KR102472457B1 - Light scattering resin composition, scattering layer and image display device using the same - Google Patents
Light scattering resin composition, scattering layer and image display device using the same Download PDFInfo
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- KR102472457B1 KR102472457B1 KR1020190029449A KR20190029449A KR102472457B1 KR 102472457 B1 KR102472457 B1 KR 102472457B1 KR 1020190029449 A KR1020190029449 A KR 1020190029449A KR 20190029449 A KR20190029449 A KR 20190029449A KR 102472457 B1 KR102472457 B1 KR 102472457B1
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- South Korea
- Prior art keywords
- light
- group
- resin composition
- scattering
- scattering resin
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- 238000000149 argon plasma sintering Methods 0.000 title claims abstract description 51
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
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- 125000004103 aminoalkyl group Chemical group 0.000 claims description 6
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
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- -1 aromatic vinyl compound Chemical class 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
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- C09B47/085—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex substituting the central metal atom
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/015—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on semiconductor elements having potential barriers, e.g. having a PN or PIN junction
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Abstract
본 발명은 광흡수제, 중합성 화합물 및 용제를 포함하는 광산란 수지 조성물로서, 상기 광흡수제는 무기입자와 염료가 결합된 것인 광산란 수지 조성물, 이의 경화물을 포함하는 산란층 및 상기 산란층을 포함하는 화상표시장치에 관한 것이다. The present invention is a light-scattering resin composition comprising a light absorber, a polymerizable compound and a solvent, wherein the light absorber is a light-scattering resin composition in which inorganic particles and a dye are combined, a scattering layer including a cured product thereof, and the scattering layer It relates to an image display device that does.
Description
본 발명은 광산란 수지 조성물, 이를 이용하여 제조된 산란층 및 상기 산란층을 포함하는 화상표시장치에 관한 것이다.The present invention relates to a light-scattering resin composition, a scattering layer prepared using the same, and an image display device including the scattering layer.
발광 소자(Light Emitting Diode, LED)를 백라이트 유닛(Back Light Unit, BLU)으로 사용하는 LCD(Liguid Crystal Diplay) TV에서, LED BLU는 빛을 실제로 발하는 부분으로써 LCD TV에서 가장 중요한 부분 중 하나이다.In a Liquid Crystal Display (LCD) TV using a Light Emitting Diode (LED) as a Back Light Unit (BLU), the LED BLU is a part that actually emits light and is one of the most important parts of the LCD TV.
백색의 LED BLU를 형성하는 방법으로는 적색(Red, R), 녹색(Green, G) 및 청색(Blue, B) LED 칩을 조합하여 백색의 LED BLU를 형성하는 방법이 있으나, 적색, 녹색, 청색의 LED 칩을 조합하는 경우에는 LED 칩의 개수가 늘어남에 따라, 복잡한 공정이 요구되어 제조비용이 높은 문제가 있다.As a method of forming a white LED BLU, there is a method of forming a white LED BLU by combining red (R), green (G), and blue (Blue, B) LED chips. In the case of combining blue LED chips, as the number of LED chips increases, a complicated process is required, resulting in high manufacturing cost.
한편, 광변환층에 입사된 청색 광원을 녹색광 및 적색광으로 광변환하여 백색을 구현하는 방법이 있다. 관련하여 도 1은 산란층이 도입된 광변환층의 모식도로, 광변환층에 입사된 청색 광원이 형광체에 의해 녹색광 및 적색광으로 광변환되는 것을 나타낸다. 그러나, 종래 광변환층에 의해 변환된 녹색광 및 적색광은 반치폭이 넓어 다른 색에 영향을 주기 때문에 높은 색순도 및 색재현성을 구현하지 못하는 문제가 있었다.On the other hand, there is a method of implementing white light by photoconverting a blue light source incident on a light conversion layer into green light and red light. In relation to this, FIG. 1 is a schematic diagram of a light conversion layer in which a scattering layer is introduced, and shows that a blue light source incident on the light conversion layer is photoconverted into green light and red light by a phosphor. However, since the green light and red light converted by the conventional light conversion layer have a wide half width and affect other colors, there is a problem in that high color purity and color reproducibility cannot be implemented.
대한민국 등록특허 제10-1795141호는 무기형광체에 비해 발광 스펙트럼이 다양하고 양자효율이 우수하며 특히 가격이 저렴한 장점이 있어 광전환 소자로 활용 가능한 유기형광염료를 개시하고 있으나, 색순도 및 색재현성 향상이 충분치 못한 것으로 보인다. 따라서, 높은 색순도 및 색재현성을 구현할 수 있는 광변환층을 제공하기 위한 연구 개발이 요구되는 실정이다.Korean Patent Registration No. 10-1795141 discloses an organic fluorescent dye that can be used as a light conversion device because it has a diverse emission spectrum, excellent quantum efficiency, and particularly low price compared to inorganic fluorescent substances, but has improved color purity and color reproducibility. It seems not enough. Therefore, there is a need for research and development to provide a light conversion layer capable of implementing high color purity and color reproducibility.
본 발명은 광변환층의 색순도 및 색재현율 향상시키기 위하여 광변환층의 상부 내지 하부에 도입되는 산란층의 제조에 적합한 광산란 수지 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a light-scattering resin composition suitable for the manufacture of a scattering layer introduced into the top or bottom of the light-conversion layer in order to improve the color purity and color reproducibility of the light-conversion layer.
또한, 본 발명은 상기 광산란 수지 조성물을 이용하여 제조된 산란층을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a scattering layer prepared using the light scattering resin composition.
또한, 본 발명은 상기 산란층을 포함하는 화상표시장치를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an image display device including the scattering layer.
본 발명은 광흡수제, 중합성 화합물 및 용제를 포함하는 광산란 수지 조성물로서, 상기 광흡수제는 무기입자와 염료가 결합된 것인 광산란 수지 조성물을 제공한다.The present invention provides a light scattering resin composition comprising a light absorber, a polymerizable compound and a solvent, wherein the light absorber is a combination of inorganic particles and a dye.
또한, 본 발명은 상기 광산란 수지 조성물의 경화물을 포함하는 산란층을 제공한다.In addition, the present invention provides a scattering layer including a cured product of the light scattering resin composition.
또한, 본 발명은 상기 산란층을 포함하는 화상표시장치를 제공한다.In addition, the present invention provides an image display device including the scattering layer.
본 발명에 따른 광산란 수지 조성물은 무기입자와 염료가 결합된 광흡수제를 포함함으로써, 색순도 저하를 유발하는 녹색광과 적색광 사이의 540 내지 620 nm 파장 영역의 빛을 흡수할 수 있다. 이에 따라 청색 광원으로부터 변환된 녹색광과 적색광의 색순도를 높일 수 있으며, 결과적으로 높은 색재현율을 달성할 수 있다.The light-scattering resin composition according to the present invention may absorb light in a wavelength range of 540 to 620 nm between green light and red light, which causes a decrease in color purity, by including a light absorber in which inorganic particles and a dye are combined. Accordingly, color purity of the green light and red light converted from the blue light source may be increased, and as a result, a high color reproduction rate may be achieved.
