KR20160044153A - Compensate film and Organic dots for compensate film - Google Patents

Abstract

The present invention relates to novel organic dots for a compensation film, and to a compensation film using the same. The organic dots for a compensation film of the present invention can improve color reproducing ability by having the small half width. The novel material can improve color reproducing ability especially for red.

Description

{Compensate film and organic dots for compensate film}

The present invention relates to an organic dot for a compensation film having a red series PL wavelength and a narrow half width, and a compensation film comprising 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 for replacing existing CdSe quantum dots or CdTe quantum dots. Indium sulfide (In ₂ S ₃ ) quantum dots are one of them.

In particular, indium sulfide (InS ₂ ) has a bulk band gap of 2.1 eV, and InS ₂ Since the quantum dot can emit light in the visible light region, it can be used for manufacturing a high-luminance light emitting diode element or the like. 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, the demand for the development of new quantum dots without using cadmium is increasing.

OLEDs and LCDs have strengths and weaknesses. OLEDs have excellent color reproduction performance for R (red), G (green), and B (blue) , Whereas LCDs capable of high resolution display have a problem that the RGB color reproduction power is lower than that of OLEDs. Recently, as the UHD TV market has been activated, there is a growing demand for materials having high color reproduction and excellent optical efficiency.

U.S. Published Patent Application No. 2014-0246689 (published September 4, 2014)

Accordingly, the present inventors have made efforts to manufacture a new material capable of replacing quantum dots of existing inorganic materials, and as a result, have developed a new organic dot having a single molecule structure made of an organic material. That is, the present invention provides an organic dot having a PL (photoluminescence) wavelength of a red series and a narrow half width, and a compensation film using the organic dot.

According to an aspect of the present invention, there is provided a compensation film comprising organic dots in a monomolecular shape having a narrow half width.

In one preferred embodiment of the present invention, the compensation film of the present invention may have a PL wavelength of 580 nm to 680 nm and a half-width of 60 nm or less at the time of measuring PL (photoluminescence).

As a preferred embodiment of the present invention, the compensation film of the present invention has a temperature of 60? ~ 85? And a color deviation of 5 / 10,000 ~ 30 / 10,000 when the NTSC color coordinate change ratio is measured after being left for 192 hours under a relative humidity of 75% ~ 85%.

As a preferred embodiment of the present invention, in the compensation film of the present invention, the organic dot may include a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ¹ , R ² , R ³ And R ⁴ are each independently 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, and R ⁵ is (C 1 to C 3 alkoxy) dialkylamino of C1 ~ C3) group, (dialkylamino) phenyl group of C1 ~ C3, (a trialkyl) phenyl group or a phenol group of C1 ~ C3, R ⁶ And R ⁷ are each independently -Br, -F, -Cl, -OH, a C1-C5 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or a naphthalene group.

In one preferred embodiment of the present invention, R ¹ , R ² , R ³ And R ⁴ is each independently an alkyl group of C1 ~ C5, R ⁵ is a phenyl group or a phenyl group (trialkyl of C1 ~ C3) (alkoxy of C1 ~ C2) (dialkylamino of C1 ~ C2), R ⁶ And R ⁷ is -Br, -F, -Cl or a C1-C3 alkyl group, and preferably R ¹ , R ² , R ³ And R ⁴ is an alkyl group having 1 to 3 carbon atoms and R ⁵ is a 4-methoxy-2,6-dimethylphenyl group, a 4-methoxy-2,6-diethylphenyl group, a 4-ethoxy- Methylphenyl group, 4-ethoxy-2,6-diethylphenyl group, 2,4,6-trimethylphenyl group or 2,4,6-triethylphenyl group, R ⁶ And R < ⁷ > are -F or C1-C2 alkyl groups.

As a preferred embodiment of the present invention, the compensation film of the present invention may further comprise at least one selected from the group consisting of Quantum dots, Polymer dots and Dye in addition to the organic dots. have.

Another aspect of the present invention relates to the organic dot for a compensation film as described above, and can be characterized by including a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ¹ , R ² , R ³ And R ⁴ are each independently 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, and R ⁵ is (C 1 to C 3 alkoxy) dialkylamino of C1 ~ C3) group, (dialkylamino) phenyl group of C1 ~ C3, (a trialkyl) phenyl group or a phenol group of C1 ~ C3, R ⁶ And R ⁷ are each independently -Br, -F, -Cl, -OH, a C1-C5 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or a naphthalene group.

