KR102609848B1 - Hard Coating Film and Flexible Display Having the Same - Google Patents
Hard Coating Film and Flexible Display Having the Same Download PDFInfo
- Publication number
- KR102609848B1 KR102609848B1 KR1020160177306A KR20160177306A KR102609848B1 KR 102609848 B1 KR102609848 B1 KR 102609848B1 KR 1020160177306 A KR1020160177306 A KR 1020160177306A KR 20160177306 A KR20160177306 A KR 20160177306A KR 102609848 B1 KR102609848 B1 KR 102609848B1
- Authority
- KR
- South Korea
- Prior art keywords
- hard coating
- coating layer
- coating film
- transparent substrate
- weight
- Prior art date
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
Abstract
본 발명은 투명 기재; 상기 투명 기재의 한면에 형성된 제1 하드코팅층; 상기 투명 기재의 다른 한면에 형성된 제2 하드코팅층; 상기 투명 기재와 제1 하드코팅층 사이에 위치하는 제3 하드코팅층; 상기 투명 기재와 제2 하드코팅층 사이에 위치하는 제4 하드코팅층; 상기 투명 기재와 제3 하드코팅층 사이에 위치하는 제5 하드코팅층; 및 상기 투명 기재와 제4 하드코팅층 사이에 위치하는 제6 하드코팅층을 포함하고, 상기 제1 하드코팅층 내지 제6 하드코팅층은 각각 두께가 5 내지 50 ㎛ 이고, 가교강직성 값의 범위가 1.2 내지 15 kPa·m인 플렉시블 디스플레이용 하드코팅 필름, 및 상기 하드코팅 필름이 구비된 플렉시블 디스플레이를 제공한다. 본 발명에 따른 하드코팅 필름은 경도가 높으면서도 유연성이 뛰어나다.The present invention relates to a transparent substrate; A first hard coating layer formed on one side of the transparent substrate; a second hard coating layer formed on the other side of the transparent substrate; A third hard coating layer located between the transparent substrate and the first hard coating layer; A fourth hard coating layer located between the transparent substrate and the second hard coating layer; A fifth hard coating layer located between the transparent substrate and the third hard coating layer; And a sixth hard coating layer located between the transparent substrate and the fourth hard coating layer, wherein the first to sixth hard coating layers each have a thickness of 5 to 50 ㎛, and a crosslink stiffness value in the range of 1.2 to 15. Provided is a hard coating film for a flexible display having kPa·m, and a flexible display equipped with the hard coating film. The hard coating film according to the present invention has high hardness and excellent flexibility.
Description
본 발명은 하드코팅 필름 및 이를 구비한 플렉시블 디스플레이에 관한 것으로, 보다 상세하게는 경도가 우수하면서 유연성을 가지는 하드코팅 필름 및 상기 하드코팅 필름을 구비한 플렉시블 디스플레이에 관한 것이다.The present invention relates to a hard coating film and a flexible display equipped with the same. More specifically, it relates to a hard coating film having excellent hardness and flexibility and a flexible display equipped with the hard coating film.
하드코팅 필름은 액정 표시장치, 일렉트로루미네센스(EL) 표시장치, 플라즈마 디스플레이(PD), 전계 방출 디스플레이(FED: Field Emission Display) 등의 화상표시장치에 표면 보호 등의 목적으로 이용되고 있다.Hard coating films are used for surface protection in image display devices such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PD), and field emission displays (FED).
최근에는 기존의 유연성이 없는 유리기판 대신에 플라스틱 등과 같이 유연성 있는 재료를 사용하여 종이처럼 휘어져도 표시 성능을 그대로 유지할 수 있는 플렉시블(flexible) 디스플레이가 차세대 표시장치로 급부상하면서, 경도(hardness)가 높고 내찰상성이 좋을 뿐만 아니라, 제조 공정이나 사용 중에 필름 가장자리의 컬(curl) 현상이 일어나지 않고, 적당한 유연성을 갖추어 크랙이 발생하지 않는 하드코팅 필름이 요구되고 있다.Recently, flexible displays, which can maintain display performance even when bent like paper by using flexible materials such as plastic instead of the existing inflexible glass substrate, have emerged as a next-generation display device, with high hardness and high hardness. There is a need for a hard coating film that not only has good scratch resistance, but also does not curl at the edges of the film during the manufacturing process or during use, and has appropriate flexibility to prevent cracks.