또한, 상기 광산란 수지 조성물의 경화물을 포함하는 산란층 및 상기 산란층을 포함하는 화상표시장치는 색재현율이 향상됨과 동시에, 산란각도 및 내광성이 우수한 효과를 제공한다.In addition, the scattering layer including the cured product of the light-scattering resin composition and the image display device including the scattering layer have improved color gamut and excellent scattering angle and light resistance.
도 1은 종래의 산란층이 도입된 광변환층(A) 및 본원발명에 따른 산란층이 도입된 광변환층(B)을 나타내는 모식도이다.
도 2는 본 발명의 합성예 2에 따라 합성된 광흡수제의 광흡수 스펙트럼 측정 결과를 나타낸 도이다.
도 3은 광원, 산란층이 도입되지 않은 종래의 광변환층, 본 발명의 실시예 및 비교예에 따른 도막의 광흡수 스펙트럼 측정 결과를 나타낸 도이다.1 is a schematic view showing a light conversion layer (A) to which a conventional scattering layer is introduced and a light conversion layer (B) to which a scattering layer according to the present invention is introduced.
2 is a diagram showing the measurement result of the light absorption spectrum of the light absorber synthesized according to Synthesis Example 2 of the present invention.
Figure 3 is a diagram showing the light absorption spectrum measurement results of a light source, a conventional light conversion layer in which a scattering layer is not introduced, and coating films according to Examples and Comparative Examples of the present invention.
본 발명은 광흡수제, 중합성 화합물 및 용제를 포함하는 광산란 수지 조성물로서, 상기 광흡수제는 무기입자와 염료가 결합된 것인 광산란 수지 조성물, 이의 경화물을 포함하는 산란층 및 상기 산란층을 포함하는 화상표시장치에 관한 것으로, 본 발명에 따른 광산란 수지 조성물은 무기입자와 염료가 결합된 광흡수제를 포함함으로써, 색순도 저하를 유발하는 녹색광과 적색광 사이의 540 내지 620 nm 파장 영역의 빛을 흡수하여 청색 광원으로부터 변환된 녹색광과 적색광의 색순도를 높일 수 있고, 상기 광산란 수지 조성물의 경화물을 포함하는 산란층을 양자점 광변환층의 상부 내지 하부에 도입함으로써, 산란각도 및 내광성이 우수하고, 색재현율이 향상된 화상표시장치를 제공할 수 있다.The present invention is a light-scattering resin composition comprising a light absorber, a polymerizable compound and a solvent, wherein the light absorber is a light-scattering resin composition in which inorganic particles and a dye are combined, a scattering layer including a cured product thereof, and the scattering layer The light scattering resin composition according to the present invention absorbs light in the wavelength range of 540 to 620 nm between green light and red light, which causes color purity degradation, by including a light absorber in which inorganic particles and dyes are combined. It is possible to increase the color purity of green light and red light converted from a blue light source, and by introducing a scattering layer containing a cured product of the light scattering resin composition to the top or bottom of the quantum dot light conversion layer, the scattering angle and light resistance are excellent, and the color gamut is excellent. This improved image display device can be provided.
이하, 본 발명의 구성을 상세히 설명한다. Hereinafter, the configuration of the present invention will be described in detail.
<광산란 수지 조성물><Light Scattering Resin Composition>
광흡수제light absorber
본 발명의 광산란 수지 조성물은 광흡수제를 포함한다. 상기 광흡수제는 무기입자와 염료가 결합된 것으로, 특정 파장 영역의 빛을 흡수하여 색영역을 향상시키고, 상기 흡수된 파장 영역 외의 빛을 산란시켜 변환율을 향상시키는 역할을 한다. 상기 무기입자와 염료는 화학결합에 의해 결합된 것을 특징으로 할 수 있다. The light scattering resin composition of the present invention includes a light absorber. The light absorber is a combination of inorganic particles and a dye, and serves to improve a color gamut by absorbing light in a specific wavelength range and improve conversion rate by scattering light outside the absorbed wavelength range. The inorganic particle and the dye may be characterized in that they are bonded by a chemical bond.
본 발명의 광흡수제는 540nm 내지 620nm 에서 최대흡광도를 가질 수 있고, 바람직하게는 560nm 내지 600nm 에서 최대흡광도를 가질 수 있으며, 더욱 바람직하게는 580nm 내지 590nm 에서 최대흡광도를 가질 수 있다. 광흡수제의 최대흡광도가 상기 범위에 해당하는 경우, 색재현율 향상이 극대화 될 수 있으므로 바람직하다.The light absorber of the present invention may have a maximum absorbance at 540 nm to 620 nm, preferably a maximum absorbance at 560 nm to 600 nm, and more preferably a maximum absorbance at 580 nm to 590 nm. When the maximum absorbance of the light absorber falls within the above range, it is preferable because improvement in color reproduction rate can be maximized.
상기 무기입자는 당 업계에서 일반적으로 사용되는 것을 특별히 제한 없이 사용할 수 있으나, 일 예로 금속산화물을 사용할 수 있고, 상기 금속산화물은 예를 들면 Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상의 산화물일 수 있다. 보다 구체적으로는, Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, ITO, IZO, ATO, ZnO-Al, Nb2O3, SnO, MgO 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상을 포함할 수 있으며, 필요에 따라 아크릴레이트와 같은 불포화 결합을 갖는 화합물로 표면처리된 것들도 사용될 수 있으나, 이에 한정되는 것은 아니다.The inorganic particles commonly used in the art may be used without particular limitation, but metal oxides may be used as an example, and the metal oxides are, for example, Li, Be, B, Na, Mg, Al, Si, K , Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd , at least one oxide selected from the group consisting of Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In, and combinations thereof. can More specifically, Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO-Al, Nb 2 O 3 , SnO , MgO, and combinations thereof, and may include one or more selected from the group consisting of, and, if necessary, those surface-treated with a compound having an unsaturated bond such as acrylate may also be used, but are not limited thereto.
상기 산란입자는 평균입경이 10 내지 1000nm 일 수 있고, 바람직하게는 10 내지 800nm 일 수 있으며, 보다 바람직하게는 100 내지 500nm 일 수 있다. 산란입자의 평균입경이 상기 범위를 만족하는 경우, 광원으로부터 방출된 빛의 충분한 산란효과를 기대할 수 있으며, 조성물 내에 산란입자가 가라 앉는 것을 방지하고, 균일한 품질의 산란층 표면을 얻을 수 있으므로 바람직하다.The scattering particles may have an average particle diameter of 10 to 1000 nm, preferably 10 to 800 nm, and more preferably 100 to 500 nm. When the average particle diameter of the scattering particles satisfies the above range, a sufficient scattering effect of the light emitted from the light source can be expected, the sinking of the scattering particles in the composition can be prevented, and the surface of the scattering layer of uniform quality can be obtained. do.
