 in the master batch had a concentration of 3,500 ppm and the concentration of the red organic phosphor of preparation example 2-1 was 280 ppm.

Next, the mixture was poured into a twin screw extruder of 300 psi L / D 30 and melted at 280.

The extruder can use both a single screw and a twin screw type, but a co-rotating twin screw method is used to uniformly disperse the added organic phosphor. / B / B in both skin layers, the melted polymer was located in the sub-extruder and the molten polymer of the main extruder in the core layer was located.

Next, the molten masterbatch is controlled to be fed in a feeding device at a weight ratio of 1: 9 with a base resin, and is extruded into a continuous phase. Thereafter, the extruded extrudate is quenched through a 110 casting roll, After the molded sheet is stretched 4 times in the MD direction by adjusting the restraint ratio of the rear end roll before the temperature of the molded sheet is lowered to Tg (glass transition temperature) or lower, the sheet is passed again through the 180 chamber in the tenter process, The temperature of the stretched film was heated again to stretch it four times in the TD direction so that the thickness of the final film became 300 占 퐉. The sheet was passed through a heat fixing zone of 150 to fix the sheet. The sheet was then heated to a glass transition temperature (Tg) And quenched to prepare a color-compensated extruded optical film (green-based organic phosphor of 350 ppm and red-based organic phosphor of 28 ppm) having a single-layer structure with an average thickness of 300 μm.

Comparative Manufacturing Example  One

The green-based organic fluorescent substance of Preparation Example 1-1, the red-based organic fluorescent substance of Preparation Example 2, the UV-curable urethane acrylic-based mixed binder and toluene (solvent) were mixed to prepare a coating solution. At this time, the contents of the green organic phosphor of Preparative Example 1-1 and the red organic phosphor of Preparation Example 2 in the coating liquid were adjusted to 350 ppm and 28 ppm, respectively.

Next, the coating solution was coated on a 100 탆 PET stretched film for optical use by a gravure coating method to form a coating film having a thickness of 100 탆 so that the organic phosphor coating film was 100 탆. Then, a 100 탆 PET film was placed on the coating film so that no bubbles were formed, And the binder was cured through a curing unit at a light quantity of 300 mJ / cm 2 to prepare a coating film.

The PET stretched film was obtained by longitudinally stretching four times in the MD direction, then transversely stretching four times in the TD direction, and then thermally fixing the stretched film to obtain a commercially available optical transparent film.

Comparative Manufacturing Example  2

A green-based organic phosphor represented by the formula (5) prepared in Comparative Preparation Example 1 was used instead of the green-based phosphor prepared in Preparation Example 1 to prepare a color-compensated extruded optical film in the same manner as in Example 1-1,占 퐉 of a color-compensation extruded optical film having a single-layer structure.

Comparative Manufacturing Example  3

A green color organic phosphor represented by the formula (6) prepared in Comparative Preparation Example 2 was used instead of the green color phosphor of Preparation Example 1 to prepare a color-compensated extruded optical film in the same manner as in Example 1-1,占 퐉 of a color-compensation extruded optical film having a single-layer structure.

Comparative Manufacturing Example  4

A CdSe quantum dot having a particle size of 2.8 nm having a main wavelength of 520 nm, a CdSe quantum dot having an average particle diameter of 5.6 nm having a main wavelength of 610 nm, a UV curing type urethane acrylic binder, and toluene (solvent) were mixed to prepare a coating solution. At this time, the content of each of the green organic phosphor of Preparation Example 1 and the red organic phosphor of Preparation Example 5-1 in the coating liquid was adjusted to 1,950 ppm and 180 ppm.

Next, the coating solution was coated on a 100 탆 PET stretched film for optical use by a gravure coating method to form a coating film having a thickness of 100 탆 so that the organic phosphor coating film was 100 탆. Then, a 100 탆 PET film was placed on the coating film so that no bubbles were formed, And the binder was cured through a curing unit at a light quantity of 300 mJ / cm 2 to prepare a coating film.

The PET stretched film was obtained by longitudinally stretching four times in the MD direction, then transversely stretching four times in the TD direction, and then thermally fixing the stretched film to obtain a commercially available optical transparent film.