대한민국 공개특허 제2014-0027023호에는 지지 기재; 상기 기재의 일면에 형성되며, 제1 광경화성 가교 공중합체를 포함하는 제1 하드코팅층; 및 상기 기재의 다른 일면에 형성되며, 제2 광경화성 가교 공중합체, 및 상기 제2 광경화성 가교 공중합체 내에 분산되어 있는 무기 미립자를 포함하는 제2 하드코팅층을 포함하는 하드코팅 필름이 개시되어 있으며, 상기 하드코팅 필름은 고경도, 내충격성, 내찰상성 및 고투명도를 나타낸다고 기재되어 있다.Support is described in Korean Patent Publication No. 2014-0027023; A first hard coating layer formed on one side of the substrate and comprising a first photocurable crosslinked copolymer; and a second hard coating layer formed on the other side of the substrate and comprising a second photocurable crosslinked copolymer and inorganic fine particles dispersed in the second photocurable crosslinked copolymer. , the hard coating film is described as exhibiting high hardness, impact resistance, scratch resistance, and high transparency.
그러나, 이러한 하드코팅 필름은 플렉시블 디스플레이에 적용하기에는 유연성이 충분하지 않은 문제점이 있었다.However, this hard coating film had a problem in that it was not flexible enough to be applied to a flexible display.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 본 발명의 한 목적은 경도가 우수하면서 유연성을 가지는 플렉시블 디스플레이용 하드코팅 필름을 제공하는 것이다.The present invention is intended to solve the above problems, and one object of the present invention is to provide a hard coating film for flexible displays that has excellent hardness and flexibility.
본 발명의 다른 목적은 상기 하드코팅 필름이 구비된 플렉시블 디스플레이를 제공하는 것이다.Another object of the present invention is to provide a flexible display equipped with the hard coating film.
한편으로, 본 발명은 투명 기재; 상기 투명 기재의 한면에 형성된 제1 하드코팅층; 상기 투명 기재의 다른 한면에 형성된 제2 하드코팅층; 상기 투명 기재와 제1 하드코팅층 사이에 위치하는 제3 하드코팅층; 상기 투명 기재와 제2 하드코팅층 사이에 위치하는 제4 하드코팅층; 상기 투명 기재와 제3 하드코팅층 사이에 위치하는 제5 하드코팅층; 및 상기 투명 기재와 제4 하드코팅층 사이에 위치하는 제6 하드코팅층을 포함하고, On the one hand, the present invention provides a transparent substrate; A first hard coating layer formed on one side of the transparent substrate; a second hard coating layer formed on the other side of the transparent substrate; A third hard coating layer located between the transparent substrate and the first hard coating layer; A fourth hard coating layer located between the transparent substrate and the second hard coating layer; A fifth hard coating layer located between the transparent substrate and the third hard coating layer; And a sixth hard coating layer located between the transparent substrate and the fourth hard coating layer,
상기 제1 하드코팅층 내지 제6 하드코팅층은 각각 두께가 5 내지 50 ㎛ 이고, 하기 수학식 1로 정의되는 가교강직성 값의 범위가 1.2 내지 15 kPa·m인 플렉시블 디스플레이용 하드코팅 필름을 제공한다.
The first to sixth hard coating layers each have a thickness of 5 to 50 ㎛, and the crosslinking stiffness value range of 1.2 to 15 kPa·m, defined by Equation 1 below, is provided.
[수학식 1][Equation 1]
가교강직성(kPa·m) = 압축 탄성율(GPa)×층 두께(㎛)×가교밀도
Crosslink stiffness (kPa·m) = Compressive modulus (GPa) × Layer thickness (㎛) × Crosslink density
본 발명의 일 실시형태에서, 1000g의 하중으로 평가한 제1 하드코팅층의 연필경도는 3H 이상일 수 있다.
In one embodiment of the present invention, the pencil hardness of the first hard coating layer evaluated with a load of 1000 g may be 3H or more.
본 발명의 일 실시형태에서, 상기 하드코팅 필름은 상기 제2 하드코팅층이 점착제와 접하도록 점착제에 부착한 상태에서 1000g의 하중으로 평가한 연필경도가 H 이상일 수 있다.In one embodiment of the present invention, the hard coating film may have a pencil hardness of H or higher when evaluated under a load of 1000 g when the second hard coating layer is attached to the adhesive so that the second hard coating layer is in contact with the adhesive.
다른 한편으로, 본 발명은 상기 하드코팅 필름이 구비된 플렉시블 디스플레이를 제공한다.On the other hand, the present invention provides a flexible display equipped with the hard coating film.