상기 염료는 아크리딘계, 아릴메탄계, 테트라아자포피린계, 프탈로시아닌계, 폴리시클릭 방향족 탄화수소계, 폴리시클릭 헤테로방향족계, 피렌계, 피롤계, 로다민계, 페녹사존계, 크산텐계, 트리아졸계 및 페릴렌계로 이루어진 군으로부터 선택되는 하나 이상일 수 있으며, 바람직하게는 테트라아자포피린 또는 프탈로시아닌계일 수 있고, 더욱 바람직하게는 하기 화학식 1로 표시되는 화합물일 수 있다.The dyes are acridine-based, arylmethane-based, tetraazaporphyrin-based, phthalocyanine-based, polycyclic aromatic hydrocarbon-based, polycyclic heteroaromatic, pyrene-based, pyrrole-based, rhodamine-based, phenoxazone-based, xanthene-based, triazole-based and It may be at least one selected from the group consisting of perylene-based compounds, preferably tetraazaporphyrin or phthalocyanine-based compounds, and more preferably a compound represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서, R1 내지 R8은 각각 독립적으로 수소; 비치환된 페닐기; 탄소수 1 내지 8의 알킬기; 탄소수 1 내지 8의 알콕시기; 니트로기; 할로겐 원자; 시아노기; 탄소수 1 내지 8의 알킬아미노기; 탄소수 1 내지 8의 아미노알킬기; 또는 탄소수 1 내지 8의 알콕시기, 탄소수 1 내지 8의 알킬기, 니트로기, 할로겐 원자, 탄소수 1 내지 8의 알킬아미노기, 탄소수 1 내지 8의 아미노알킬기, 시아노기, 카르복실기, 술폰기, 페놀성 수산기 및 인산기 중에서 선택된 하나 이상의 치환기를 갖는 페닐기이고, 상기 R1 내지 R8 중 적어도 하나는 말단에 카르복실기, 술폰기, 페놀성 수산기 및 인산기 중에서 선택된 하나 이상의 치환기를 갖는 페닐기이다.In Formula 1, R 1 to R 8 are each independently hydrogen; unsubstituted phenyl group; an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; nitro group; halogen atom; cyano group; Alkylamino group having 1 to 8 carbon atoms; An aminoalkyl group having 1 to 8 carbon atoms; or an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a halogen atom, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, a sulfone group, a phenolic hydroxyl group, and A phenyl group having at least one substituent selected from a phosphoric acid group, and at least one of R 1 to R 8 is a phenyl group having at least one substituent selected from a carboxyl group, a sulfone group, a phenolic hydroxyl group, and a phosphoric acid group at a terminal.
상기 화학식 1에서, M은 Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th 및 U로 이루어지는 군으로부터 선택되는 어느 하나이다. 또한 상기 M은 암모니아, 물 및 할로겐 원소 중에서 선택된 하나 이상의 리간드를 가질 수 있다. In
상기 염료는 상기 무기입자의 총 중량 대비 0.1 내지 30 중량%로 포함될 수 있으며, 바람직하게는 1 내지 25 중량%로 포함될 수 있다. 염료가 상기 함량범위로 포함되는 경우, 염료와 상기 무기입자의 비중을 고려하여 화학적결합을 적합한 형태로 유지할 수 있기 때문에 바람직하며, 상기 함량 이상으로 포함되면 염료의 응집이 발생하여 코팅 후 표면 불량등의 문제가 발생 할 수 있다.The dye may be included in an amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, based on the total weight of the inorganic particles. When the dye is included in the above content range, it is preferable because the chemical bonding can be maintained in a suitable form in consideration of the specific gravity of the dye and the inorganic particles. of problems may arise.
상기 광흡수제는 예를 들면, 하기 화학식 2로 표시되는 화합물일 수 있다. The light absorber may be, for example, a compound represented by Chemical Formula 2 below.
[화학식 2][Formula 2]
상기 화학식 2에서, R1 내지 R4는 각각 독립적으로 수소; 비치환된 페닐기; 탄소수 1 내지 8의 알킬기; 탄소수 1 내지 8의 알콕시기; 니트로기; 할로겐 원자; 시아노기; 탄소수 1 내지 8의 알킬아미노기; 탄소수 1 내지 8의 아미노알킬기; 또는 탄소수 1 내지 8의 알콕시기, 탄소수 1 내지 8의 알킬기, 니트로기, 할로겐 원자, 탄소수 1 내지 8의 알킬아미노기, 탄소수 1 내지 8의 아미노알킬기, 시아노기, 카르복실기, 술폰기, 페놀성 수산기 및 인산기 중에서 선택된 하나 이상의 치환기를 갖는 페닐기이다. In
상기 화학식 2에서, M은 Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th 및 U로 이루어지는 군으로부터 선택되는 어느 하나이다. 또한 상기 M은 암모니아, 물 및 할로겐 원소 중에서 선택된 하나 이상의 리간드를 가질 수 있다.In
상기 광흡수제는 광산란 수지 조성물 총 중량에 대하여 1 내지 30 중량%, 바람직하게는 3 내지 25 중량%로 포함될 수 있다. 광흡수제가 상기 함량범위를 만족하는 경우, 광산란 특성이 우수하며 염료의 응집도 발생하지 않음으로 바람직하다. 상기 범위의 이상이 되면 염료의 응집이 발생하여 산란도 및 표면 불량의 문제가 발생 할 수 있다.The light absorber may be included in an amount of 1 to 30% by weight, preferably 3 to 25% by weight, based on the total weight of the light scattering resin composition. When the light absorber satisfies the above content range, it is preferable because light scattering properties are excellent and dye aggregation does not occur. When the amount exceeds the above range, aggregation of the dye may occur, resulting in scattering problems and poor surface quality.
중합성 화합물polymeric compound
상기 중합성 화합물는, 특별히 한정되지 않으나, 카르복실기 함유 불포화 단량체의 중합체, 카르복실기 함유 불포화 단량체 및 이와 공중합 가능한 불포화 결합을 갖는 단량체와의 공중합체 및 이들의 조합으로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.The polymerizable compound is not particularly limited, but at least one selected from the group consisting of a polymer of a carboxyl group-containing unsaturated monomer, a copolymer of a carboxyl group-containing unsaturated monomer and a monomer having an unsaturated bond copolymerizable therewith, and combinations thereof may be used. .
상기 카르복실기 함유 불포화 단량체로는 불포화 모노카르복실산, 불포화 디카르복실산, 불포화 트리카르복실산 등이 사용가능하다. 구체적으로, 불포화 모노카르복실산으로서는, 예를 들면 아크릴산, 메타크릴산, 크로톤산, α-클로로아크릴산, 신남산 등을 들 수 있다. 불포화 디카르복실산으로서는, 예를 들면 푸마르산, 메사콘산, 이타콘산, 시트라콘산 등을 들 수 있다. 불포화 다가 카르복실산은 산무수물일 수도 있으며, 구체적으로는 말레산 무수물, 이타콘산 무수물, 시트라콘산 무수물 등을 들 수 있다. 또한, 불포화 다가 카르복실산은 ω-카르복시폴리카프로락톤모노(메타)아크릴레이트 등의 양 말단에 카르복실기와 수산기를 갖는 폴리머의 모노(메타)아크릴레이트류, 모노메틸말레인산, 5-노보넨-2-카르복실산, 모노-2-((메타)아크릴로일옥시)에틸프탈레이트, 모노-2-((메타)아크릴로일옥시)에틸숙시네이트 등이 가능하다. 이들 불포화 카르복실기를 갖는 화합물들은 각각 단독으로 또는 둘 이상을 조합하여 사용할 수 있으며, 그중 아크릴산 및 메타크릴산이 공중합 반응성 및 현상액에 대한 용해성이 우수하여 바람직하게 사용될 수 있다.As the carboxyl group-containing unsaturated monomer, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids can be used. Specifically, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include fumaric acid, mesaconic acid, itaconic acid, and citraconic acid. An acid anhydride may be sufficient as an unsaturated polyhydric carboxylic acid, and maleic acid anhydride, itaconic acid anhydride, a citraconic acid anhydride, etc. are mentioned specifically. In addition, unsaturated polyhydric carboxylic acids include mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, monomethylmaleic acid, and 5-norbornene-2- carboxylic acids, mono-2-((meth)acryloyloxy)ethylphthalate, mono-2-((meth)acryloyloxy)ethylsuccinate, and the like are possible. These compounds having an unsaturated carboxyl group may be used individually or in combination of two or more, and among them, acrylic acid and methacrylic acid may be preferably used because of their excellent copolymerization reactivity and solubility in a developing solution.