Comparative Manufacturing Example  5

A green-based organic phosphor represented by the formula (7) prepared in Comparative Preparation Example 3 was used instead of the green-based phosphor prepared in Preparation Example 1 to prepare a color-compensated extruded optical film in the same manner as in Example 1-1,占 퐉 of a color-compensation extruded optical film having a single-layer structure.

division Green system
Organic phosphor Red
Organic phosphor Transparent resin Stretching
Degree film
How to form Of the final film
Overall average thickness Kinds content Kinds content Manufacturing example
One Preparation Example
1-1 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Manufacturing example
2 Preparation Example
1-2 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Manufacturing example
3 Preparation Example
1-3 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Manufacturing example
4 Preparation Example
1-4 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Manufacturing example
5 Preparation Example
1-1 350ppm Preparation Example
2 28ppm PC resin with MI = 30 Unleaded Extrusion 300 탆 Manufacturing example
6 Preparation Example
1-1 350ppm Preparation Example
2 28ppm PET resin with an intrinsic viscosity of 0.8 MD direction 4 times
4 times in TD Extrusion 300 탆 Comparative Manufacturing Example
One Preparation Example
1-1 350ppm Preparation Example
2 28ppm Urethane acrylic resin MD direction 4 times
4 times in TD coating 300 탆 Comparative Manufacturing Example
2 Example of comparison preparation
One 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Comparative Manufacturing Example
3 Example of comparison preparation
2 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆 Comparative Manufacturing Example
4 CdSe quantum dots with an average particle diameter of 2.8 nm CdSe quantum dots with an average particle diameter of 5.6 nm Urethane resin - coating 300 탆 Comparative Manufacturing Example
5 Example of comparison preparation
3 350ppm Preparation Example
2 28ppm PC resin with MI = 10 Unleaded Extrusion 300 탆

Experimental Example  2 : Color compensation  Measurement of physical properties of optical film

The color reproducibility, the luminance, the light stability, the thermal decomposition analysis, the dispersibility (luminance uniformity), the mass productivity and the high temperature and high humidity stability of the color compensation optical films prepared in the above Production Examples and Comparative Production Examples were measured by the following methods. The results are shown in Tables 3 to 5 below.

(One) Color Reproducibility  Measurement experiment

By measuring the color range that can be expressed by the liquid crystal display device with the TFT panel mounted on the BLU module, it is possible to measure the color coordinates and luminance of the red, green, and blue states, have. 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.

(2) Measurement of brightness (Nit)

The optical films of Examples and Comparative Examples were fixed by constituting and fixing a diffusion film and a prism reflective polarizing film on a Blue LED BLU having a center wavelength of 450 nm and then BLU was formed into a white color. Using SR3 luminometer of TOPCON Japan, Was divided into 12 points, and the luminance of each point was measured to obtain an average value.

(3) Light stability  Measurement experiment

The color variation (x, y) after the driving of the room temperature was measured before and after driving the color compensation optical film to the BLU module mounted with the TFT in the same manner as the color reproducibility evaluation, and the degree of change of the color coordinates x, y was evaluated , And CA-310 of KONICA MINOLTA, Japan were used.

(4) Thermal decomposition measurement experiment

The color compensating optical film was evaluated by measuring the temperature (T _d ) at which the weight loss was 5% while heating by using a thermogravimetric analysis (TGA).

(5) Measurement experiment of dispersibility (luminance uniformity)

The SR3 camera of TOPCON Co., Ltd. was used to measure the brightness of 9 points over the entire backlight, and the difference between the maximum value and the minimum value was compared and evaluated.

(6) Mass production (workability) measurement experiment

The productivity was measured by integrating the handling from the preparation of the raw material to the final product and the complexity in the process yield process. The evaluation criteria were as follows: ⊚: very excellent, ◯: excellent, △: normal,

(7) High Temperature and Humidity Stability WHTS , Wet High Temperature Storage)

After assembling the BLU module in the same way as the optical stability measurement, the blue screen was driven for 500 hours in a chamber of relative humidity 60% and 75, and the uniformity of the whole screen and the stain phenomenon due to film deformation were qualitatively evaluated , Evaluation criteria were as follows:?: Very good,?: Good,?: Poor, and X: not used.

division Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Color Reproducibility 109% 108.7% 108.1% 109.8% 108.3% 107.9% Brightness (Nit) 228 228 226 222 224 223 Gwangan
Qualitative ΔX 0.0003 0.0005 0.0009 0.0003 0.0005 0.0007 Y 0.0008 0.0009 0.0018 0.0005 0.0009 0.0010 T _d 5 wt% 330 ℃ 325 DEG C 330 ℃ 324 ° C 328 ° C 319 ° C Dispersibility 92.2% 91.5% 90.4% 92.4% 90.8% 90.1% Mass production property ◎ ◎ ◎ ◎  ◎ ○ WHTS ◎ ◎ ◎ ◎ ◎ ◎ ~ ○

division Comparative Preparation Example 1 Comparative Production Example 2 Comparative Production Example 3 Comparative Production Example 4 Comparative Preparation Example 5 Color Reproducibility 110% 101.8% 98.7% 108.9% 65.1% Brightness (Nit) 228 228 200 220 200 Gwangan
Qualitative ΔX 0.0017 0.0017 0.0021 0.0015 Not measurable Y 0.0073 0.0043 0.0051 0.0029 Not measurable T _d 5 wt% 323 DEG C 323 DEG C 294 ° C 1,485 ℃ 210 ℃ Dispersibility 91.5% 91.5% 90.2% 85.2% Not measurable Mass production property × ○ ○ △ × WHTS △ ○ ○ ○ Not measurable

The x-coordinate of the color deviation (x, y) ranges from 0.0012 to less than 0.0012 in the case of Production Examples 1 to 6 as well as high color reproducibility and high luminance characteristics of not less than 95% The y-coordinate was 0.0020 or less, confirming that the optical stability was excellent. In addition, in the case of the examples, the dispersibility, the mass productivity, and the high temperature and humidity stability all showed excellent results.

On the other hand, the optical film of Comparative Production Example 1 produced by the coating method has excellent mechanical and optical properties as a whole, but it has a problem that the productivity is inferior due to the manufacturing method.

In Comparative Production Example 2 and Comparative Production Example 3 produced using green organic phosphors different from those in the production example, the light stability tended to be inferior, It is judged that the phosphor is not suitable for the film production by the extrusion process because the heat resistance is low.

In Comparative Production Example 4 produced using existing quantum dots, the thermal decomposition temperature was high and the heat resistance was good, but the mass productivity was greatly reduced and the dispersibility was poor.

Further, in Comparative Production Example 5 prepared using the organic phosphor represented by Formula 7 above, the organic phosphor was decomposed during the extrusion process proceeding at a high temperature, and it was impossible to measure and disperse the color coordinates of the organic phosphor. Is very low in heat resistance.

It can be seen from the above Examples and Experiments that the color-compensated extruded optical film can be produced with excellent mass productivity through the extrusion process in spite of the fact that the organic fluorescent material is used, It was confirmed that the optical film had excellent optical properties and thermal properties. By using the color-compensated extruded optical film of the present invention, it is possible to provide an LED lighting, an LED display, an LCD, etc. excellent in color reproducibility It is expected.

Claims (22)

An organic phosphor including at least one selected from a green organic phosphor having a PL wavelength of 500 to 570 nm and a red organic phosphor having a PL wavelength of 580 to 680 nm in a monomolecular form; And a transparent resin,
The green-based organic fluorescent substance includes an organic fluorescent substance represented by the following formula (1):
[Chemical Formula 1]

In the formula 1, wherein R ¹ is a straight-chain alkyl group or branched alkyl group of C3 ~ C10 ~ C10 of the C3, A, B, C and D each independently represent a halogen atom or an -OR ^2, R ² is C3 ~ C10 straight-chain alkyl group, C3-C10 branched alkyl group, C5-C10 cycloalkyl group,

or

R ³ is a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and n is 0 to 3.
The color-compensated extrusion optical film according to claim 1, wherein the red-based organic fluorescent material comprises an organic fluorescent material represented by the following formula (2):
(2)