또 다른 한편으로, 본 발명은 상기 하드코팅 필름이 구비된 플렉시블 디스플레이의 윈도우를 제공한다.On the other hand, the present invention provides a window of a flexible display equipped with the hard coating film.
본 발명에 따른 하드코팅 필름은 경도가 높으면서도 유연성이 뛰어나므로 플렉시블 디스플레이에 효과적으로 사용될 수 있다.The hard coating film according to the present invention has high hardness and excellent flexibility, so it can be effectively used in flexible displays.
이하, 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 투명 기재; 상기 투명 기재의 한면에 형성된 제1 하드코팅층; 상기 투명 기재의 다른 한면에 형성된 제2 하드코팅층; 상기 투명 기재와 제1 하드코팅층 사이에 위치하는 제3 하드코팅층; 상기 투명 기재와 제2 하드코팅층 사이에 위치하는 제4 하드코팅층; 상기 투명 기재와 제3 하드코팅층 사이에 위치하는 제5 하드코팅층; 및 상기 투명 기재와 제4 하드코팅층 사이에 위치하는 제6 하드코팅층을 포함하고, The present invention relates to a transparent substrate; A first hard coating layer formed on one side of the transparent substrate; a second hard coating layer formed on the other side of the transparent substrate; A third hard coating layer located between the transparent substrate and the first hard coating layer; A fourth hard coating layer located between the transparent substrate and the second hard coating layer; A fifth hard coating layer located between the transparent substrate and the third hard coating layer; And a sixth hard coating layer located between the transparent substrate and the fourth hard coating layer,
상기 제1 하드코팅층 내지 제6 하드코팅층은 각각 두께가 5 내지 50 ㎛ 이고, 하기 수학식 1로 정의되는 가교강직성 값의 범위가 1.2 내지 15 kPa·m인 플렉시블 디스플레이용 하드코팅 필름을 제공한다.
The first to sixth hard coating layers each have a thickness of 5 to 50 ㎛, and the crosslinking stiffness value range of 1.2 to 15 kPa·m, defined by Equation 1 below, is provided.
[수학식 1][Equation 1]
가교강직성(kPa·m) = 압축 탄성율(GPa)×층 두께(㎛)×가교밀도
Crosslink stiffness (kPa·m) = Compressive modulus (GPa) × Layer thickness (㎛) × Crosslink density
본 발명의 일 실시형태에 따른 하드코팅 필름은 그 양면에 두께가 5 내지 50 ㎛의 범위로 얇으면서 가교강직성 값이 1.2 내지 15 kPa·m인 하드코팅층이 형성되어 있어 경도가 우수하면서 유연성을 갖게 된다. 특히, 접거나 구부릴 때 바깥 방향에서의 인장응력이 가해지기 때문에 하드코팅층에서 크랙 발생이 완화된다. 상기 가교강직성의 값이 1.2 kPa·m 미만인 경우에는 경도 향상이 어렵고, 15 kPa·m를 초과하는 경우에는 굽힘 특성 발현이 어려울 수 있다.
The hard coating film according to an embodiment of the present invention has a thin hard coating layer in the range of 5 to 50 ㎛ in thickness and a crosslinking stiffness value of 1.2 to 15 kPa·m on both sides, so that it has excellent hardness and flexibility. do. In particular, the occurrence of cracks in the hard coating layer is alleviated because tensile stress is applied in the outward direction when folding or bending. If the crosslink stiffness value is less than 1.2 kPa·m, it is difficult to improve hardness, and if it exceeds 15 kPa·m, it may be difficult to develop bending properties.
본 발명의 일 실시형태에서, 상기 제1 하드코팅층의 압축 탄성율은 10,000 내지 15,000 MPa이고, 상기 제3 하드코팅층의 압축 탄성율은 5,000 내지 10,000 MPa이며, 상기 제5 하드코팅층의 압축 탄성율은 3,000 내지 5,000 MPa이다. 또한, 상기 제2 하드코팅층의 압축 탄성율은 3,000 내지 5,000 MPa이고, 상기 제4 하드코팅층의 압축 탄성율은 5,000 내지 7,000 MPa이며, 상기 제6 하드코팅층의 압축 탄성율은 7,000 내지 10,000 MPa일 수 있다. In one embodiment of the present invention, the first hard coating layer has a compressive elastic modulus of 10,000 to 15,000 MPa, the third hard coating layer has a compressive elastic modulus of 5,000 to 10,000 MPa, and the fifth hard coating layer has a compressive elastic modulus of 3,000 to 5,000. It is MPa. In addition, the compressive elastic modulus of the second hard coating layer is 3,000 to 5,000 MPa, the compressive elastic modulus of the fourth hard coating layer is 5,000 to 7,000 MPa, and the compressive elastic modulus of the sixth hard coating layer may be 7,000 to 10,000 MPa.