또한, 카르복실기 함유 불포화 단량체와 공중합이 가능한 불포화 결합을 갖는 단량체로는 방향족 비닐 화합물, 불포화 카르복실레이트 화합물, 불포화 아미노알킬카르복실레이트 화합물, 비닐시아나이드 화합물, 불포화 옥세탄카르복실레이트 화합물 등이 사용될 수 있으며, 이들은 1종 단독으로 또한 2종 이상을 조합하여 사용할 수 있다. 구체적으로, 상기 카르복실기 함유 불포화 단량체와 공중합이 가능한 단량체로는 스티렌, α-메틸스티렌, 비닐톨루엔 등의 방향족 비닐 화합물; 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 부틸메타크릴레이트, 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타크릴레이트, 벤질아크릴레이트, 벤질메타크릴레이트 등의 불포화 카르복실레이트 화합물; 아미노에틸아크릴레이트 등의 불포화 아미노알킬카르복실레이트 화합물; 글리시딜메타크릴레이트 등의 불포화 글리시딜카르복실레이트 화합물; 비닐아세테이트, 비닐프로피오네이트 등의 비닐카르복실레이트 화합물; 아크릴로니트릴, 메타크릴로니트릴, α-클로로아크릴로니트릴 등의 비닐시아나이드 화합물; 3-메틸-3-아크릴옥시메틸옥세탄, 3-메틸-3-메타크릴옥시메틸옥세탄, 3-에틸-3-아크릴옥시메틸옥세탄, 3-에틸-3-메타크릴옥시메틸옥세탄, 3-메틸-3-아크릴옥시에틸옥세탄, 3-메틸-3-메타크릴옥시에틸옥세탄, 3-메틸-3-아크릴옥시에틸옥세탄, 3-메틸-3-메타크릴옥시에틸옥세탄 등의 불포화 옥세탄카르복실레이트 화합물 등을 들 수 있다.In addition, as a monomer having an unsaturated bond copolymerizable with a carboxyl group-containing unsaturated monomer, an aromatic vinyl compound, an unsaturated carboxylate compound, an unsaturated aminoalkyl carboxylate compound, a vinyl cyanide compound, an unsaturated oxetane carboxylate compound, etc. may be used. These can be used alone or in combination of two or more. Specifically, monomers copolymerizable with the carboxyl group-containing unsaturated monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate unsaturated carboxylate compounds such as acrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. Unsaturated oxetane carboxylate compounds of , etc. are mentioned.
상기 중합성 화합물은 광산란 수지 조성물 총 중량에 대하여, 1 내지 30 중량%, 바람직하게는 2 내지 15 중량% 로 포함될 수 있다. 중합성 화합물의 함량범위는 최종적으로 얻어지는 광산란 수지 조성물의 코팅성이나 평활성이 양호하게 되는 경향 등을 다각적으로 고려하여 선정된 범위로서, 상기 함량범위를 만족하는 경우, 강도 및 평활성이 양호하고, 코팅불량 등이 발생하지 않아 코팅이 용이하므로 바람직하다.The polymerizable compound may be included in an amount of 1 to 30% by weight, preferably 2 to 15% by weight, based on the total weight of the light scattering resin composition. The content range of the polymerizable compound is a range selected in consideration of various aspects such as the tendency for coating properties and smoothness of the finally obtained light-scattering resin composition to be good, and when the above content range is satisfied, the strength and smoothness are good, and the coating This is preferable because no defects or the like occur and coating is easy.
용제solvent
상기 용제는 상기 언급한 바의 조성을 용해 또는 분산시킬 수 있고, 다른 구성성분들과 반응하지 않는 것이면 어느 것이든 사용이 가능하며, 특별히 한정되지 않는다. 바람직하게는 도포성 및 건조성 면에서 비점이 100 내지 200℃인 유기 용제를 사용할 수 있다.Any solvent can be used as long as it can dissolve or disperse the above-mentioned composition and does not react with other constituents, and is not particularly limited. Preferably, an organic solvent having a boiling point of 100 to 200° C. may be used in terms of coating properties and drying properties.
대표적으로, 사용 가능한 용제로는 알킬렌글리콜 모노알킬에테르류, 알킬렌글리콜알킬에테르아세테이트류, 방향족 탄화수소류, 케톤류, 저급 및 고급 알코올류, 환상 에스테르류 등을 들 수 있다. 보다 구체적으로, 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노프로필에테르, 에틸렌글리콜 모노부틸에테르 등의 알킬렌글리콜 모노알킬에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜 디에틸에테르, 디에틸렌글리콜 디프로필에테르, 디에틸렌글리콜 디부틸에테르 등의 디에틸렌글리콜 디알킬에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 모노프로필에테르아세테이트, 메톡시부틸아세테이트 및 메톡시펜틸아세테이트 등의 알킬렌글리콜 알킬에테르아세테이트류; 벤젠, 톨루엔, 크실렌, 메시틸렌 등의 방향족 탄화수소류; 메틸에틸케톤, 아세톤, 메틸아밀케톤, 메틸이소부틸케톤, 시클로헥사논 등의 케톤류; 에탄올, 프로판올, 부탄올, 헥사놀, 시클로헥산올, 에틸렌글리콜, 글리세린 등의 알코올류; 3-에톡시프로피온산 에틸, 3-메톡시프로피온산 메틸 등의 에스테르류; γ-부티로락톤 등의 환상 에스테르류 등을 들 수 있다.Typically, usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons, such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.
상기 용제는 광산란 수지 조성물의 고형분 총 중량에 대하여, 100 내지 500 중량%, 바람직하게는 200 내지 400 중량%로 포함될 수 있다. 용제가 상기 함령범위로 포함되는 경우, 광산란 수지 조성물은 16.6 내지 50.0 중량%, 바람직하게는 20 내지 33.3 중량%의 고형분 함량으로 제조될 수 있으며, 이는 제조하고자 하는 도막의 두께를 고려하여 선정된 범위이다.The solvent may be included in an amount of 100 to 500% by weight, preferably 200 to 400% by weight, based on the total weight of the solid content of the light scattering resin composition. When the solvent is included in the above range, the light scattering resin composition may be prepared with a solid content of 16.6 to 50.0% by weight, preferably 20 to 33.3% by weight, which is a range selected in consideration of the thickness of the coating film to be produced. to be.
