KR20170107278A

KR20170107278A - Color compensating integrated diffusing functions and extruding optical film and Preparing method thereof

Info

Publication number: KR20170107278A
Application number: KR1020160031035A
Authority: KR
Inventors: 양인영; 김효석; 배중석; 김지환
Original assignee: 도레이케미칼 주식회사
Priority date: 2016-03-15
Filing date: 2016-03-15
Publication date: 2017-09-25

Abstract

The present invention relates to a novel color-compensated extrusion optical film and a method for producing the same, and more specifically, it relates to a novel color-compensated extrusion optical film which can be produced by an extrusion process by introducing a specific organic phosphor and a specific resin, The present invention relates to a color-compensated extrusion optical film and a method of manufacturing the same, which are manufactured by a co-extrusion method and are integrated with a light diffusion surface layer and an organic phosphor layer without a separate adhesive layer.

Description

Technical Field [0001] The present invention relates to a color compensating optical film and a manufacturing method thereof,

The present invention relates to a color-compensated extrusion optical film in which a specific organic phosphor can be introduced and manufactured by an extrusion process, and a light diffusion function is integrated, and a method for manufacturing the same.

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 to the existing CdSe quantum dots or CdTe quantum dots. Indium sulfide (In ₂ S ₃ ) quantum dots are one of them.

Particularly, since indium sulfide (InS ₂ ) has a bulk band gap of 2.1 eV and InS ₂ quantum dot can emit light in a visible light region, it can be used for manufacturing a high-luminance light emitting diode device. However, since Group 13 and Group 16 are generally difficult to synthesize, it is not only difficult to mass-produce indium sulfide quantum dots, but also has a disadvantage in that the particle size uniformity is secured and the quantum yield (QY) is poorer than that of 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 in that the characteristic deterioration is large and practically impossible to use.

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 on the extrusion can be produced, and the present invention has been completed. 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.

According to an aspect of the present invention, there is provided a color-compensated color-compensation extruded optical film, comprising: an organic phosphor layer including a single-molecule organic phosphor having a PL (photoluminescence) wavelength of 500 nm to 680 nm and a transparent resin; And a light diffusion surface structure layer on one side or both sides of the organic phosphor layer, wherein the organic fluorescent layer and the light diffusion surface structure layer are integrated by coextrusion, and the organic phosphor layer as a core portion is a single layer or multi- Structure.

Further, the light diffusion function integrated color compensation extrusion optical film of the present invention has a single layer structure including an organic phosphor having a PL wavelength of 500 to 570 nm and an organic phosphor having a PL wavelength of 580 to 680 nm; Or a multilayer structure comprising a first organic phosphor layer containing an organic phosphor having a PL wavelength of 500 to 570 nm and a second organic phosphor layer containing an organic phosphor having a PL wavelength of 580 to 680 nm, 1 organic phosphor layer and / or the second organic phosphor layer) may have an optical acid surface structure formed on one surface or both surfaces thereof.

In a preferred embodiment of the present invention, the multi-layer structure may be formed by alternately laminating the first organic phosphor layer and the second organic phosphor layer, or in a laminated manner.

As a preferred embodiment of the present invention, a skin layer may be further formed under the organic phosphor layer.

In one preferred embodiment of the present invention, the light diffusing surface structure layer and / or the light diffusing surface structure has an arithmetic mean roughness (R _a ) of 0.1 탆 to 10 탆, a ten point average roughness (R _z ) May be 1 탆 to 50 탆.

In a preferred embodiment of the present invention, the light-diffusing surface structure layer and / or the optical acid surface structure are mat-shaped; And at least one lens shape selected from hemispheres, prisms, lenticules, and pyramids; Polygonal pattern; Embossing pattern; And shapes mixed therewith; And the like.

In one preferred embodiment of the present invention, the transparent resin of the organic phosphor layer and the transparent resin that constitutes the light-diffusing surface structure layer are each formed of a polycarbonate resin, a polyethylene terephthalate resin, (PMMA), co-polymethyl methacrylate (co-PMMA), ABS (acrylonitrile-butadiene-styrene) resin and PS (polystyrene) resin.

In a preferred embodiment of the present invention, the transparent resin of the organic phosphor layer and the transparent resin constituting the light-diffusing surface structure layer may be the same resin or different kinds of resins.

In one preferred embodiment of the present invention, the polycarbonate resin has a MI (melting index) of 1 to 40, a glass transition temperature (Tg) of 130 ° C to 160 ° C, and the polyethylene terephthalate resin has an intrinsic viscosity of 0.5 - Lt; RTI ID = 0.0 > dl / g. &Lt; / RTI >

In one preferred embodiment of the present invention, the monomolecular organic phosphor has a specific gravity of 1.0 to 2.0 g / cm 3 and a pyrolysis temperature of 300 ° C or higher.

As a preferred embodiment of the present invention, in the color-compensated extruded optical film of the present invention, the monomolecular organic fluorescent substance is an organic fluorescent substance having a PL wavelength of 500 to 570 nm and an organic fluorescent substance having a PL wavelength of 580 to 680 nm Or more species.

In one preferred embodiment of the present invention, the organic phosphor having a PL wavelength of 500 to 570 nm includes a perylene-based organic phosphor represented by the following Formula 1, a perylene-based organic phosphor represented by the following Formula 2, an anthracene- An organic phosphor and a tetracene-based organic phosphor represented by the following general formula (4).

[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)

R ² and R ⁴ are 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, C5 branched alkyl group, 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.

(3)

In Formula 3, R ¹ and R ² are each independently

,

,

,

or

, R ¹¹ to R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n and m are each independently an integer of 0 to 4, each of R ³ to R ¹⁰ independently represents a hydrogen atom, a C1 A C5 alkyl group, a C2-C5 olefin group, a halogen atom or -CN,

[Chemical Formula 4]

In Formula 4, R ¹ and R ² are each independently

,

,

,

or

Each of R ¹³ to R ¹⁴ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n and m are each independently an integer of 0 to 4, R ³ to R ¹² are each independently a hydrogen atom, C5 alkyl group, C2-C5 olefin group, halogen atom or -CN.

In one preferred embodiment of the present invention, the organic phosphor having a PL wavelength of 580 to 680 nm may be a perylene-based organic phosphor represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, R^OneAnd R⁴Each independently represent a hydrogen atom, 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, and R², R³, R⁵ And R⁶ Each independently represents a hydrogen atom, a C1-C5 alkoxy group, a C5-C10 cyclic alkoxy group,

,

or

, But R³And R⁶thisWhen it is a hydrogen atomR²And R⁵Is not a hydrogen atom, and the R⁷ And R⁸Are each independently a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R⁹ And R¹⁰Each independently represent a hydrogen atom, -SO₃H, -COOH, -CH₂COOH, -CH₂CH₂COOH, - CH₂CH₂CH₂COOH, -NR¹¹R¹², -CH₂NR¹¹R¹², Or -CH₂ CH₂NR¹¹R¹², And R¹¹ And R¹²Are each independently a hydrogen atom or a straight-chain alkyl group having from 1 to 3 carbon atoms.