In one preferred embodiment of the present invention, R ¹ , R ² , R ³ And R ⁴ is each independently an alkyl group of C1 ~ C5, R ⁵ is a phenyl group or a phenyl group (trialkyl of C1 ~ C3) (alkoxy of C1 ~ C2) (dialkylamino of C1 ~ C2), R ⁶ And R ⁷ is -Br, -F, -Cl or a C1-C3 alkyl group, and preferably R ¹ , R ² , R ³ And R ⁴ is an alkyl group having 1 to 3 carbon atoms and R ⁵ is a 4-methoxy-2,6-dimethylphenyl group, a 4-methoxy-2,6-diethylphenyl group, a 4-ethoxy- Methylphenyl group, 4-ethoxy-2,6-diethylphenyl group, 2,4,6-trimethylphenyl group or 2,4,6-triethylphenyl group, R ⁶ And R < ⁷ > are -F or C1-C2 alkyl groups.

In one preferred embodiment of the present invention, the organic dot for a compensation film of the present invention has a PL wavelength of 580 nm to 680 nm and a half width of 60 nm or less.

Another aspect of the present invention relates to the use of the organic dot and / or compensation film, wherein the organic and / or inorganic light emitting diode (LED) display comprising organic dot and / or compensation film of the invention, organic and / Or an inorganic light emitting diode (LED) illumination device, and / or a liquid crystal display device (LCD).

The present invention is a luminescent material that does not use an inorganic material such as cadmium and does not cause environmental problems. In addition, the compensatory film of the present invention has a PL wavelength of 580 nm to 680 nm when measuring PL (photoluminescence) (Color reproduction ratio) of 65 nm or less, preferably 60 nm or less, it is possible to increase the light efficiency and the color reproducibility, and is excellent in high temperature / high humidity / light stability. . The compensation film of the present invention can be used in various fields such as a biosensor, a lighting device, a display device such as an LCD, an LED, and the like.

Each of Figs. 1 to 4 shows the PL measurement graphs of Production Examples 1 to 2 and Comparative Production Examples 1 to 2 conducted in Experimental Example 1.
Fig. 5 shows the color coordinates used in Experimental Example 2. Fig.

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

The term " C1 ", "C2 ", etc. used in the present invention means a carbon number, and 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,

In the formula represented by " R ₁ is independently a hydrogen atom, a methyl group or an ethyl group, a is 1 to 3, "when a is 3, a plurality of R ¹ , that is, R ¹ As there are three substituents, each of a plurality of R ¹ which are the same or different, R ¹ in each of both may be a hydrogen atom, methyl or ethyl, or R ¹ as each of the other, R ¹ One of 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 부위, 또는 다른 화합물과의 연결부위를 의미한다.
Further, in the present invention,

"In the chemical formulas represented by" * "means a site to which a substituent is connected or a linkage site to another compound.

Hereinafter, the present invention will be described in detail.

The present invention relates to a compensation film comprising organic dots in the form of monomolecules, wherein the compensation film of the present invention has a PL wavelength of 580 nm to 680 nm, preferably 600 nm To 650 nm, and can have a full width at half maximum of 65 nm or less, preferably 60 nm or less, more preferably 45 nm to 60 nm within the PL wavelength range, Lt; / RTI > film.

The monomolecular organic dot used in the compensation film of the present invention will be described.

The present invention relates to a novel organic dot, wherein the organic dot of the present invention comprises a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ¹ , R ² , R ³ And / or R ⁴ may be each independently is C1 ~ C5 alkyl group, an olefinic group of C2 ~ C5, may be a cycloalkyl group, a styrene group, a phenyl group, a phenol group or a benzyl date of C5 ~ C6, the preferred R ^1, R ² , R ³ And / or R ⁴ may each independently be an alkyl group having 1 to 3 carbon atoms, more preferably R ¹ , R ² , R ³ And / or R < ⁴ > may each independently be a methyl group or an ethyl group.

The R ⁵ in Formula 1 may be a (C1-C3 alkoxy) (C1-C3 dialkyl) phenyl group, a C1-C3 dialkylphenyl group or a C1-C3 trialkylphenyl group, wherein R ⁵ is a phenyl group or a phenyl group (trialkyl of C1 ~ C3), more preferably the R ⁵ (alkoxy of C1 ~ C2) (dialkylamino of C1 ~ C2) are 4-methoxy-2,6 Methoxy-2,6-diethylphenyl group, 4-ethoxy-2,6-dimethylphenyl group, 4-ethoxy-2,6-diethylphenyl group, 2,4,6-trimethyl A phenyl group or a 2,4,6-triethylphenyl group.

In addition, R < ⁶ > And / or R ⁷ are each independently selected from -Br, -F, -Cl, -OH, an alkyl group of C1 ~ C5, cycloalkyl group of C5 ~ C6, can be a phenyl group or a naphthalene group, preferably R ⁶ And / or R ⁷ may each independently be -Br, -F, -Cl, a C1-C3 alkyl group or a naphthalene group, more preferably R ⁶ And R < ⁷ > may be an alkyl group of -F or C1-C2.