산란입자scattering particles
본 발명의 광산란 수지 조성물은 산란입자를 더 포함할 수 있다. 상기 산란입자는 상기 광흡수제에 포함되는 무기입자와 함께, 광원으로부터 방출되는 광을 산란하는 역할을 한다.The light-scattering resin composition of the present invention may further include scattering particles. The scattering particles together with the inorganic particles included in the light absorber serve to scatter light emitted from a light source.
상기 산란입자는 당 업계에서 일반적으로 사용되는 것을 특별히 제한 없이 사용할 수 있으나, 일 예로 금속산화물을 사용할 수 있고, 상기 금속산화물은 예를 들면 Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상의 산화물일 수 있다. 보다 구체적으로는, Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, ITO, IZO, ATO, ZnO-Al, Nb2O3, SnO, MgO 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상을 포함할 수 있으며, 필요에 따라 아크릴레이트와 같은 불포화 결합을 갖는 화합물로 표면처리된 것들도 사용될 수 있으나, 이에 한정되는 것은 아니다.The scattering particles generally used in the art may be used without particular limitation, but, for example, metal oxides may be used, and the metal oxides may be, for example, Li, Be, B, Na, Mg, Al, Si, K , Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd , at least one oxide selected from the group consisting of Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In, and combinations thereof. can More specifically, Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO-Al, Nb 2 O 3 , SnO , MgO, and combinations thereof, and may include one or more selected from the group consisting of, and, if necessary, those surface-treated with a compound having an unsaturated bond such as acrylate may also be used, but are not limited thereto.
상기 산란입자는 평균입경이 10 내지 1000nm 일 수 있고, 바람직하게는 10 내지 800nm 일 수 있으며, 보다 바람직하게는 100 내지 500nm 일 수 있다. 산란입자의 평균입경이 상기 범위를 만족하는 경우, 광원으로부터 방출된 빛의 충분한 산란효과를 기대할 수 있으며, 조성물 내에 산란입자가 가라 앉는 것을 방지하고, 균일한 품질의 산란층 표면을 얻을 수 있으므로 바람직하다. The scattering particles may have an average particle diameter of 10 to 1000 nm, preferably 10 to 800 nm, and more preferably 100 to 500 nm. When the average particle diameter of the scattering particles satisfies the above range, a sufficient scattering effect of the light emitted from the light source can be expected, the sinking of the scattering particles in the composition can be prevented, and the surface of the scattering layer of uniform quality can be obtained. do.
본 발명에서 "평균입경"이란, 수평균 입경일 수 있으며, 예컨대 전계방출 주자전자현미경(FE-SEM) 또는 투과 전자 현미경(TEM)에 의해 관찰한 상으로부터 구할 수 있다. 구체적으로, FE-SEM 또는 TEM의 관찰 화상으로부터 몇 개의 샘플을 추출하고 이들 샘플의 직경을 측정하여 산술 평균한 값으로 얻을 수 있다.In the present invention, the "average particle diameter" may be a number average particle diameter, and may be obtained from an image observed by, for example, a field emission electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples are extracted from observation images of FE-SEM or TEM, and the diameters of these samples are measured, and an arithmetic average value can be obtained.
본 발명의 광산란 수지 조성물이 상기 산란입자를 더 포함하는 경우, 상기 산란입자는 상기 광산란 수지 조성물 총 중량에 대하여, 1 내지 30 중량%로 포함될 수 있으며, 바람직하게는 5 내지 20 중량% 로 포함될 수 있다. 산란입자가 상기 함량범위를 만족하는 경우, 산란각도와 색특성이 우수하므로 바람직하다. When the light-scattering resin composition of the present invention further includes the scattering particles, the scattering particles may be included in an amount of 1 to 30% by weight, preferably 5 to 20% by weight, based on the total weight of the light-scattering resin composition. have. When the scattering particles satisfy the above content range, it is preferable because the scattering angle and color characteristics are excellent.
첨가제additive
본 발명의 광산란 수지 조성물은 첨가제를 더 포함할 수 있다. The light-scattering resin composition of the present invention may further include an additive.
상기 첨가제의 종류는 사용자의 필요에 따라 정해질 수 있는 것으로 본 발명에서 특별히 한정하는 것은 아니나, 기판과의 접착성을 향상시키기 위해 카르복실기, 메타크릴로일기, 이소시아네이트기, 에폭시기 등의 반응성 치환기를 갖는 실란 커플링제 또는 코팅성 향상을 위한 계면활성제를 포함할 수 있다. The type of the additive may be determined according to the needs of the user and is not particularly limited in the present invention, but has a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc. to improve adhesion with a substrate. A silane coupling agent or a surfactant for improving coating properties may be included.
상기 실란 커플링제의 구체적인 예로서는 트리메톡시실릴벤조산, γ-메타크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아네이트프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 함께 사용하는 것이 좋다.Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxy propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and it is preferable to use one of these alone or in combination of two or more.
상기 실란 커플링제는 광산란 수지 조성물 100 중량부에 대해 0.001 내지 5 중량부로 포함되는 것이 바람직하다.The silane coupling agent is preferably included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the light scattering resin composition.
상기 계면 활성제로는 BM-1000, BM-1100(BM Chemie사 제품), 메카 팩 F 142D, 동 F 172, 동 F 173, 동 F 183, 동 F 475(다이닛폰잉키 가가꾸 고교(주) 제품), 프로라드 FC-135, 동 FC-170C, 동 FC-430, 동 FC-431(스미토모 스리엠(주) 제품), 사프론 S-112, 동 S-113, 동 S-131, 동 S-141, 동 S-145(아사히 가라스(주) 제품), SH-28PA, 동-190, 동-193, SZ-6032, SF-8428(도레 시리콘(주) 제품), S-510(치소(Chisso)사 제품), KP-321, KP-322, KP-323, KP-324, KP-326, KP-340, KP-341(신에츠화학공업(주) 제품) 등의 계면 활성제를 들 수 있으며, 이들 중 1종 단독으로 또는 2종 이상을 함께 사용하는 것이 좋다.As the surfactant, BM-1000, BM-1100 (product of BM Chemie), Meka Pack F 142D, F 172, F 173, F 183, F 475 (product of Dainippon Ink Chemical Industry Co., Ltd.) ), Prorad FC-135, Copper FC-170C, Copper FC-430, Copper FC-431 (Sumitomo 3M Co., Ltd.), Saffron S-112, Copper S-113, Copper S-131, Copper S -141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, I-190, I-193, SZ-6032, SF-8428 (manufactured by Tore Silicon Co., Ltd.), S-510 ( Surfactants such as Chisso (manufactured by Chisso), KP-321, KP-322, KP-323, KP-324, KP-326, KP-340, KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) It is preferable to use one of these alone or in combination of two or more.