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 >

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, R ¹ and R ² of the anthracene-based organic phosphor represented by Formula 3 are each independently

or

, And R ³ to R ¹⁰ are each independently a hydrogen atom, an alkyl group having ¹ to ³ carbon atoms or -CN.

In one preferred embodiment of the present invention, R ¹ and R ² of the tetracene-based organic phosphor represented by Formula 4 are each independently

or

And R ³ to R ¹² are each independently a hydrogen atom, an alkyl group having ¹ to ³ carbon atoms or -CN.

In one preferred embodiment of the present invention, R ¹ and R ⁴ of the perylene-based organic phosphor represented by Formula 5 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 color-compensated extruded optical film of the present invention may contain 0.005 to 2% by weight of the organic phosphor.

In another preferred embodiment of the present invention, the color-compensated extrusion optical film of the present invention comprises the organic phosphor having the PL wavelength of 500 to 570 nm and the organic phosphor having the PL wavelength of 580 to 680 nm in a weight ratio of 1: 0.02 to 0.8 .

In one preferred embodiment of the present invention, the organic phosphor layer of the color-compensated extrusion optical film of the present invention has an average thickness of 10 to 500 μm and an average thickness of the light diffusion surface layer is 10 to 200 μm.

As a preferred embodiment of the present invention, the color-compensated extruded optical film of the present invention may have a color reproduction rate of 98% or more, a luminance of 500 nit or more, and a luminance uniformity of 90% or more.

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 for producing the above-mentioned optical diffusion-function-integrated color-compensated extrusion optical film of various embodiments, which comprises mixing a monomolecular organic phosphor having a PL wavelength of 500 nm to 680 nm and a transparent resin, , And a resin for a skin layer, respectively; Two steps of putting the resin for the masterbatch and the skin layer into an extruder and then melting them; A third step of coextruding the molten master batch and the resin for the skin layer into a continuous phase to form a pneumatic depression formed with a skin layer on one side or both sides of the organic phosphor layer formed by the masterbatch; After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And quenching and quenching to form a film. The optical acid function-integrated color-compensated extruded optical film can be produced by a process comprising the steps of:

Another method of producing the light diffusing function integrated color-compensated extruded optical film of the present invention is a method comprising the steps of: preparing a first master batch in which a green organic phosphor having a PL wavelength of 500 to 570 nm and a transparent resin are mixed, a red organic phosphor having a PL wavelength of 580 to 680 nm A second master batch in which a transparent resin is mixed, and a resin for a skin layer; A first master batch, a second master batch, and a skin layer resin in an extruder and then melting the mixture; The molten first master batch, the second master batch and the resin for the skin layer are co-extruded in a continuous phase to form a skin layer on one or both sides of the outermost layer of the organic phosphor layer of the multilayer structure formed by the first master batch and the second master batch Forming a pneumatic depression formed; After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And a step of quenching and film-forming the optical color function-compensated extruded optical film having the multi-layer structure of the organic phosphor layer as the core portion.

Another method for producing a light-diffusing function integrated color-compensated extruded optical film of the present invention comprises the steps of: 1) preparing a master batch by mixing a single molecule type organic phosphor having a PL wavelength of 500 nm to 680 nm 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 calendering the continuous extrudate, and then one surface or both surfaces of the extrudate is subjected to a roughing treatment to form a surface structure, or a surface of the extrudate is structured at the same time as the calendering; And 5) a step of quenching and filming the color-compensated function-integrated color-compensated extruded optical film.

Another method of producing the optical diffusing function-integrated color-compensated extruding optical film of the present invention is a method comprising the steps of: preparing a first master batch in which a green organic phosphor having a PL wavelength of 500 to 570 nm is mixed with a transparent resin, a first master batch in which a PL wavelength is in a range of 580 to 680 nm, A first master batch in which a phosphor and a transparent resin are mixed, and a resin for a skin layer; A first master batch and a second master batch are charged into an extruder and then melted; Co-extruding the molten first master batch and the second master batch in a continuous phase to form a pneumatic effluent of a multi-layer structure; A step of calendering a pneumatic depression of a continuous phase and then roughing or surface-structuring one surface or both surfaces of the extrudate or surface-structuring the surface of the extrudate simultaneously with the calendering; And quenching and quenching to form a film. The optical acid function-integrated color-compensated extruded optical film can be produced by a process comprising the steps of:

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 can be performed using a calender roll at a temperature of 100 ° C to 140 ° C.

In one preferred embodiment of the present invention, the roughing treatment may be carried out by a sand blasting method or an imprinting method.

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 generally uses a specific organic phosphor excellent in thermal stability, an optical film can be produced through an extrusion process, though an organic phosphor having a poor thermal stability is used. Since the organic fluorescent material having a low specific gravity is used, the dispersibility in the resin is excellent and the optical uniformity and optical stability of the optical film are excellent. In addition, the optical film It is possible to manufacture. Further, after the co-extrusion, the light diffusion surface structure layer can be formed through the continuous roughness treatment process, so that the light diffusion function can be integrated to provide a laminated color-compensated extrusion optical film without a separate adhesive layer . 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.

1A to 1C are schematic views of a light-diffusing function integrated color-compensated extrusion optical film in which the organic phosphor layer is a single-layer structure, according to an embodiment of the present invention.
Each of Figs. 2A to 2C is a schematic view of a color-compensated extrusion optical film in which the organic phosphor layer has a multilayer structure, according to an embodiment of the present invention.
3 is an NTSC color coordinate graph.

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.

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.

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, by introducing a specific organic phosphor 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 phosphor layer comprising a single-molecule type organic phosphor having a PL (photoluminescence) wavelength of 500 nm to 680 nm and a transparent resin; And a light diffusion surface structure layer on one side or both sides of the organic phosphor layer.

The color-compensated extrusion optical film of the present invention has a light-diffusing surface structure layer 3 on one side of the organic phosphor layer 1 or a light-diffusing surface layer 3 on the organic phosphor layer 1 The light diffusion surface structure layer 3 may be formed on one surface of the substrate 2 and the skin layer 2 may be formed on the other surface.

1C and Fig. 2C, the light diffusion surface structure may be formed directly on the organic phosphor layer 1. Fig.

The color-compensated extrusion optical film of the present invention may be a multilayer structure in which two or more organic phosphor layers are stacked as shown schematically in Figs. 2A to 2C. In the case of a multilayer structure, an adhesive layer may not be formed between the laminated film and the film as produced by coextrusion.