The organic dot comprising the compound of Formula 1 of the present invention may be surface-treated with PEI (polyethylenimine) or aminopolystyrene (APS). In this case, the organic dot may have a light efficiency, a light stability, Can be obtained.

The compensation film of the present invention can be produced by additionally using at least one selected from Quantum dots, Polymer dots and Dye in addition to the various types of organic dots described above.

The quantum dots generally used in the industry can be used without any particular limitation.

The polymer dot may further include at least one selected from a random copolymer represented by the following formula (2) and a random copolymer represented by the following formula (3).

(2)

을 포함하는 C2 ~ C4의 올레핀기이고, 여기서, R¹⁴는 메틸기 또는 에틸기이며, n은 0 ~ 3의 정수이며,R⁶ ~ R¹¹ 각각은 독립적으로 C1 ~ C12의 직쇄형 알킬기, C4 ~ C12의 분쇄형 알킬기 또는 C2 ~ C12의 올레핀기이며, R¹² ~ R¹³는 독립적으로 C1 ~ C5의 알킬기고, R¹⁵는 ?H, -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, and R ⁶ ~ R ¹¹ each independently represent a group of C1 ~ C12 olefins in the straight-chain alkyl group, C4 ~ C12 alkyl group or a C2 ~ C12 crushing of, ¹² R ~ R ¹³ are independently an alkyl group and a C1 ~ C5, R ¹⁵ is? Is H, -OCH ₃ or _{-OCH 2 CH 3, a, b} , c, d are shown as the molar ratio between the monomers constituting the polymer, a wherein the molar ratio of b, c, and d is 1: 1 to 1.5: 5 to 25: 1 to 1.5, and A and B are independently at least one end group selected from the group consisting of phenyl, phenyl, biphenyl, anthracene and naphthalene , And L is a rational number satisfying the 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 (2) 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 is a methyl group, To R < ¹¹ > are all the same and R < ⁶ > To R < ¹¹ > is a straight chain alkyl group of C6 to C10 or a branched alkyl group of C6 to C10, and A and B are phenyl groups.

(3)

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 몰비는 1 :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.In Formula 3, R ¹ is a hydrogen atom or a C1 to C5 alkyl group, and R ² And R ³ are independently a hydrogen atom, a methyl group or an ethyl group, and R ⁴ and R ⁵ independently represent a hydrogen atom, a C 1 to C 5 alkyl group, a C 2 to C 5 olefin group, a C 5 to C 6 cycloalkyl group,

, Wherein R ⁸ is a methyl group or an ethyl group, n is an integer of 0 to 3, and R ⁶ And R ⁷ C12 linear alkyl group or C2-C12 olefin group, the molar ratio of a and b is 1: 5 to 15, A and B independently represent a phenyl group, a bivalent 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 100,000.

Preferably, R ¹ in the above formula (3) is a methyl group, and R ² And R ³ is independently a hydrogen atom or an alkyl group C1 ~ C2, R ⁴ and R ⁵ are independently an alkyl group of a hydrogen atom, C1 ~ C5, R ⁶ And R < ⁷ > are each independently a C6 to C10 linear alkyl group or a C6 to C10 branched alkyl group, and A and B are phenyl groups.

The dyes may be dyes for optical films used in the art. Preferably, the dyes may include at least one selected from coumain, green and rhodamine.

In addition, the compensation film composition of the present invention as described above may further comprise one kind selected from additives such as 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, Or more.

Compensation films can be prepared by the general methods used in the art using the compensation film compositions described above. For example, the compensating film composition of the present invention may be coated on at least one surface of a base material by a conventional method such as Meyer bar or comma coater method, and then dried and cured An organic dye layer can be formed.

As one embodiment, a brightness enhancement film (or sheet) of the type shown in FIG. 6 can be manufactured using the compensation film of the present invention in the form of FIG. The brightness enhancement film includes the compensation film of the present invention as a compensation film layer 101, and the compensation film layer may include the organic dots and / or beads 104 of the present invention as described above. The compensation film layer 101 may be formed on the upper surface of the substrate 102. The above substrate is not particularly limited, but a material of polyethylene terephthalate (PET) can be used. The bead coating layer 103 may be formed on the lower end surface of the base material 102 or the base layer. The bead coating layer 103 may include the same or different kinds of beads as the bead 104. The compensation film and / or the brightness enhancement film may be used as an optical film of a back light unit. For example, the compensation film and / or the brightness enhancement film may be used as a light guide plate Thereby improving the efficiency and brightness of the LCD or the like, as well as improving the color reproducibility.

The average thickness of the compensation film of the present invention may be 0.1 to 200 탆, preferably 2 to 100 탆, more preferably 2 to 70 탆, and when the average thickness of the compensation film is less than 0.1 탆 It may be difficult to realize white light. If it exceeds 200 탆, there may be a problem that the luminance and color reproducibility decrease even if the light transmittance is too low. Therefore, it is preferable to have a thickness within the above range.