상기 계면 활성제는 광산란 수지 조성물 100 중량부에 대해 0.001 내지 5 중량부로 포함되는 것이 바람직하다.The surfactant is preferably included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the light scattering resin composition.
본 발명의 광산란 수지 조성물의 제조 방법은 당 업계에 알려진 통상적인 방법으로 제조될 수 있는 것으로, 본 발명에서 특별히 한정하는 것은 아니나, 일 예를 들면, 하기와 같은 방법으로 제조될 수 있다.The method for preparing the light scattering resin composition of the present invention may be prepared by a conventional method known in the art, and is not particularly limited in the present invention, but may be prepared by, for example, the following method.
산란입자를 미리 용제와 혼합하여 평균입경이 30 내지 300nm가 될 때까지 비드 밀 등을 이용하여 분산시킨다. 이때, 필요에 따라 분산제를 추가로 사용할 수 있다. 얻어진 분산액(이하, 밀 베이스라고 하는 경우도 있음)에 광흡수제, 중합성 화합물, 필요에 따라 사용되는 그밖의 성분과 필요에 따라 추가의 용제를 소정의 농도가 되도록 더 첨가하여 목적하는 광산란 수지 조성물을 얻을 수 있다.The scattering particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter is 30 to 300 nm. At this time, a dispersant may be additionally used as needed. To the obtained dispersion (hereinafter sometimes referred to as mill base), a light absorber, a polymerizable compound, other components used as needed, and additional solvents as needed are further added to a predetermined concentration to obtain the desired light scattering resin composition. can be obtained.
<산란층><Scattering layer>
또한, 본 발명은 본 발명에 따른 광산란 수지 조성물의 경화물을 포함하는 산란층을 제공한다. In addition, the present invention provides a scattering layer comprising a cured product of the light-scattering resin composition according to the present invention.
본 발명의 산란층 형성 방법은 당 업계에 알려진 통상의 방법을 적용할 수 있는 것으로 그 방법을 특별히 한정하지는 않으며, 일반적으로 열경화를 통한 도막의 형성방법을 통해 제조될 수 있지만, 필요에 따라 광경화 과정이 추가로 도입될 수도 있다.The scattering layer formation method of the present invention can apply a conventional method known in the art, and the method is not particularly limited. Generally, it can be manufactured through a method of forming a coating film through thermal curing, but if necessary, light An additional process may be introduced.
본 발명에 따른 산란층은 색순도 저하를 유발하는 특정 파장 영역의 빛을 흡수할 수 있는 광흡수제를 포함함으로써 색재현율이 향상되고, 산란각도 및 내광성이 우수한 효과를 제공한다.The scattering layer according to the present invention includes a light absorber capable of absorbing light in a specific wavelength region causing a decrease in color purity, thereby improving color reproduction and providing excellent scattering angle and light resistance.
<화상표시장치><Image display device>
또한, 본 발명은 본 발명에 따른 산란층을 포함하는 화상표시장치를 제공한다. In addition, the present invention provides an image display device including the scattering layer according to the present invention.
상기 화상표시장치는 예를 들면, 상기 화상 표시 장치는 구체적으로, 액정 디스플레이(액정표시장치; LCD), 유기 EL 디스플레이(유기 EL 표시장치), 퀀텀닷 디스플레이, 액정 프로젝터, 게임기용 표시장치, 휴대전화 등의 휴대단말용 표시장치, 디지털 카메라용 표시장치, 카 네비게이션용 표시장치 등의 표시장치 등을 들 수 있으며, 본 발명의 일 실시형태에 따른 화상표시장치는 퀀텀닷 디스플레이일 수 있다.The image display device, for example, the image display device specifically, a liquid crystal display (liquid crystal display; LCD), an organic EL display (organic EL display device), a quantum dot display, a liquid crystal projector, a display device for a game machine, a portable A display device for a mobile terminal such as a phone, a display device for a digital camera, a display device for a car navigation system, and the like, and the like, may be used.
상기 화상표시장치는 광원 등과 같은 발광 장치, 도광판, 컬러필터를 포함하는 액정표시부 등과 같이 통상적으로 화상표시장치에 포함될 수 있는 그 밖의 구성들을 포함할 수 있으며, 본 발명에서 이를 한정하지는 않는다.The image display device may include other components that may be included in a conventional image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter, but the present invention is not limited thereto.
본 발명에 따른 화상표시장치는 본 발명에 따른 산란층을 양자점 광변환층의 상부 내지 하부에 도입함으로써, 색순도 저하를 유발하는 특정 파장 영역의 빛을 흡수하여 색재현율이 향상되고, 산란각도 및 내광성이 우수한 이점이 있다.The image display device according to the present invention absorbs light in a specific wavelength region that causes a decrease in color purity by introducing the scattering layer according to the present invention to the top or bottom of the quantum dot light conversion layer, thereby improving the color reproduction rate, improving the scattering angle and light resistance. This has great advantages.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 이하의 실시예 및 비교예에서 함량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. In the following Examples and Comparative Examples, "%" and "parts" representing contents are based on weight unless otherwise specified.
<실시예><Example>
합성예 1: 염료의 합성Synthesis Example 1: Synthesis of Dye
[반응식 1][Scheme 1]
유기 용매인 디메틸포름아미드(N,N-dimethylformamide; DMF) 25g에 하기 화학식 3으로 표시되는 화합물 0.02 mol과, 금속염인 CuCl2 dihydrate 0.04 mol을 넣은 후 160℃에서 4시간 가량 반응시켜 합성한다. 0.02 mol of the compound represented by
[화학식 3][Formula 3]
반응이 종료되면 실온까지 냉각시킨 후 암모니아수 30㎖를 추가하고, 침전물이 생성되면 감압 여과하여 침전물을 거른 뒤, 암모니아수를 이용하여 여액의 색이 맑아질 때까지 세척한다. 세척이 완료되면 열풍 건조기에서 약 8 시간 건조시켜 입자 크기가 균일한 하기 화학식 4로 표시되는 화합물인 염료 분말 1.82g을 얻었다. 상기 제조된 화합물의 수율은 중량기준 70.3%로 측정되었다.When the reaction is complete, cool to room temperature, add 30 ml of ammonia water, and when a precipitate is formed, filter the precipitate by filtering under reduced pressure, and then wash with ammonia water until the color of the filtrate becomes clear. After the washing was completed, the mixture was dried in a hot air dryer for about 8 hours to obtain 1.82 g of a dye powder having a uniform particle size represented by
[화학식 4][Formula 4]
합성예 2: 광흡수제의 합성Synthesis Example 2: Synthesis of Light Absorber
상기 화학식 4로 표시되는 화합물을 0.3 mM의 농도로 MeOH에 용해 시킨 용액 100g에 TiO2(Chemours사 Ti-Pure R960) 50g를 넣어서 10시간 침지 후, MeOH로 세척하여 건조하여 광흡수제를 제조하였다. 상기 제조된 광흡수제 중의 염료의 함량은 중량 열무게 분석법을 통하여 측정할 수 있고, TA사의 Q50제품을 사용하여 질소 분위기에서 10℃/min의 측정속도로 측정하였으며, 측정된 염료의 함량은 무기입자 중량 대비 4.5 중량% 이었다. 또한, 상기 제조된 광흡수제의 광흡수 스펙트럼을 측정하였으며, 그 결과를 도 2에 나타내었다.A light absorber was prepared by adding 50 g of TiO 2 (Ti-Pure R960 from Chemours) to 100 g of a solution in which the compound represented by
실시예 1~3 및 비교예 1~5: 광산란 수지 조성물의 제조Examples 1 to 3 and Comparative Examples 1 to 5: Preparation of light scattering resin composition
하기 표 1에 기재된 각 구성 및 함량으로 광산란 수지 조성물을 제조하였다.A light scattering resin composition was prepared with each composition and content shown in Table 1 below.