Each of the organic phosphor layers includes organic phosphors having different wavelength ranges, and organic phosphor layers including organic phosphors having different wavelengths may be alternately stacked. In more detail, , A first organic phosphor layer including an organic phosphor having a PL wavelength of 500 to 570 nm and a second organic phosphor layer containing an organic phosphor having a PL wavelength of 580 to 680 nm are sequentially stacked, And the first organic phosphor layer may be sequentially stacked.

Or each of the organic phosphor layers including organic phosphors having different wavelengths may be randomly stacked.

In the present invention, the light-diffusing surface structure layer (3) and / or light-diffusing surface structure is formed directly on an organic phosphor layer is the arithmetic average roughness (R _a) 0.1㎛ ~ 10㎛, preferably 0.3 ~ 5㎛ , and can have the more preferably 0.3 ~ 3㎛, ten-point average roughness (R _z, ten point average roughness) is 1㎛ ~ 50㎛, preferably 2㎛ ~ is ~ 15 to 2㎛ 25㎛, more preferably Lt; / RTI >

The surface shape formed on the light diffusing surface structure layer 3 may have a shape for diffusing light generally used in the art, and preferably a mat shape; And at least one lens shape selected from hemispheres, prisms, lenticules, and pyramids; And the like.

Since the color-compensated extruded optical film of the present invention is manufactured in an integrated form through co-extrusion, the organic phosphor layer is formed between the organic phosphor layer and the organic phosphor layer, between the organic phosphor layer and the light diffusion surface structure layer, The adhesive layer may not be formed between the layers.

The organic phosphor layer of the color-compensated extrusion optical film of the present invention may have an average thickness of 10 to 500 占 퐉, preferably 50 to 500 占 퐉, more preferably 50 to 250 占 퐉 based on a single layer. Each of the light diffusion surface structure layer and / or the skin layer is preferably 10 to 200 占 퐉, and preferably 20 to 150 占 퐉.

In the color-compensated extruded optical film of the present invention, the transparent resin constituting the organic fluorescent substance layer, the light-diffusing surface structure layer and / or the skin layer may be the same or different resins, It is advantageous in terms of interlayer bonding strength.

For example, the transparent resin may be selected from the group consisting of polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polymethyl methacrylate At least one selected from among methacrylate (PMMA), co-polymethyl methacrylate (co-PMMA), acrylonitrile-butadiene-styrene (ABS) resin and PS (polystyrene) A resin, a polyethylene terephthalate resin, and a polymethyl methacrylate resin.

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 phosphor will be specifically described.

The organic phosphor constituting the organic phosphor layer of the color-compensated extrusion optical film of the present invention uses an organic phosphor in the form of a single molecule having a PL (photoluminescence) wavelength of 500 nm to 680 nm, preferably a green phosphor having a PL wavelength of 500 to 570 nm Based organic phosphors and red organic phosphors having a PL wavelength of 580 to 680 nm may be mixed and used.

The content of the organic fluorescent substance in the color-compensated extrusion optical film is preferably 0.005 to 2% by weight, preferably 0.005 to 1.8% by weight, more preferably 0.05 to 1.6% by weight, If the content of the phosphor is less than 0.005% by weight, the amount of the phosphor is too small to achieve a sufficient color compensation effect, and it is uneconomical to use the phosphor in an amount exceeding 2% by weight.

When the organic phosphors having different wavelength ranges are mixed and used, the green organic phosphor and the red organic phosphor are mixed at a weight ratio of 1: 0.02 to 0.8, preferably 1: 0.05 to 0.45, more preferably 1: 0.05 to 0.35 weight ratio. At this time, when the weight ratio of the red organic phosphor is less than 0.02 weight ratio or more than 0.8 weight ratio, the white light for the blue light source outside the x coordinate range of 0.20 to 0.50 and the y coordinate range of 0.15 to 0.40 on the NTSC color coordinate of FIG. It 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 300 ° C or higher, preferably 320 ° C or higher, wherein the specific gravity of the organic phosphor is 1.0 g / cm < 3 > or a specific gravity of more than 2.0 g / cm < 3 >, the dispersibility in the transparent resin deteriorates and the workability is deteriorated and the organic phosphor in the organic phosphor layer is not uniformly dispersed.

If the pyrolysis temperature of the organic phosphor is less than 300 ° 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.

The green organic phosphor having a PL wavelength of 500 to 570 nm as the organic phosphor satisfying these characteristics may be a perylene-based organic phosphor represented by the following Formula 1, a perylene-based organic phosphor represented by the following Formula 2, Anthracene organic phosphor and tetracene organic phosphor represented by the following formula (4) may be used in combination.

[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)

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.

(3)

Each of R < ¹ > and R < ² > in the above formula (3)

,

,

,

or

, And preferably

or

to be. Each of R ¹¹ and R ¹² is independently a hydrogen atom or a C1 to C3 alkyl group, preferably a hydrogen atom. Each of n and m is independently an integer of 0 to 4, preferably an integer of 0 to 2.

Each of R ³ to R ¹⁰ in the formula (3) is independently a hydrogen atom, a C 1 to C 5 alkyl group, a C 2 to C 5 olefin group, a halogen atom or -CN, preferably a hydrogen atom, A halogen atom, and more preferably a hydrogen atom.

[Chemical Formula 4]

Each of R < ¹ > and R < ² &

,

,

,

or

, And preferably

or

to be. And, each of the R ¹³ and R ¹⁴ are independently a hydrogen atom or an alkyl group C1 ~ C3, preferably a hydrogen atom. Each of n and m is independently an integer of 0 to 4, preferably an integer of 0 to 2.

Each of R ³ to R ^{12 in the general} formula (4) is independently a hydrogen atom, a C 1 to C 5 alkyl group, a C 2 to C 5 olefin group, a halogen atom or -CN, preferably a hydrogen atom, Atom, more preferably a hydrogen atom.

As the organic fluorescent substance satisfying the above characteristics, the organic fluorescent substance having a PL wavelength of 580 to 680 nm may be a perylene organic fluorescent substance represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, 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 cycloalkyl group of C 5 to C 6,

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

, And more preferably

to be.

Each of R ² , R ³ , R ⁵ and R ^{6 in the general} formula (5) independently represents 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 (5) 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.

The color-compensating optical film of the present invention may further include beads in addition to the organic phosphor and the transparent resin in a monomolecular form having a PL wavelength of 500 nm to 680 nm as described above; 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 (6) and a random copolymer represented by the following formula (7).

[Chemical Formula 6]

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.

Preferably, R ¹ in the general formula (6) 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.

(7)

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 the formula (7) 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 of manufacturing the optical diffusion function integrated color compensation extruded optical film of the present invention described above will be described.