In Formula 2, R ¹ , R ^2, R ³ and R ⁴ are each independently selected from the olefin group of C1 ~ C5 alkyl group, C2 ~ C5 of, a cycloalkyl group of C5 ~ C6, a styrene group, a phenyl group, a phenol group or a benzyl group, R ⁵ is a phenyl group, ( alkoxy of C1 ~ C3) (a trialkyl) phenyl group or a phenol group of C1 ~ C3 of dialkyl) group, a phenyl group, a (C1 ~ C3 (dialkylamino of C1 ~ C3), R ⁶ and R ⁷ are each independently - Each of R ⁸ and R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

to be.
The compound according to claim 1, wherein R ¹ in the formula (1) is a linear alkyl group having 3 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, each of A, B, C and D is independently a halogen atom or -OR ² , R ² is

or

, R ³ is -CH ₃ , -CH ₂ CH ₃ , -C (CH ₃ ) ₃ or -CH (CH ₃ ) ₂ , and n is 0 to 3. The color- film.
The compound according to claim 2, wherein R ¹ , R ² , R ³ and R ⁴ are each a C1 to C3 alkyl group or a phenyl group, R ⁵ is a phenyl group, a 4-methoxy-2,6-dimethylphenyl group, a 4-methoxy- An ethoxy-2,6-dimethylphenyl group, a 4-ethoxy-2,6-diethylphenyl group, a 2,4,6-trimethylphenyl group or a 2,4,6-triethylphenyl group, R ⁶ and R ⁷ is -F or an alkyl group of C1 ~ C2, R ⁸ and R ⁹ is a hydrogen atom or

Wherein the color-compensated extruded optical film is excellent in light stability.
The color-compensated extrusion optical film according to claim 1, wherein each of the green-based organic fluorescent substance and the red-based organic fluorescent substance has a specific gravity of 1.0 to 2.0 g / cm 3 and a pyrolysis temperature of 250 ° C or more.
The organic electroluminescent device according to claim 1, wherein the green organic phosphor is 100 to 2,500 ppm,
Wherein the red-based organic phosphor is contained in an amount of 10 to 1,000 ppm.
The method of claim 1, wherein the transparent resin is selected from the group consisting of a polycarbonate resin, a polyethylene terephthalate resin, polymethyl methacrylate (PMMA), co-polymethyl methacrylate (co-PMMA) -butadiene-styrene resin, and PS (polystyrene) resin. The color-compensated extruded optical film is excellent in light stability.
The color-compensated extrusion optical film according to claim 1, wherein the color-compensated extrusion optical film has a single-layer structure of an organic fluorescent substance layer including a green organic fluorescent substance and a red organic fluorescent substance, or a multilayer structure in which a plurality of organic fluorescent substance layers of the single- Color-compensated extruded optical film with excellent light stability.
The color-compensated extrusion optical film as claimed in claim 1, wherein the color-compensated extrusion optical film is formed by alternately laminating a green organic fluorescent substance layer containing a green organic fluorescent substance and a red organic fluorescent substance layer including a red organic fluorescent substance, Layer is a multi-layer structure in which layers are randomly laminated.
The color-compensated extruded optical film according to claim 8 or 9, characterized in that a light diffusion pattern or a condensed light pattern is formed on the upper surface of the uppermost organic fluorescent layer of the color-compensated extruded optical film, Compensated extrusion optical film.
The color-compensated extrusion optical film according to claim 8 or 9, further comprising a skin layer on one side or both sides of the color-compensated extrusion optical film.
11. The color-compensated extrusion optical film according to claim 10, wherein an optical acid pattern or a light condensing pattern is formed on the surface of the skin layer.
10. The color difference measurement method according to any one of claims 1 to 9, wherein, when measuring a color deviation based on a National Television System Committee (NTSC) color coordinate system under a blue light source, the deviation range of the x-coordinate is 0.0001 to 0.0020, And the deviation range is 0.0002 to 0.0022.
The method of any one of claims 1 to 9, wherein a temperature (T _d ) at which a weight loss of 5% is lost is measured at a temperature at which a weight loss of 5% is lost using a thermogravimetric analyzer (TGA) Wherein the color-compensated extruded optical film has excellent light stability.
A first step of preparing a master batch by mixing a green organic phosphor having a PL wavelength of 500 to 570 nm in a single molecule form, a red organic phosphor having a PL wavelength of 580 to 680 nm in a monomolecular form, and a transparent resin;
A second step of putting the master batch in an extruder and then melting it;
3) extruding the molten master batch into a continuous phase; And
And four steps of calendaring and quenching the continuous extrudate to produce a film,
Wherein the green organic phosphor comprises an organic phosphor represented by Formula 1,
Wherein the red organic phosphor comprises an organic phosphor represented by the following formula (2): < EMI ID = 1.0 >
[Chemical Formula 1]