The substrate is not particularly limited and can be used as a material used as a substrate of conventional optical films. Examples thereof include a polyester film such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, a polyethylene film, A polyvinyl alcohol film, an ethylene-vinyl acetate copolymer film, a polystyrene film, a polyvinylidene chloride film, a polyvinyl alcohol film, a polyvinyl alcohol film, a polyvinyl alcohol film, a polyvinyl alcohol film, a polypropylene film, a cellophane, a diacetylcellulose film, a triacetylcellulose film, an acetylcellulose butyrate film, A polyether ether ketone film, a polyether sulfone film, a polyether imide film, a polyimide film, a fluororesin film, a polyamide film, an acrylic resin film, a norbornene resin film, a polyimide film, Cycloolefin resin film The can be used.

In addition, the bead coating layer 103 may further include an antistatic agent for antistatic effect in a coating liquid containing a thermosetting polyurethane resin. The polymeric antistatic agent may be used in an amount of 20 parts by weight or less, preferably 3 to 12 parts by weight, based on 100 parts by weight of the coating liquid. The antistatic agent may be a quaternary ammonium salt based antistatic agent, , And more preferably 5 to 9 parts by weight. Examples of the polymeric antistatic agent include ELECON-100ED, ELECON-1700 manufactured by NANOCAMTEC, MORESTAT ES-7205, MORESTAT ES-7500 manufactured by Moakhem, JISTAT 2000 / 2000N manufactured by Sinoil Oil Co., PU 101 and the like. Further, the bead coating layer may further include a light stabilizer added to the coating liquid for the UV stability of the diffusion film and the coating liquid for the protective film. Examples of the light stabilizer that can be used include commercially available Tinuvin 144, Tinuvin 144 manufactured by Ciba Geigy 292, Tinuvin 327, Tinuvin 329, Tinuvin 5050, and Tinuvin 5151, and LOWILITE 22, LOWILITE 26, LOWILITE 55, LOWILITE 62, LOWILITE 94 and the like.

The bead coating layer may be prepared by appropriately containing at least one additive such as an ultraviolet absorber, a lubricant, a leveling agent, a defoaming agent, a polymerization promoter, an antioxidant, a flame retardant, an infrared absorbent, a surfactant, and a surface modifier.

As described above, the compensation film including organic dots of the present invention can be applied to an organic or inorganic light emitting diode (LED) display, an organic or inorganic light emitting diode (LED) illumination device and / or a liquid crystal display device (including LCD, LED display, UHD display) And can be widely used. For example, it relates to a new material which can improve the color reproduction performance of a red series by applying to a prism film, a diffusion film, a light guide plate, a compensation film, etc. of backlight units (BLUs). The present invention is particularly suitable for use in a display compensation film such as an LCD (including an LED display and a UHD display) for red color reproduction enhancement.

The compensation film of the present invention is a luminescent material that does not use an inorganic material such as cadmium and does not cause an environmental problem. In addition, the organic dots of the present invention exhibit a PL (photoluminescence) nm and a half width of the PL wavelength range of 60 nm or less, preferably 45 nm to 60 nm, so that the color reproducibility and the quantum efficiency (light efficiency) are increased. Therefore, it can be used in various fields such as a biosensor, a lighting device, a display device and the like by applying it in the form of an organic dye itself or a compensation film.

In addition, the compensation film of the present invention has the color deviations (x and y) at the time of measuring the change rate of CIE x and CIE y in the NTSC color coordinates after being left at a temperature of 60 ° C to 85 ° C and a relative humidity of 75% to 85% (Or durability) under high temperature and high humidity is 5/100 to 30/100, preferably 10/100 to 28/100, more preferably 12/100 to 26/100.

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 ]

Example  One : Organic dot  Produce

(1) A three-necked flask was charged with 8-mesityl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora 3-3a, 4a- 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 thereto, 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 (2).

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

(2)

(2) To a three-necked flask was added 1 g of the red solid (1.615 mmol) of the above-described Formula 2, 1.018 g of thiophene bornic acid pinacol ester (4.845 mmol) and 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 a vacuum treatment and then purged with nitrogen. Next, a solvent (THF: H ₂ O = 9: 1 by volume) was added thereto, followed by overnight reflux at 85 ° C.

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

^{_{1 H NMR (CDCl 3, 400}} MHz): 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, 6H), 1.40 (s, 6H)

[Formula 1-1]

Example  2

(1) A three-necked flask was charged with 8- (4-methoxy-2,6-dimethylphenyl) -1,3,5,7-tetramethyl-4,4-difluoro-4- 4-methoxy-2,6-dimethylphenyl) -1,3,5,7-tetramethyl-4,4-difluoro-4-bora3-3a, 4a-diaza-s -indacene) (2.61 mmol) was added, CH ₂ Cl ₂ was added, and stirring was performed.