First, the color-compensated extruded optical film of the present invention has a PL wavelength of 500 nm to 680 nm (hereinafter, referred to as " A step of preparing a master batch and a resin for a skin layer by mixing an organic phosphor in the form of phosphorus monomers and a transparent resin; Two steps of putting the resin for the masterbatch and the skin layer into an extruder and then melting them; A third step of coextruding the molten master batch and the resin for the skin layer into a continuous phase to form a pneumatic depression formed with a skin layer on one side or both sides of the organic phosphor layer formed by the masterbatch; After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And a step of quenching and film-forming.

A method of producing a color-compensated extruded optical film (hereinafter referred to as Production Method 2) for a case where the organic phosphor layer has a multilayer structure will be described. A green organic phosphor having a PL wavelength of 500 to 570 nm and a transparent resin are mixed A first master batch, a second master batch in which a red organic phosphor having a PL wavelength of 580 to 680 nm and a transparent resin are mixed, and a resin for a skin layer; A first master batch, a second master batch, and a skin layer resin in an extruder and then melting the mixture; The molten first master batch, the second master batch and the resin for the skin layer are co-extruded in a continuous phase to form a skin layer on one or both sides of the outermost layer of the organic phosphor layer of the multilayer structure formed by the first master batch and the second master batch Forming a pneumatic depression formed; After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And a step of quenching and film-forming.

A method of producing a color-compensated extruded optical film (hereinafter referred to as Production Method 3) which is surface-structured in the organic phosphor layer itself will be described. An organic phosphor in the form of a single molecule having a PL wavelength of 500 nm to 680 nm and a transparent resin A first step of mixing to prepare a master batch; 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 calendering the continuous extrudate, and then one surface or both surfaces of the extrudate is subjected to a roughing treatment to form a surface structure, or a surface of the extrudate is structured at the same time as the calendering; And a step of quenching and film-forming.

A description will now be given of a method for producing a color-compensated extruded optical film surface-structured on the organic phosphor layer itself (hereinafter, referred to as Production Method 4). A method of producing a color-compensated extruded optical film having a PL wavelength of 500 to 570 nm, A first master batch, a second master batch in which a red organic phosphor having a PL wavelength of 580 to 680 nm and a transparent resin are mixed, and a resin for a skin layer; A first master batch and a second master batch are charged into an extruder and then melted; Co-extruding the molten first master batch and the second master batch in a continuous phase to form a pneumatic effluent of a multi-layer structure; A step of calendering a pneumatic depression of a continuous phase and then roughing or surface-structuring one surface or both surfaces of the extrudate or surface-structuring the surface of the extrudate simultaneously with the calendering; And 5 steps of quenching and filming; And the like.

The kind of the organic phosphor used in the production of each of the master batch, the first master batch and the second master batch in the first step of each of the above-mentioned Production Process 1 to Production Process 4, the content thereof, 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 master batch which is a highly concentrated compounding.

In addition, additives such as a dispersant and an antioxidant may be further added to the master batch, the first master batch and / or the second master batch, respectively. When the additive is added, Preferably from 1 to 20 parts by weight, based on 100 parts by weight of the total weight of the organic phosphor, and more than 60 parts by weight of the organic phosphor may deteriorate the dispersibility of the organic phosphor.

In the above Production Method 3 and Production Method 4, in Step 1, the resin for the skin layer is prepared in addition to the masterbatch, and then the pneumatic pressure After preparing the sapphire, the surface of the organic phosphor layer may be subjected to surface treatment by irradiating the surface of the organic phosphor layer in step 4.

Production process 1 to process steps 4 to 2 are steps of melting the master batch, the first master batch and / or the second master batch to extrude them, respectively, and the master batch and the transparent resin are put into the main extruder or the sub-extruder together. At this time, a general extruder may be used or an optical film having a multilayer structure may be manufactured by using a co-extruder according to the structure of the optical film to be produced. The melting is preferably carried out at a temperature of from 250 to 320, preferably from 260 to 300. If the melting temperature is less than 250, unmelted polymer tends to be generated, If the molecular weight exceeds 320, the polymer may be thermally deformed and may be deteriorated or carbonized, and the functionalities may be lost due to deformation and decomposition of the additive. Therefore, It is better to melt the batch.

In Processes 1 to 2, Step 3 is a process for forming a pneumatic depression having a skin layer formed on one side or both sides of the organic phosphor layer formed by masterbatches. In this case, depending on the structure of the film to be produced, A master batch and a transparent resin are fed into the main extruder, and the master extruder is fed into the sub-extruder. The main extruder and the sub- After the resin for the skin layer is charged, it is melted and coextruded to form a skin layer on one side or both sides of the core.

The calendering of the four steps of the three steps of Manufacturing 1 and Manufacturing 2, Manufacturing 3, and Manufacturing 4 may be calendering by a general method used in the art, and a preferred example is calendering at a temperature of 100 ° C to 140 ° C The render can be used to perform calendering while quenching the continuous extrudate.

The third step of Manufacturing 1 and Manufacturing Step 2 and / or Step 4 of Manufacturing Step 3 further includes a step of stretching the calendared pneumatic spool to ensure reliability when the transparent resin used for the masterbatch is a PET resin The stretching method may be a general method used in the art. As a preferable example, the calendered pneumatic depressions may be stretched in the MD and / or TD directions by 2 to 6 times, preferably by 3 times To 5 times is advantageous in terms of securing the reliability of the color-compensated extrusion optical film.

When a PET resin is used as the transparent resin, it is preferable to conduct the roughing treatment after performing the kel rendering and stretching process.

For example, a sandblasting process or an imprinting process is preferably used for the roughing process of the manufacturing process 1 to the manufacturing process 4, preferably a roll-to-roll printing process, A surface structure may be formed on one surface or both surfaces of the layer to convert the skin layer into a light diffusion surface structure layer or to form a surface structure directly on the surface of the organic phosphor layer.

The shape of the surface structure is not particularly limited, and may be, for example, a mat shape; And at least one lens shape selected from hemispheres, prisms, lenticules, and pyramids; Polygonal pattern; Embossing pattern; And a mixed form thereof can be formed.

Then, the production method 1 and production method 2 of the light-diffusing surface structure layer, a production method and production method 3 of the light-diffusing surface structure 4, and the arithmetic average roughness (R _a) 0.1㎛ ~ 10㎛ as described above, preferably 0.3 to 5㎛, more preferably may be formed to have a 0.3 to ~ 3㎛, also, ten-point average roughness (R _z, ten point average roughness) is 1㎛ ~ 50㎛, preferably 2㎛ ~ 25㎛, more preferably , It is preferable that the thickness is 2 mu m to 15 mu m in terms of luminance increase and luminance uniformity.

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.

In addition, the light diffusing function integrated color-compensated extruded optical film of the present invention may have a luminance of 480 nit or more, preferably 500 nit or more, more preferably 510 to 550 nit.