In the formula 1, wherein R ¹ is a straight-chain alkyl group or branched alkyl group of C3 ~ C10 ~ C10 of the C3, A, B, C and D each independently represent a halogen atom or an -OR ^2, R ² is C3 ~ C10 straight-chain alkyl group, C3-C10 branched alkyl group, C5-C10 cycloalkyl group,

or

R ³ is a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, n is 0 to 3,
(2)

In Formula 2, R ¹ , R ^2, R ³ and R ⁴ are each independently selected from the olefin group of C1 ~ C5 alkyl group, C2 ~ C5 of, a cycloalkyl group of C5 ~ C6, a styrene group, a phenyl group, a phenol group or a benzyl group, R ⁵ is a phenyl group, ( alkoxy of C1 ~ C3) (a trialkyl) phenyl group or a phenol group of C1 ~ C3 of dialkyl) group, a phenyl group, a (C1 ~ C3 (dialkylamino of C1 ~ C3), R ⁶ and R ⁷ are each independently - Each of R ⁸ and R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

to be.
A green masterbatch containing a green organic phosphor and a transparent resin having a PL wavelength of 500 to 570 nm in a single molecule form, a red base master batch containing a red organic phosphor having a PL wavelength of 580 to 680 nm in a monomolecular form and a transparent resin, Respectively;
The green system master batch and the red system master batch are put into an extruder and then melted;
Three steps of extruding or co-extruding the molten green masterbatch and the red base masterbatch into a continuous phase; And
And four steps of calendaring and quenching the continuous extrudate to produce a film,
Wherein the green organic phosphor comprises an organic phosphor represented by Formula 1,
Wherein the red organic phosphor comprises an organic phosphor represented by the following formula (2): < EMI ID = 1.0 >
[Chemical Formula 1]

In the formula 1, wherein R ¹ is a straight-chain alkyl group or branched alkyl group of C3 ~ C10 ~ C10 of the C3, A, B, C and D each independently represent a halogen atom or an -OR ^2, R ² is C3 ~ C10 straight-chain alkyl group, C3-C10 branched alkyl group, C5-C10 cycloalkyl group,

or

R ³ is a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, n is 0 to 3,
(2)

In Formula 2, R ¹ , R ^2, R ³ and R ⁴ are each independently selected from the olefin group of C1 ~ C5 alkyl group, C2 ~ C5 of, a cycloalkyl group of C5 ~ C6, a styrene group, a phenyl group, a phenol group or a benzyl group, R ⁵ is a phenyl group, ( alkoxy of C1 ~ C3) (a trialkyl) phenyl group or a phenol group of C1 ~ C3 of dialkyl) group, a phenyl group, a (C1 ~ C3 (dialkylamino of C1 ~ C3), R ⁶ and R ⁷ are each independently - Each of R ⁸ and R ⁹ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

to be.
The method according to claim 15 or 16, wherein the master batch for the skin layer is further prepared in step 1, the master batch for the skin layer is further introduced into the extruder in step 2, and co-extruded with the organic phosphor batch in step 3 Wherein the optical compensation film is formed on the surface of the substrate.
17. The method according to claim 15 or 16, wherein the melting in the second step is carried out at a temperature of 250 ° C to 320 ° C,
Wherein the calendering of the four steps is performed using a calender roll at a temperature of 100 ° C to 140 ° C.
The method of claim 15 or 16, wherein the step 4 further comprises a step of stretching the film after calendering and quenching and then thermally fixing the film.
A light emitting diode (LED) display comprising the color-compensated extruded optical film of claim 13.
14. A light emitting diode (LED) illumination device comprising the color-compensated extruded optical film of claim 13.
A liquid crystal display (LCD) comprising the color-compensated extrusion optical film of claim 13.

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