Next, 2.64 g of NIS (N-iodosuccinimide, 11.74 mmol) was added thereto, 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 (4).

^{_{1 H NMR (CDCl 3, 400}} MHz): 6.72 (s, 2H), 3.86 (s, 3H), 2.66 (s, 6H), 2.09 (s, 6H), 1.45 (s, 6H)

[Chemical Formula 4]

(2) To a three-necked flask was added 1 g of the red solid (1.57 mmol) of the above-described Formula 4, 990 mg of thiophene bornic acid pinacol ester (4.71 mmol), K ₂ CO ₃ mmol) 1.08 g, Pd (PPh 3) 4 (0.157 mmol) was loaded to 181 mg, and then, a vacuum process, was blown nitrogen. 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), the solvent was removed using a rotary evaporator, and the obtained material was subjected to a column to obtain a dark red solid represented by the following formula 1-2 .

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.09 (d, 2H), 6.82 (m, 2H), 6.70 (s, 2H), 6.61 (m, 2H), 3.85 (s, 6H), 2.65 (s, 3H), 2.08 (s, 6H), 1.45 (s, 6H)

[Formula 1-2]

Comparative Example  One

(1) A three-necked flask was charged with 8-phenyl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora 3-3a, 4a-diaz- a put -1,3,5,7-tetramethyl-4,4-difluoro- 4-bora3-3a, 4a-diaza-s-indacene) (3.08 mmol, 1 g), added to CH ₂ Cl _2, and then, Stirring was carried out.

Then, 3.11 g of NIS (N-iodosuccinimide, 13.83 mmol) was added thereto, 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 (5).

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.51 (m, 3H), 7.23 (m, 2H), 2.63 (s, 6H), 1.39 (s, 6H)

[Chemical Formula 5]

(2) To a three-necked flask was added 1 g of the red solid (1.733 mmol), 1.1 g of thiophene bornic acid pinacol ester (5.199 mmol) and K ₂ CO ₃ 8.665 mmol) 1.2 g, Pd ( PPh 3) 4 (0.173 mmol) was loaded to 200 mg, and then, a vacuum process, was blown nitrogen. 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), the solvent was removed using a rotary evaporator, and the obtained material was subjected to a column to obtain a dark red solid represented by the following formula 1-3 .

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.50 (d, 3H), 7.33 (m, 4H), 7.08 (t, 2H), 6.86 (d, 2H), 2.61 (s, 6H), 1.40 (s, 6H)

 [Formula 1-3]

Comparative Example  2

(1) A three-necked flask was charged with 1,3,5,7,8-pentamethyl-4,4-difluoro-4-bora-3a, 4a-diaza- 4,8-Pentamethyl-4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene) (3.80 mmol) were added. CH ₂ Cl ₂ was added and stirring was carried out.

Next, 3.85 g of NIS (N-iodosuccinimide, 17.1 mmol) was added thereto, followed by stirring at room temperature (about 25 ° C) for 6 hours. Next, the solvent was removed by a rotary evaporator, and the obtained material was subjected to a column to obtain a red solid represented by the following formula (6).

¹ H NMR ( CDCl ₃ , 400 MHz ): 2.62 (s, 3H), 2.60 (s, 6H)

[Chemical Formula 6]

(2) To a three-necked flask was added 1 g of the red solid (1.94 mmol), 1.22 g of thiophene bornic acid pinacol ester (5.82 mmol) and K ₂ CO ₃ 9.7 mmol) 1.34 g, Pd ( PPh 3) 4 (0.194 mmol) was loaded to 224 mg, and then, a vacuum process, was blown nitrogen. 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 temperature was lowered to room temperature (about 25 ° C), the solvent was removed using a rotary evaporator, and the resulting material was subjected to a column to obtain a dark red solid represented by the following Formula 1-4 .

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.42 (d, 2H), 7.14 (m, 2H), 6.93 (d, 2H), 2.71 (d, 2H), 2.57 (s, 6H), 2.40 (s, 6H)

 [Formula 1-4]

Comparative Example  3

(1) A three-necked flask was charged with 8- (4-methoxy) -1,3,5,7-tetramethyl-4,4-difluoro-4-bora 3-3a, 4a-diaza- Line (8- (4-Methoxy) -1,3,5,7 -tetramethyl-4,4-difluoro-4-bora3-3a, 4a-diaza-s-indacene) into a (2.81mmol) 1g, CH ₂ Cl ₂ was added, followed by stirring.

Next, 2.84 g of NIS (N-iodosuccinimide, 12.64 mmol) was added thereto, followed by stirring at room temperature (about 25 ° C) for 6 hours. Next, the solvent was removed by a rotary evaporator, and the obtained material was subjected to a column to obtain a red solid represented by the following formula (7).