The light-diffusing function-integrated color-compensated extruded optical film of the present invention has a color reproduction rate of 98% or more, preferably 99% to 105%, more preferably 100 to 104%, and can have extremely high color reproducibility.

In addition, the optical diffusing function integrated color-compensated extruded optical film of the present invention has a temperature (T _d ) at which a weight loss of 5% is lost when measuring a temperature at which a weight loss of 5% is lost using a thermogravimetric analyzer (TGA) And can have excellent thermal stability.

The color-compensated extrusion optical film of the present invention may have a brightness uniformity of 90% or more, preferably 91% or more, and the color-compensated extrusion optical film of the present invention is excellent in high-temperature and high-humidity stability.

The above-described light diffusing function integrated color compensation extruded optical film of the present invention can be widely used by being applied to a light emitting diode (LED) display, a light emitting diode (LED) illumination device and / or a liquid crystal display (LCD) (BLUs) of an edge type display or a direct-type display to improve the color reproducibility and luminance of a part in R (red), G (Green).

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 at 65 ° C for 3 hours and reacted Respectively.

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 2: Preparation of Green Organic Phosphor represented by Formula (2-1)

(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 DEG C for 12 hours, then cooled to 24 to 25 DEG 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 ° C 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 (ppm) = 9.58 (d, 2H, perylene-H), 9.03 (s, 2H, perylene-H), 8.82 (d, 2H, perylene-H), 4H, isopropyl-H), 1.20-1.18 (m, 24H, isopropyl-H), 7.38 (d,

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 ml of an 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 the mixture was stirred and refluxed for a minute. 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).

[Formula 2-1]

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.

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

Preparation Example 3-1: Preparation of Green Organic Phosphor Represented by Formula 3-1

5 g (14.9 mmol) of 9,10-dibromoanthrancane and 7.05 g (35.7 mmol) of di-p-tolyl-amine were added to a three-necked flask. ₂ (dba) ₃ , t-BuONa compound, 50 ml of toluene was added, and the mixture was stirred to obtain a homogeneous mixture.

Next, a solution of 5 mol% of P (t-Bu) ₃ in 2.6 ml of toluene was added to the mixed solution, and the mixture was reacted at 130 ° C. After 12 hours, the solution was dissolved at 25 占 폚 to obtain a compound represented by the following formula (3-1).

[Formula 3-1]

In Formula 3-1, R ¹ and R ² are

And R ³ to R ¹⁰ are hydrogen atoms.

¹ H NMR (500 MHz, CDCl ₃ ) :? (Ppm) = 2.24 (s, 12 H), 6.98-6.99 (d, J = 1.2 Hz, 16 H), 7.30-7.44 8.19 (m, 4 H),

¹³ C NMR (125 MHz, CDCl ₃ ): 20.6, 120.1, 121.1, 126.6, 129.8, 130.3, 131.9, 137.5, 145.6;

EI MS (m / e): 568 (M < + >).

Preparation Example 3-2: Preparation of Green Organic Phosphor represented by Formula 3-2

3 mmol of CuI, 1 mmol of 18-crown-6, 120 mmol of K ₂ CO ₃ and 2 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidine (DMPU1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone), 30 mmol of dibromoanthracene and 60 mmol of carbazole in a nitrogen gas 0.0 > 170 C < / RTI > for 11 hours. After cooling it at about 25 ℃ and then, dropwise addition of 1N HCl, and washed and then the precipitate was filtered off NH ₃ H ₂ O and water. This was recrystallized twice from chloroform to obtain 19.3 g of a compound represented by the following formula (3-2). At this time, the compound was obtained as a colorless crystal in a yield of 79%.

[Formula 3-2]

In Formula 3-2, R ₁ and R ₂ are

And R ³ to R ¹⁰ are hydrogen atoms.

^{_{1 H NMR (400MHz / CDCl 3}} ): δ (ppm) = 8.55 (2H, dd), 8.19 (2H, dd), 8.14 (4H, m), 7.94 (2H, dd), 7.58 (2H, dd), 7.50 (4H, m), 7.35 (2H, m), 7.20 (2H, m), 7.16

¹³ C NMR (100 MHz, CDCl ₃ ): 139.7, 134.9, 128.1, 122.7, 126.6, 125.6, 122.7, 121.4, 119.8, 109.5

Preparation Example 4: Preparation of Green Organic Phosphor represented by Formula 4-1

3 mmol of CuI, 1 mmol of 18-crown-6, 120 mmol of K ₂ CO ₃ and 2 mL of 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidine A mixture of 30 mmol of dibromo tetracene and 60 mmol of carbazole was dissolved in a mixture of nitrogen (NMP), dimethylformamide (DMPU) 1,3-dimethyl-3,4,5,6-tetrahydro- 0.0 > 170 C < / RTI > for 11 hours. After cooling it at about 25 ℃ and then, dropwise addition of 1N HCl, and washed and then the precipitate was filtered off NH ₃ H ₂ O and water. This was recrystallized twice from chloroform to obtain a compound represented by the following formula 4-1. At this time, the compound was obtained as colorless crystals in a yield of 79%.

[Formula 4-1]

In the formula (4-1), R ¹ and R ² are

And R ³ to R ¹² are hydrogen atoms.

^{_{1 H NMR (CD 3 OD,}} 400MHz): δ (ppm) = 8.57 (2H, dd), 8.23 (2H, dd), 8.16 (4H, m), 8.01 (2H, dd), 7.97 (2H, dd) , 7.58 (2H, dd), 7.50 (4H, m), 7.35 (2H, m), 7.22

¹³ C NMR (125 MHz, CDCl ₃ ): 139.7, 134.9, 128.1, 122.7, 126.6, 125.6, 122.7, 121.4, 119.8, 109.5

Preparation Example 5-1: Preparation of red-based organic phosphor represented by Formula 5-1

(1) Synthesis of Compound Represented by Formula 5-1a

, 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 5-1a.

^{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

[Formula 5-1a]

(2) Synthesis of Compound Represented by Formula 5-1b

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 solid obtained by the filtration 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 measurement that the compound was represented by the following formula 5-1b.

^{1 H-NMR spectrum (250 MHz} , C 2 D 2 Cl 4): δ (ppm) = 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 5-1b]

(3) Synthesis of Compound Represented by Formula 5-1

N-methyl-2-pyrrolidone (NMP) was added to the flask, and then 1.0 g of the compound of Formula 5-1b (1.199 mmol) and 828 mg of K ₂ CO ₃ (5.995 mmol) did.

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 5-1.

[Formula 5-1]

In Formula 5-1, 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.