화합물polymeric
compound
A: 합성예 2의 광흡수제A: Light absorber of Synthesis Example 2
B: TiO2 (Chemours사 Ti-Pure R960)B: TiO 2 (Chemours Ti-Pure R960)
C: 합성예 1의 염료C: dye of Synthesis Example 1
D: KAYARAD DPHA (NIPPON KAYAKU CO.LTD사 제품)D: KAYARAD DPHA (manufactured by NIPPON KAYAKU CO.LTD)
E-1: KBM-502 (ShinEtsu사 제품)E-1: KBM-502 (manufactured by ShinEtsu)
E-2: KP-323 (ShinEtsu사 제품)E-2: KP-323 (manufactured by ShinEtsu)
F: 프로필렌글리콜모노메틸에테르아세테이트(PGMEA)F: Propylene glycol monomethyl ether acetate (PGMEA)
제조예: 도막의 제조Production example: production of coating film
실시예 및 비교예에서 제조된 광산란 수지 조성물을 이용하여 도막을 제조하였다. 즉, 상기 각각의 광산란 수지 조성물을 스핀 코팅법으로 유리 기판 위에 도포한 다음, 가열판 위에 놓고 100℃의 온도에서 2분간 유지하여 용제를 휘발시켰다. 230℃의 가열 오븐에서 20분 동안 가열하여 도막을 제조하였다. 상기에서 제조된 도막의 두께는 5.0㎛이었다. 또한, 상기에서 제조된 도막에 청색 광원을 비추어 광흡수 스펙트럼을 측정하였으며, 그 결과를 도 3에 나타내었다.Coating films were prepared using the light scattering resin compositions prepared in Examples and Comparative Examples. That is, each of the light-scattering resin compositions was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 2 minutes to volatilize the solvent. A coating film was prepared by heating in a heating oven at 230° C. for 20 minutes. The thickness of the coating film prepared above was 5.0 μm. In addition, the light absorption spectrum was measured by illuminating the coating film prepared above with a blue light source, and the results are shown in FIG. 3 .
<실험예><Experimental example>
실험예 1: 산란각도 평가Experimental Example 1: Scattering angle evaluation
상기에서 제조된 도막에 도막 면에 수직으로 광을 비추고, Ez-Con(EZContrast XL88)를 사용하여 휘도가 50% 수준이 되는 각도를 측정하였으며, 그 결과를 하기 표 2에 기재하였다. Light was irradiated perpendicularly to the surface of the coating film prepared above, and the angle at which the luminance reached 50% was measured using Ez-Con (EZContrast XL88), and the results are shown in Table 2 below.
직광을 기준으로 얼마나 많은 각도까지 빛을 산란시키는지를 평가하는 것으로, 각도가 크다는 것은 광을 더 많은 각도로 산란시킬 수 있다는 의미이며 우수한 성능이다. It evaluates how many angles light is scattered based on direct light. A larger angle means that more angles can scatter light, which is an excellent performance.
실험예 2: 색좌표 측정Experimental Example 2: Color coordinate measurement
상기에서 제조된 도막의 광 spectrum을 Spectrum meter(Ocean Optics사 제)를 이용하여 측정하였다. Blue/Green/Red 각 광원의 색 값을 CIE1931 색좌표계에서의 x, y 좌표값으로 나타내었으며, 그 결과는 하기 표 2에 기재하였다. The light spectrum of the coating film prepared above was measured using a spectrum meter (manufactured by Ocean Optics). The color values of each light source of Blue/Green/Red were expressed as x, y coordinate values in the CIE1931 color coordinate system, and the results are shown in Table 2 below.
실험예 3: 색재현율 평가Experimental Example 3: Evaluation of color gamut
NTSC 색좌표인 Blue(0.1400, 0.0800) Green(0.2100, 0.7100) Red(0.6700, 0.3300)의 색재현율을 100%라고 기준을 잡아, 상기에서 측정한 색좌표를 사용하여 상대적인 색재현율 면적을 계산하였으며, 그 결과를 하기 표 2에 기재하였다. 계산된 값이 클수록 더 넓은 영역의 색을 표현할 수 있다는 의미이다.Based on the color gamut of NTSC color coordinates Blue (0.1400, 0.0800) Green (0.2100, 0.7100) Red (0.6700, 0.3300) as 100%, the relative color gamut area was calculated using the color coordinates measured above. are listed in Table 2 below. A larger calculated value means that a wider range of colors can be expressed.
실험예 4: 내광성 평가Experimental Example 4: Evaluation of light fastness
상기에서 제조된 도막의 휘도를 내광성 장비에서 1일(24h)의 간격으로 측정하였다. 상기 휘도는 Spectrum meter(Ocean Optics사 제)를 이용하여 측정하였고, 초기 대비 5%가 하락하는 시점을 측정하여 하기 표 2에 기재하였다. 측정된 숫자가 클수록 휘도의 초기 대비 5% 이하로 변화하는데 더 많은 시간이 필요한 것이므로, 내광성이 우수하다는 의미이다. The luminance of the coating film prepared above was measured at intervals of 1 day (24 h) in a light fastness equipment. The luminance was measured using a spectrum meter (manufactured by Ocean Optics), and the time point at which 5% decreased compared to the initial value was measured and listed in Table 2 below. The larger the measured number, the more time is required for the luminance to change to 5% or less compared to the initial value, which means that the light fastness is excellent.
상기 표 2를 참조하면, 광흡수제를 포함하는 실시예 1 내지 3의 경우, 산란각도, 색재현율 및 내광성이 모두 우수한 효과를 나타내고 있으며, 특히 광흡수제와 산란입자를 동시에 포함하는 실시예 2 및 3의 경우, 산란각도, 색재현율 및 내광성면에서 광흡수제만을 포함하는 실시예 1 보다 더 우수한 효과를 나타내고 있음을 확인할 수 있다.Referring to Table 2, in the case of Examples 1 to 3 including the light absorber, scattering angle, color gamut and light fastness are all excellent, and in particular, Examples 2 and 3 including the light absorber and scattering particles at the same time In the case of , it can be confirmed that the scattering angle, color gamut and light fastness show a better effect than Example 1 including only the light absorber.