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.07 (d, 2H), 6.89 (d, 2H), 2.64 (s, 3H), 2.55 (s, 6H), 1.44 (s, 6H)

(7)

(2) To a three-necked flask was added 1 g of the red solid (1.647 mmol), the above prepared Thiophene bornic acid pinacol ester (4.941 mmol), K ₂ CO ₃ 8.235 mol) 1.14g, Pd (PPh 3) 4 (0.165 mmol) was loaded to 190 mg, and then, a vacuum process, was blown nitrogen. 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 obtained material was subjected to a column to obtain a dark red solid represented by the following formula (1-5) .

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.48 (d, 2H), 7.21 (m, 2H), 7.09 (d, 2H), 7.01 (m, 2H), 6.91 (d, 2H), 2.63 (s, 3H), 2.54 (s, 6H), 1.43 (s, 6H)

 [Formula 1-5]

Comparative Example  4

0.59 ml of 2,4,6-trimethylbenzaldehyde (4 mmol) was added to a three-necked flask, and the mixture was vacuumed, and then dried CH ₂ Cl ₂ was added 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 was 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 (8).

^{_{1 H NMR (CDCl 3, 400}} MHz): 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]

Comparative Example  5

After adding 1.0 g of 4-formylbenzonitrile (7.626 mmol) into a three-necked flask, the mixture was vacuumed, and dried CH ₂ Cl ₂ was added thereto and stirred.

Next, 1.80 g of 2,4-dimethyl-1H-pyrrole (19.065 mmol) was added thereto, and then trifluoroacetic acid (44 U) and dried CH ₂ Cl ₂ was 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, 7.626 mmol), 1.73 g, and the mixture was stirred at 25 DEG C for 1 hour.

Next, 15.0 ml of triethylamine (NEt ₃ , 109.814 mmol) was added thereto, and 16.0 ml of BF ₃ .Et ₂ O (129.642 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 (9).

^{_{1 H NMR (CDCl 3, 400}} MHz): 7.87 (d, 2H), 7.56 (d, 2H), 5.75 (s, 2H), 2.67 (s, 6H), 1.45 (s, 6H)

[Chemical Formula 9]

Comparative Example  6

1 g of the red solid (1.733 mmol), 634 mg of phenyl bornic acid (5.20 mmol) and K ₃ PO ₄ .H ₂ O (8.665 mmol) were added to the _three- necked flask, , 39 mg of Pd (OAc) ₂ (0.173 mmol), and the mixture was vacuum-treated and then blown with nitrogen. Next, a solvent (Toluene: Ethanol) was added thereto, and the mixture was refluxed at 80 ° C for 8 hours.

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 a column to obtain a dark red solid represented by the following formula (10).

¹ H NMR ( CDCl ₃ , 400 MHz ): 7.48 (m, 3H), 7.37 (m, 6H), 7.32 (m, 2H), 7.17 6H)

 [Chemical formula 10]

Manufacturing example  One : Organic dot  Surface Treatment and Preparation of Compensation Film Using It

500 parts by weight of a silicone monodisperse bead (Gentsu, SI-020) having an average particle diameter of 2 占 퐉 and 100 parts by weight of methyl ethyl ketone (MEK) as a solvent were added to 100 parts by weight of a liquid type thermosetting urethane resin having a weight average molecular weight of 2,000, , 1 part by weight of a leveling improver (BYK Cmemie Co., Ltd. (BYK-377)), 9 parts by weight of quaternary ammonium salt-based antistatic agent (PU101 manufactured by Japan Industrial Chemicals Co., Ltd.) 0.1 part by weight of the organic dots prepared were mixed and stirred at 1,000 rpm for 30 minutes to prepare a coating composition for preparing a compensation film.

Next, the above-mentioned coating composition for preparing a compensation film was coated on the upper surface of a PET substrate by a gravure coating method and coated with an average film thickness of 50 탆. Next, the substrate having the coating layer formed thereon was placed in an oven, and then cured at 100 DEG C for 10 minutes to prepare a compensation film.

Manufacturing example  2 and Comparative Manufacturing Example  1 to 6

Production Example 2 and Comparative Production Examples 1 to 6 were carried out by using the organic dots of Example 2 and Comparative Examples 1 to 6, respectively, in the same manner as in Production Example 1 above.

Experimental Example  One : UV  Absorption wavelength, PL  Measurement and Half width  Measurement experiment

(One) UV  Absorption wavelength measurement

The UV absorbance of the films prepared in the above Production Examples and Comparative Production Examples was measured using a UV spectrometer (VARIAN, CARY 100 Conc.).

In this case, 0.01 g of each of the organic dots was taken, dissolved in 3 ml of toluene, placed in a test tube, and the emission spectrum was measured according to UV absorbance. The results are shown in Table 1 below.