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

Preparation Example 5-2: Preparation of the red organic dots represented by the formula 5-2

(4-hydroxyphenyl) ethanol (11.99 mmol), 795 mg of K ₂ CO ₃ (5.755 mmol), 1.0 g of the compound of the formula 5-1b (1.199 mmol) 1.65 g was added, and the mixture was vacuum-poured. Then, nitrogen was added thereto, and NMP (n-methyl-2-pyrrolidone) was added thereto and stirred. The mixture was heated to 90 DEG C and stirred at this temperature for 12 hours to complete the reaction. Water, methanol and HCl were added to the three-necked flask and stirred for 2 hours. After stirring, the precipitate was filtered. The dried reaction product was then subjected to column chromatography to obtain a compound represented by the following formula (5-2).

[Formula 5-2]

In Formula 5-2, 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

And R ⁹ is -CH ₂ CH ₂ OH.

^{_{1 H NMR (CD 3 Cl,}} 400MHz): 8H), 2.74 (t, 8H), 2.74 (t, 8H), 2.65 (d, (m, 4H), 1.09 (d, 24H)

Preparation Example 5-3: Preparation of red organic dots represented by Formula 5-3

3-hydroxypyridine (9.592 mmol) (912 mg) was charged in a three-necked flask, and 1.0 g of the compound represented by the formula 5-1b (1.199 mmol), 828 mg of K ₂ CO ₃ NMP was added and stirred.

Next, the temperature was heated to 100 DEG C, and then the reaction was completed by stirring at this temperature for 15 hours.

Next, after cooling to 25 ° C, hydrochloric acid was added, and the solid was filtered, and the filtered solid was washed with water. The washed solid was vacuum dried, and the dried reaction product was subjected to column chromatography to obtain a compound represented by the following Formula 5-3.

[Formula 5-3]

In Formula 5-3, 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

And R < ¹⁰ > is a hydrogen atom.

¹ H NMR (C ₂ D ₂ Cl ₄ , 400 MHz) : 2H), 7.286 (m, 4H), 7.179 (d, 4H), 7.182 (d, 4H), 2.577 (d, (m, 4H), 1.037 (d, 24H)

Comparative Preparation Example 1: Preparation of Green Organic Phosphor represented by Formula 8

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 (2-1).

^{_{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 8]

Wherein R ² , R ⁴ , R ⁷ and R ¹⁰ are hydrogen atoms, and R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹¹ are methyl groups.

EXPERIMENTAL EXAMPLE 1 Experiment of UV Absorption Wavelength and PL Wavelength of Organic Phosphor

(1) UV absorption wavelength measurement

0.01 g of each of the organic phosphors of Preparation Example 1 to Preparation Example 5-3 and Comparative Preparation Example 1 was dissolved in 3 ml of toluene and placed in a test tube to measure the emission spectra 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 Preparative Examples 1 to 5 and Comparative Preparative Example 1 was subjected to PL measurement using DarsaPro5200OEM PL (PSI Trading Co.) and 500 W ARC Xenon Lamp, Respectively.

division UV absorption wavelength
(nm) PL wavelength measurement
(nm) Preparation Example 1 475 530 Preparation Example 2 510 555 Preparation Example 3-1 474 535 Preparation Example 3-2 472 530 Preparation Example 4 490 545 Preparation Example 5-1 574 610 Preparation Example 5-2 576 615 Preparation Example 5-3 565 608 Comparative Preparation Example 1 501 523

Example 1: Fabrication of a light diffusion function integrated color compensation extruded optical film

The green organic phosphor represented by Formula 1-1 prepared in Preparation Example 1 and the red organic phosphor represented by Formula 5-1 prepared in Preparation Example 5-1 were mixed with a polycarbonate (PC) resin having an MI of 10 The master batch was prepared by high concentration compounding.

Separately, a polycarbonate (PC) resin having an MI of 10 was prepared as a resin for a skin layer.

Next, a master batch and a PC resin (base resin, MI = 10) were fed into a main extruder at a weight ratio of 1: 9 using a feeding device to an extruder composed of a twin extruder of 300 psi L / D 30 , And the resin for the skin layer was put into the first sub-extruder and the second sub-extruder, respectively, and melted at 280 ° C.

In the extruder, a co-rotating twin screw method was used to uniformly disperse the organic phosphor, and the structure of the layer was B / A / B type and the both skin layers were melted (Resin for the skin layer) was placed and the molten polymer constituting the core layer was positioned in the main extruder.

Next, the molten masterbatch was extruded into a continuous phase by controlling with a feeding device, and the extruded extrudate was calendered at a calender roll (upper part) matted at 130 DEG C to form an average thickness of 100 mu m (A green organic phosphor content of 10% by weight and a red organic phosphor content of 1% by weight), a surface structured layer having an average thickness of 50 [micro] m on the organic phosphor layer, and a skin layer having an average thickness of 50 [ Layered light-diffusing function integrated color-compensated extrusion optical film having a three-layer structure

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 1.21 탆 and R _z was 6.13 탆 (see Table 3).

Example 2

A color-compensated color-compensated extruded optical film was produced in the same manner as in Example 1, except that a calender roll patterned in hemispherical shape was used.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 1.50 탆 and R _z was 7.32 탆.

Example 3

An optical diffusing function integrated color-compensated extruded optical film was produced in the same manner as in Example 1 except that a pattern roll patterned in a lenticular shape was used.

At this time, the surface roughness of the surface structure of the extruded optical film layer R _a is 1.62㎛, R _z was 8.54㎛.

Example 4

A color-compensated color-compensated extrusion optical film was produced in the same manner as in Example 1 except that a calender roll patterned in a prism shape was used.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 1.91 탆 and R _z was 9.23 탆.

Example 5

A color-compensated color-compensated extruded optical film was produced in the same manner as in Example 1, except that a calender roll patterned in a pyramid shape was used.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 1.60 탆, and the R _z was 8.32 탆.

Examples 6 to 11 and Comparative Example 1

A three-layered light diffusing function integrated color-compensated extruded optical film was prepared in the same manner as in Example 1 except that the green organic phosphor and the red organic phosphor were different as shown in Table 2 below.

division Green organic phosphor Red organic phosphor Example 1 Preparation Example 1 Preparation Example 5-1 Example 2 Preparation Example 1 Preparation Example 5-1 Example 3 Preparation Example 1 Preparation Example 5-1 Example 4 Preparation Example 1 Preparation Example 5-1 Example 5 Preparation Example 1 Preparation Example 5-1 Example 6 Preparation Example 1 Preparation Example 5-2 Example 7 Preparation Example 1 Preparation Example 5-3 Example 8 Preparation Example 2 Preparation Example 5-1 Example 9 Preparation Example 3-1 Preparation Example 5-1 Example 10 Preparation Example 3-2 Preparation Example 5-1 Example 11 Preparation Example 4 Preparation Example 5-1 Comparative Example 1 Comparative Preparation Example 1 Preparation Example 5-1

Comparative Example 2

The same procedure as in Example 1 was carried out to prepare a color diffusion function integrated color compensation extruded optical film having a green organic phosphor content of 29.5 wt% and a red organic phosphor content of 0.5 wt% in the organic phosphor layer.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 0.03 탆 and R _z was 0.16 탆.