이에 반하여, 광흡수제를 포함하지 않는 비교예 1 내지 3의 경우, 실시예 1 내지 3 대비 산란각도, 색재현율 및 내광성이 모두 현저히 저하되는 것을 확인할 수 있다. 또한, 본원 실시예 상의 광흡수제를 이루는 산란입자 및 염료를 각각 포함하는 비교예 4 및 5의 경우, 내광성 및 색재현율이 현저히 저하되어 산란각도, 색재현율 및 내광성을 동시에 향상시키고자 하는 본원발명이 목적하는 효과를 얻을 수 없음을 확인할 수 있다. On the other hand, in the case of Comparative Examples 1 to 3 not containing a light absorber, it can be seen that the scattering angle, color gamut and light fastness are all significantly lowered compared to Examples 1 to 3. In addition, in the case of Comparative Examples 4 and 5 each including the scattering particles and dye constituting the light absorber of the present embodiment, the light fastness and color gamut are significantly lowered, so that the scattering angle, color gamut and light fastness are simultaneously improved. It can be confirmed that the desired effect cannot be obtained.
한편, 도 3을 참조하면, 실시예 1 및 2가 종래의 광변환층 및 비교예 1과 대비하여 적색광, 녹색광 및 청색광 파장에서 보다 높은 흡수 피크를 나타내며, 색순도 저하를 유발하는 540~620nm 파장에서 보다 낮은 흡수 피크를 나타내는 점을 확인할 수 있다. 이와 같은 결과로부터 본원발명의 광산란 수지 조성물은 540~620nm 파장의 빛을 투과시키지 않으며, 이에 따라 청색 광원으로부터 변환된 녹색광과 적색광의 색순도를 높일 수 있고, 결과적으로 높은 색재현율을 달성할 수 있음을 알 수 있다. On the other hand, referring to FIG. 3, Examples 1 and 2 exhibit higher absorption peaks at red light, green light, and blue light wavelengths compared to the conventional photoconversion layer and Comparative Example 1, and at a wavelength of 540 to 620 nm that causes a decrease in color purity. It can be confirmed that a lower absorption peak is exhibited. From these results, it can be seen that the light-scattering resin composition of the present invention does not transmit light with a wavelength of 540 to 620 nm, thereby increasing the color purity of green light and red light converted from a blue light source, and consequently achieving a high color gamut. Able to know.
Claims (13)
상기 광흡수제는 무기입자와 염료가 결합된 것인 광산란 수지 조성물.A light scattering resin composition comprising a light absorber, a polymerizable compound and a solvent,
The light absorber is a light-scattering resin composition in which inorganic particles and dyes are combined.
상기 염료는 아크리딘계, 아릴메탄계, 테트라아자포피린계, 프탈로시아닌계, 폴리시클릭 방향족 탄화수소계, 폴리시클릭 헤테로방향족계, 피렌계, 피롤계, 로다민계, 페녹사존계, 크산텐계, 트리아졸계 및 페릴렌계로 이루어진 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The dyes are acridine-based, arylmethane-based, tetraazaporphyrin-based, phthalocyanine-based, polycyclic aromatic hydrocarbon-based, polycyclic heteroaromatic-based, pyrene-based, pyrrole-based, rhodamine-based, phenoxazone-based, xanthene-based, triazole-based and A light scattering resin composition, characterized in that at least one selected from the group consisting of perylene.
상기 염료는 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는 광산란 수지 조성물.
[화학식 1]
(상기 화학식 1에서, R1 내지 R8은 각각 독립적으로 수소; 비치환된 페닐기; 탄소수 1 내지 8의 알킬기; 탄소수 1 내지 8의 알콕시기; 니트로기; 할로겐 원자; 시아노기; 탄소수 1 내지 8의 알킬아미노기; 탄소수 1 내지 8의 아미노알킬기; 또는 탄소수 1 내지 8의 알콕시기, 탄소수 1 내지 8의 알킬기, 니트로기, 할로겐 원자, 탄소수 1 내지 8의 알킬아미노기, 탄소수 1 내지 8의 아미노알킬기, 시아노기, 카르복실기, 술폰기, 페놀성 수산기 및 인산기 중에서 선택된 하나 이상의 치환기를 갖는 페닐기이고, 상기 R1 내지 R8 중 적어도 하나는 말단에 카르복실기, 술폰기, 페놀성 수산기 및 인산기 중에서 선택된 하나 이상의 치환기를 갖는 페닐기이다.
M은 Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th 및 U로 이루어지는 군으로부터 선택되는 어느 하나이다.)The method of claim 1,
The light-scattering resin composition, characterized in that the dye is a compound represented by the following formula (1).
[Formula 1]
(In Formula 1, R 1 to R 8 are each independently hydrogen; an unsubstituted phenyl group; an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; a nitro group; a halogen atom; a cyano group; 1 to 8 carbon atoms; an alkylamino group; an aminoalkyl group having 1 to 8 carbon atoms; or an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a halogen atom, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, A phenyl group having at least one substituent selected from a cyano group, a carboxyl group, a sulfone group, a phenolic hydroxyl group, and a phosphoric acid group, wherein at least one of R 1 to R 8 has at least one substituent selected from a carboxyl group, a sulfone group, a phenolic hydroxyl group, and a phosphoric acid group at the terminal It is a phenyl group having
M is Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, It is any one selected from the group consisting of Tb, Dy, Ho, Er, Tm, Yb, Lu, Th and U.)
상기 무기입자는 Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, ITO, IZO, ATO, ZnO-Al, Nb2O3, SnO, MgO 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The inorganic particles are Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO-Al, Nb 2 O 3 , SnO, A light scattering resin composition, characterized in that at least one selected from the group consisting of MgO and combinations thereof.
상기 염료는 상기 무기입자의 총 중량 대비 0.1 내지 30 중량%로 포함되는 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The light-scattering resin composition, characterized in that the dye is included in 0.1 to 30% by weight relative to the total weight of the inorganic particles.
상기 광흡수제는 540nm 내지 620nm 에서 최대흡광도를 가지는 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The light-scattering resin composition, characterized in that the light absorber has a maximum absorbance at 540nm to 620nm.
상기 광산란 수지 조성물은 산란입자를 더 포함하는 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The light-scattering resin composition further comprises scattering particles.
상기 광산란 수지 조성물은 실란 커플링제 및 계면활성제로 이루어진 군으로부터 선택되는 하나 이상의 첨가제를 더 포함하는 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The light-scattering resin composition further comprises at least one additive selected from the group consisting of a silane coupling agent and a surfactant.
상기 광산란 수지 조성물 총 중량에 대하여, 광흡수제 1 내지 30 중량% 및 중합성 화합물 1 내지 30 중량%를 포함하고,
광산란 수지 조성물 고형분 총 중량에 대하여, 용제 100 내지 500 중량%를 포함하는 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
Based on the total weight of the light scattering resin composition, 1 to 30% by weight of a light absorber and 1 to 30% by weight of a polymeric compound,
A light-scattering resin composition comprising 100 to 500% by weight of a solvent based on the total weight of the solid content of the light-scattering resin composition.
상기 광산란 수지 조성물은 산란층 형성용인 것을 특징으로 하는 광산란 수지 조성물.The method of claim 1,
The light-scattering resin composition is a light-scattering resin composition, characterized in that for forming a scattering layer.
상기 화상표시장치는 퀀텀닷 디스플레이인 것을 특징으로 하는 화상표시장치.The method of claim 12,
The image display device, characterized in that the image display device is a quantum dot display.
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