 (2) PL ( 광화물 ) Measurement and Half width  Measurement experiment

The organic dots of the above-mentioned production examples were prepared, and PL measurement and full width at half maximum were measured using DarsaPro5200OEM PL (PSI Trading Co.) and 500W ARC Xenon Lamp, 5 and Comparative Production Examples 1 to 3 are shown in Table 1 below.

In this case, 0.04 g of each of the organic dots was taken, dissolved in 3 ml of toluene, placed in a test tube, and the emission spectrum was measured through a Xenon lamp.

The values obtained by measuring the full width at half maximum are shown in Table 1 below. The measurement charts of Production Examples 1 and 2 and Comparative Production Examples 1 and 2 are shown in Figs. 1 to 4, respectively.

division UV absorption wavelength
(nm) PL wavelength measurement
(nm) Half width
(nm) Production Example 1 531 610 57 Production Example 2 545 639 60 Comparative Preparation Example 1 530 610 80 Comparative Preparation Example 2 522 598 87 Comparative Production Example 3 542 631 75 Comparative Production Example 4 453 521 40 Comparative Preparation Example 5 462 540 48 Comparative Preparation Example 6 530 557 71

As a result of the test results shown in Table 1, it was confirmed that the PL wavelength values of the red series were obtained in Production Examples 1 and 2 and Comparative Production Examples 1 to 3. However, in Comparative Production Examples 1 to 3, it was confirmed that the color reproducibility was lowered as compared with Production Examples 1 and 2, in which the half width was more than 80 nm and the half width was 60 nm.

In Comparative Production Examples 4 to 5, the half width was as narrow as 50 nm or less, but the PL wavelengths were 521 nm and 540 nm, respectively, and the PL wavelengths were green instead of red, In Production Example 6, there was a problem that the PL wavelength was 557 nm as well as the PL wavelength of 600 nm or less and the half bandwidth was blue-shifted.

Experimental Example  2 : High temperature and high humidity  Resistance measurement experiment

Using the compensation films prepared in the above Production Examples and Comparative Production Examples, color coordinate measurement experiments were carried out using DarsaPro5200OEM PL (PSI Trading Co.) and 500W ARC Xenon Lamp. The results are shown in Table 2 below . The color coordinates were measured based on the NTSC color coordinates shown in FIG.

In addition, each of the same compensation films The compensation film was allowed to stand in a thermo-hygrostat chamber under the conditions of 85 ° C and 85% relative humidity for 192 hours, and the color coordinates were measured in the same manner. The results are shown in Table 2 below.

division High temperature and high humidity
Before Resistance Measurement High temperature and high humidity
After the resistance measurement Color deviation
value Color coordinates CIE x CIE y CIE x CIE y Δx Δy Production Example 1 0.6055 0.2832 0.6041 0.282 0.0014 0.0012 Production Example 2 0.612 0.281 0.6094 0.2788 0.0026 0.0022 Comparative Preparation Example 1 0.6024 0.2884 0.5986 0.2844 0.0038 0.0040 Comparative Preparation Example 2 0.6029 0.2854 0.5987 0.2815 0.0042 0.0039 Comparative Production Example 3 0.6101 0.2791 0.6078 0.2761 0.0023 0.0030

As a result of the test results of Table 2, all of Production Examples 1 to 2 and Comparative Production Examples 1 to 3 had a high temperature and high humidity resistance excellent in color deviation value of 30 / 10,000 or less as a whole, It was confirmed that the deviations (Δx and Δy) were about 10 / 10,000 to 28 / 10,000, and that they had relatively high resistance to high temperature and high humidity compared with Comparative Examples 1 and 2.

Experimental Example  3: Other properties measurement experiment

(1) Adhesive strength evaluation method

Cross hatching 10 × 10 horizontally and vertically 10 mm in 1 mm increments. Attach the tape (18mm, JIS Z-1522) to the cell in 100 cells, press firmly by hand, and quickly remove it to be perpendicular to the direction of tape adhesion. At this time, the number of snow remaining on the film substrate is measured to evaluate the adhesion.

According to the ASTM D 3002 method, 5B is indicated when the degree of fall is 0%, 4B if 5%, 3B if 5-15%, 2B if 15-30%, and 0B if 35-65%.

(2) curling ( Curling ) Sex determination method

The compensation film was cut in a size of 20 cm × 20 cm (width × length), placed on a flat plate, and the height of the curled film of the flat plate and the four sides was measured and the average was obtained (unit: mm).