Comparative Example 3

A color-compensating color-compensated extrusion optical film was prepared in the same manner as in Example 2 except that the green-based organic phosphor and the red-based organic fluorescent material were contained in an amount of 29.5 wt% and 0.5 wt%, respectively.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film was 0.02 탆 and R _z was 0.12 탆.

Comparative Example 4

A color-compensating color-compensated extruded optical film was prepared in the same manner as in Example 2 except that the organic phosphor layer had a green organic phosphor content of 3.2 wt% and a red organic phosphor layer content of 2.8 wt%.

At this time, the surface roughness R _a of the surface structured layer of the extruded optical film is 14.06 탆 R _z is 60.91 탆.

division Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
2 Comparative Example
3 Comparative Example
4 Surface structured layer PC resin
(weight%) 100 100 100 100 100 100 100 100 The organic phosphor layer
(Core layer) PC resin
(weight%) 99.89 99.89 99.89 99.89 99.89 99.7 99.7 99.94 Green organic light intensity
(weight%) 0.1 0.1 0.1 0.1 0.1 0.295 0.295 0.032 Red
Organic phosphor
(weight%) 0.01 0.01 0.01 0.01 0.01 0.005 0.005 0.028 Skin layer PC resin
(weight%) 100 100 100 100 100 100 100 100 pattern mat hemisphere Lent
Jurira prism pyramid mat hemisphere hemisphere Illuminance R _a 1.21 1.50 1.62 1.91 1.60 0.03 0.02 14.06 R _z 6.13 7.32 8.54 9.23 8.32 0.16 0.12 60.91

division Example
6 Example
7 Example
8 Example
9 Example
10 Example
11 Comparative Example
One Surface structured layer PC resin
(weight%) 100 100 100 100 100 100 100 The organic phosphor layer
(Core layer) PC resin
(weight%) 99.89 99.89 99.89 99.89 99.89 99.89 99.89 Green organic light intensity
(weight%) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Red
Organic phosphor
(weight%) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Skin layer PC resin
(weight%) 100 100 100 100 100 100 100 pattern mat mat mat mat mat mat mat Illuminance R _a 1.28 1.37 1.16 1.30 1.20 1.22 1.25 R _z 6.10 6.26 6.05 6.15 6.23 6.17 6.12

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

The optical properties of the color-compensated extruded optical films prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 5 below.

(1) Measurement of brightness (Nit)

The optical films of Examples and Comparative Examples were constructed by mounting a color-compensated extrusion optical film, a prism, and a reflective polarizing film on a 55 "Blue LED BLU having a center wavelength of 450 nm and driving the panel in a white state Using the SR3 luminance meter manufactured by TOPCON, Japan, the entire screen area was divided into nine points, and the luminance of each spot was measured to obtain an average value.

(2) Measurement experiment of luminance uniformity (dispersibility)

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.

(3) Experiment to measure the color recall ratio

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.

division Luminance
(nit) Luminance
Uniformity (%) Color recall
(%) Exterior
(Color) Example 1 520.7 92.0 100.5 White Example 2 522.6 92.1 100.7 White Example 3 521.7 91.4 100.3 White Example 4 523.6 91.3 100.2 White Example 5 525.7 92.0 100.4 White Example 6 523.5 91.5 100.7 White Example 7 521.7 91.2 100.2 White Example 8 522.1 92.1 100.5 White Example 9 523.9 91.8 100.5 White Example 10 524.7 92.1 100.3 White Example 11 521.2 91.7 100.8 White Comparative Example 1 503.7 91.5 86.1 Greenish Comparative Example 2 494.0 86.3 86.5 Greenish Comparative Example 3 495.2 85.3 84.9 Greenish Comparative Example 4 402.5 79.6 102.1 Redish

As shown in Table 3, in Examples 1 to 11, the color reproduction rate was 98% or more, and the white light was emitted to the blue light source while the luminance was 5200 nit or higher.

However, when the surface roughness arithmetic average roughness (R _a) is less than 0.1㎛ was Comparative Example 2 and Comparative Example 3, as compared to the embodiment, showed a relatively low luminance, luminance uniformity even a low value of less than 90% It looked. Further, in the case of Comparative Example 4 in which the arithmetic average roughness (R _a ) exceeded 10 μm and the ten-point average roughness (R _z ) exceeded 50 μm, there was a problem in that the luminance uniformity greatly deteriorated.

In the case of Comparative Example 2 and Comparative Example 3 in which the red-based phosphor was used in a ratio of less than 1: 0.02 by weight, there was a problem that the green-based phosphor emits weak green light, and a red- In the case of Comparative Example 4 in which the weight ratio was more than 1: 0.8, there was a problem that the appearance was reddish.

In the case of Comparative Example 1, as a result of poor heat resistance of the phosphor used, the optical characteristics of the phosphor in the extrusion process were significantly lowered, resulting in a lower color reproduction rate as compared with the Examples.

It can be seen from the above Examples and Experiments that the present invention can produce a color compensation optical film with excellent mass productivity through an extrusion process in spite of using an organic fluorescent material, It can be confirmed that the film has excellent optical properties and it is expected that LED light, LED display, LCD and the like having excellent color reproducibility and the like can be provided by using the light diffusion integral type color compensation extruded optical film of the present invention .

Claims

An organic phosphor layer including an organic phosphor in the form of a single molecule having a PL (photoluminescence) wavelength of 500 nm to 680 nm and a transparent resin; And
And a light diffusion surface structure layer on or under the organic phosphor layer,
Wherein the organic fluorescent layer and the light diffusion surface structure layer are integrated by coextrusion.

A single-layer structure or a multi-layer structure film comprising an organic phosphor having a PL (photoluminescence) wavelength of 500 nm to 680 nm and a single-molecule organic phosphor and a transparent resin,
Wherein an optical acid surface structure is formed on one surface or both surfaces of the film.

The organic electroluminescent device according to claim 1, wherein the organic phosphor layer
A single layer structure including an organic phosphor having a PL wavelength of 500 to 570 nm and an organic phosphor having a PL wavelength of 580 to 680 nm; or
Layer structure including a first organic phosphor layer including an organic phosphor having a PL wavelength of 500 to 570 nm and a second organic phosphor layer including an organic phosphor having a PL wavelength of 580 to 680 nm,
Wherein the multilayer structure comprises a first organic phosphor layer and a second organic phosphor layer alternately stacked or laminated in a ramped manner.

The optical compensation film according to claim 1, wherein the organic phosphor layer is formed with a light diffusion surface layer and the skin layer is formed under the organic phosphor layer.

The light-emitting device according to claim 1, wherein the transparent resin of the organic phosphor layer and the transparent resin constituting the light-diffusing surface structure layer are homogeneous or heterogeneous resins,
The transparent resin of the organic phosphor layer and the transparent resin constituting the light-diffusing surface structure layer may be selected from the group consisting of polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate (PMMA), co-polymethyl Wherein the optical compensation film comprises at least one selected from the group consisting of methacrylate (co-PMMA), acrylonitrile-butadiene-styrene (ABS) resin and polystyrene (PS) resin.

6. The method of claim 5, wherein the polycarbonate resin has a melting index (MI) of 1 to 40, a glass transition temperature (Tg) of 130 to 160 DEG C,
Wherein the polyethylene terephthalate resin is a polyethylene terephthalate resin having an intrinsic viscosity of 0.5 to 1.0 dl / g.

The optical compensation film according to claim 1, wherein the monomolecular organic phosphor has a specific gravity of 1.0 to 2.0 g / cm 3 and a thermal decomposition temperature of 300 ° C or more.

The organic phosphor according to claim 3, wherein the organic phosphor having a PL wavelength of 500 to 570 nm is selected from the group consisting of a perylene-based organic phosphor represented by the following formula (1), a perylene-based organic phosphor represented by the following formula (2), an anthracene- And a tetracene-based organic fluorescent material represented by the following general formula (4): " (1) "
[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)

Or -CN, each of R ⁵ and R ⁶ is independently a hydrogen atom, a straight-chain alkyl group of C 1 to C 5 or a branched alkyl group of C 3 to C 5,
(3)

In Formula 3, R ¹ and R ² are each independently

,

,

,

or

, R ¹¹ to R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n and m are each independently an integer of 0 to 4, each of R ³ to R ¹⁰ independently represents a hydrogen atom, a C1 A C5 alkyl group, a C2-C5 olefin group, a halogen atom or -CN,
[Chemical Formula 4]

In Formula 4, R ¹ and R ² are each independently

,

,

,

or

The optical compensation film according to claim 3, wherein the organic phosphor having a PL wavelength of 580 to 680 nm is a perylene-based organic phosphor represented by the following formula (5):
[Chemical Formula 5]

In Formula 5, 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.

The optical compensation film according to claim 1, wherein the organic fluorescent substance is contained in an amount of 0.005 to 2% by weight.

4. The organic electroluminescent device according to claim 3, wherein the organic phosphor layer has a single layer structure, and the organic phosphor having the PL wavelength of 500 to 570 nm and the organic phosphor having the PL wavelength of 580 to 680 nm in a ratio of 1: 0.02 to 0.8 Diffusion function integrated color compensation extrusion optical film.

The optical compensation film according to claim 1, wherein the organic phosphor layer has an average thickness of 10 to 500 μm and the average thickness of the light diffusion surface layer is 10 to 200 μm.

The light diffusing surface structure layer or light diffusing surface structure according to any one of claims 1 to 3, wherein the arithmetic mean roughness (R _a ) is 0.1 탆 to 10 탆 and the ten point average roughness (R _z ) Wherein the optical compensation film has a thickness of 1 to 50 mu m.

The optical compensation film according to claim 13, wherein the color reproduction ratio is 98% or more, the luminance is 500 nit or more, and the luminance uniformity is 90% or more.

A first step of preparing a master batch and a resin for a skin layer by mixing an organic phosphor in the form of a single molecule having a PL wavelength of 500 nm to 680 nm and a transparent resin;
Two steps of putting the resin for the masterbatch and the skin layer into an extruder and then melting them;
A third step of coextruding the molten master batch and the resin for the skin layer into a continuous phase to form a pneumatic depression formed with a skin layer on one side or both sides of the organic phosphor layer formed by the masterbatch;
After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And
Wherein the step (b) comprises the steps of: (a) providing a color-compensated color-compensated extruded optical film;

A first master batch obtained by mixing a green organic phosphor having a PL wavelength of 500 to 570 nm and a transparent resin, a second master batch obtained by mixing a red organic phosphor and a transparent resin having a PL wavelength of 580 to 680 nm, and a resin for a skin layer Step one;
A first master batch, a second master batch, and a skin layer resin in an extruder and then melting the mixture;
The molten first master batch, the second master batch and the resin for the skin layer are co-extruded in a continuous phase to form a skin layer on one or both sides of the outermost layer of the organic phosphor layer of the multilayer structure formed by the first master batch and the second master batch Forming a pneumatic depression formed;
After the continuous pneumatic depressions are calendared, one surface or both surfaces of the pneumatic depressions are illuminated to convert the skin layer into a light diffusion surface structure layer, or simultaneously with the calendering, To a diffusion surface structure layer; And
Wherein the step (b) comprises the steps of: (a) providing a color-compensated color-compensated extruded optical film;

A first step of preparing a master batch by mixing an organic phosphor in the form of a single molecule having a PL wavelength of 500 nm to 680 nm 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
A step of calendering an extrudate of a continuous phase and then surface-structuring the surface or both surfaces of the extrudate by surface roughing or surface-structuring simultaneously with the calendering; And
Wherein the step (b) comprises the steps of: (a) providing a color-compensated color-compensated extruded optical film;

A first master batch obtained by mixing a green organic phosphor having a PL wavelength of 500 to 570 nm and a transparent resin, a second master batch obtained by mixing a red organic phosphor and a transparent resin having a PL wavelength of 580 to 680 nm, and a resin for a skin layer Step one;
A first master batch and a second master batch are charged into an extruder and then melted;
Co-extruding the molten first master batch and the second master batch in a continuous phase to form a pneumatic effluent of a multi-layer structure;
A step of calendering a pneumatic depression of a continuous phase and then roughing or surface-structuring one surface or both surfaces of the extrudate or surface-structuring the surface of the extrudate simultaneously with the calendering; And
5 steps of quenching and filming; Wherein the light-diffusing function-integrated color-compensating extrusion optical film is formed of a resin material.

The method according to any one of claims 15 to 18, wherein the melting of the two steps is performed at a temperature of 250 ° C to 320 ° C,
Wherein the fourth step of the roughing treatment is carried out by a sandblasting method.

The method of any one of claims 15 to 18, wherein the step (4) further comprises a step of stretching the film and then thermally fixing the film.

A light emitting diode (LED) display comprising the light diffusing function integral color-compensated extrusion optical film of claim 14.

A light emitting diode (LED) illumination device comprising the light diffusing function integral color-compensated extrusion optical film of claim 14.

A liquid crystal display (LCD) comprising the light diffusion function integral color-compensation extrusion optical film of claim 14.