(3) Antistatic function measurement

The sheet resistance (Ω / sq) was measured with a surface resistance meter (Trustat Worksurface tester, ST-3) under constant temperature and humidity at a temperature of 25 ° C. and a humidity of 50%.

division Adhesive strength
Evaluation method Curling ability
Measure
(mm) Sheet resistance
(Ω / sq) Production Example 1 5B <1 mm 1.15 x 10 ¹² Production Example 2 5B <1 mm 1.07 x 10 ¹² Comparative Preparation Example 1 5B <1 mm 1.24 × 10 ¹² Comparative Preparation Example 2 5B <1 mm 1.01 × 10 ¹² Comparative Production Example 3 5B <1 mm 1.37 x 10 ¹² Comparative Production Example 4 5B <1 mm 0.98 x 10 ¹² Comparative Preparation Example 5 4B <4 mm 0.96 x 10 ¹² Comparative Preparation Example 6 4B <5 mm 1.15 x 10 ¹²

From the results of the experiment of Table 3, it was confirmed that all of the compensation films of Production Examples and Comparative Production Examples had excellent surface resistance. However, Comparative Production Examples 5 and 6 showed relatively lower adhesive strength and curling properties than Production Examples 1 and 2 and Comparative Production Examples 1 to 3.

It was confirmed from the above Examples and Experimental Examples that the compensation film prepared from the organic dot and compensation film composition for a compensation film of the present invention had excellent physical properties. And can be used as a contrast agent, etc., and it can be applied to an optical film such as a compensating film to provide an illumination (including LED display and UHD display) display with improved color reproducibility and high temperature and high humidity resistance It is expected to be able to do.

Claims (12)

It includes organic dots in the form of monomolecules,
Characterized in that the PL wavelength is 580 nm to 680 nm and the half width is 60 nm or less when measuring PL (photoluminescence).
The film according to claim 1,
Wherein the color deviation is 5 / 10,000 to 30 / 10,000 when the NTSC color coordinate change ratio is measured after being left for 192 hours at a temperature of 60 ° C to 85 ° C and a relative humidity of 75% to 85%.
The compensation film according to claim 1, wherein the organic dot comprises a compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1, R ¹ , R ² , R ³ And R ⁴ are each independently 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, and R ⁵ is (C 1 to C 3 alkoxy) dialkylamino of C1 ~ C3) group, (dialkylamino) phenyl group of C1 ~ C3, (a trialkyl) phenyl group or a phenol group of C1 ~ C3, R ⁶ And R ⁷ are each independently -Br, -F, -Cl, -OH, a C1-C5 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or a naphthalene group.
4. The compound according to claim 3, wherein R &lt; 1 &^gt; R ² , R ³ And R ⁴ is each independently an alkyl group of C1 ~ C5, R ⁵ is a phenyl group, a (trialkyl of C1 ~ C3) phenyl (alkoxy of C1 ~ C2) (dialkylamino of C1 ~ C2), R ⁶ And R ⁷ is -Br, -F, -Cl or a C1-C3 alkyl group.
5. The compound according to claim 4, wherein R ¹ , R ² , R ³ And R ⁴ is an alkyl group having 1 to 3 carbon atoms and R ⁵ is a 4-methoxy-2,6-dimethylphenyl group, a 4-methoxy-2,6-diethylphenyl group, a 4-ethoxy- Methylphenyl group, 4-ethoxy-2,6-diethylphenyl group, 2,4,6-trimethylphenyl group or 2,4,6-triethylphenyl group, R ⁶ And R &lt; ⁷ &gt; are -F or a C1-C2 alkyl group.
The compensation film according to any one of claims 1 to 5, wherein the compensation film further comprises at least one selected from the group consisting of Quantum dots, Polymer dots and Dye. film.
An organic dye for a compensation film, which comprises a compound represented by the following formula (1);
[Chemical Formula 1]

In Formula 1, R ¹ , R ² , R ³ And R ⁴ are each independently 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, and R ⁵ is (C 1 to C 3 alkoxy) dialkylamino of C1 ~ C3) group, (dialkylamino) phenyl group of C1 ~ C3, (a trialkyl) phenyl group or a phenol group of C1 ~ C3, R ⁶ And R ⁷ are each independently -Br, -F, -Cl, -OH, a C1-C5 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or a naphthalene group.
8. The compound according to claim 7, wherein R &lt; 1 &^gt; R ² , R ³ And R ⁴ is each independently an alkyl group of C1 ~ C5, R ⁵ is a phenyl group or a phenyl group (trialkyl of C1 ~ C3) (alkoxy of C1 ~ C2) (dialkylamino of C1 ~ C2), R ⁶ And R &lt; ⁷ &gt; are -Br, -F, -Cl or a C1-C3 alkyl group.
The organic dye for a compensation film according to claim 7, wherein a PL wavelength is from 580 nm to 680 nm and a half width is 60 nm or less in PL (photoluminescence) measurement.
A light emitting diode display comprising a compensation film according to any one of claims 1 to 5.
A light emitting diode lighting device comprising the compensation film of any one of claims 1 to 5.
A liquid crystal display (LCD) comprising a compensation film according to any one of claims 1 to 5.

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