본 발명에서 상기 압축 탄성율을 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다.
In the present invention, the method of measuring the compressive elastic modulus is not particularly limited, and can be measured, for example, by the method shown in the experimental example described later.
본 발명의 일 실시형태에서, 상기 제1 하드코팅층과 제2 하드코팅층의 가교밀도는 5 내지 20%이고, 상기 제3 하드코팅층과 제4 하드코팅층의 가교밀도는 5 내지 15%이며, 상기 제5 하드코팅층과 제6 하드코팅층의 가교밀도는 2 내지 15%일 수 있다. 상기 범위의 가교밀도를 만족할 때 하드코팅층 형성시 경도 향상 및 유연성 개선 효과를 얻을 수 있다.In one embodiment of the present invention, the crosslinking density of the first hard coating layer and the second hard coating layer is 5 to 20%, the crosslinking density of the third hard coating layer and the fourth hard coating layer is 5 to 15%, and the The crosslinking density of the 5 hard coating layer and the 6th hard coating layer may be 2 to 15%. When the crosslinking density in the above range is satisfied, the effect of improving hardness and flexibility can be obtained when forming a hard coating layer.
본 발명에서 상기 가교밀도를 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다.
In the present invention, the method for measuring the crosslinking density is not particularly limited, and can be measured, for example, by the method shown in the experimental example described later.
본 발명의 일 실시형태에서, 1000g의 하중으로 평가한 제1 하드코팅층의 연필경도는 3H 이상일 수 있다. In one embodiment of the present invention, the pencil hardness of the first hard coating layer evaluated with a load of 1000 g may be 3H or more.
본 발명에서 상기 연필경도를 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다.
In the present invention, the method of measuring the pencil hardness is not particularly limited, and can be measured, for example, by the method shown in the experimental example described later.
본 발명의 일 실시형태에서, 상기 하드코팅 필름은 제2 하드코팅층이 점착제와 접하도록 점착제에 부착한 상태에서 1000g의 하중으로 평가한 연필경도가 H 이상일 수 있다. 상기 점착제는 25μm 이상의 두께를 가지고, 예들 들어 감압 점착제(PSA) 또는 광학 투명 접착제(OCA)일 수 있다.In one embodiment of the present invention, the hard coating film may have a pencil hardness of H or higher when evaluated under a load of 1000 g while attached to the adhesive so that the second hard coating layer is in contact with the adhesive. The adhesive has a thickness of 25 μm or more and may be, for example, a pressure-sensitive adhesive (PSA) or an optically clear adhesive (OCA).
본 발명에서 상기 점착제 연필경도를 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다
In the present invention, the method of measuring the pencil hardness of the adhesive is not particularly limited, and can be measured, for example, by the method shown in the experimental example described later.
본 발명의 일 실시형태에 따른 하드코팅 필름은 투명 기재의 양면에 하드코팅 조성물을 도포하고 경화시켜 제1 내지 제6 하드코팅층을 형성함으로써 제조할 수 있다.
The hard coating film according to one embodiment of the present invention can be manufactured by applying a hard coating composition to both sides of a transparent substrate and curing it to form first to sixth hard coating layers.
상기 투명 기재로는 투명성이 있는 플라스틱 필름이면 어떤 것이라도 사용 가능하다. 예를 들면, 노르보르넨이나 다환 노르보르넨계 단량체와 같은 시클로올레핀을 포함하는 단량체의 단위를 갖는 시클로올레핀계 유도체, 셀룰로오스(디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부틸레이트, 이소부틸에스테르셀룰로오스, 프로피오닐셀룰로오스, 부티릴셀룰로오스, 아세틸프로피오닐셀룰로오스), 에틸렌아세트산비닐공중합체, 폴리에스테르, 폴리스티렌, 폴리아미드, 폴리에테르이미드, 폴리아크릴, 폴리이미드, 폴리에테르술폰, 폴리술폰, 폴리에틸렌, 폴리프로필렌, 폴리메틸펜텐, 폴리염화비닐, 폴리염화비닐리덴, 폴리비닐알콜, 폴리비닐아세탈, 폴리에테르케톤, 폴리에테르에테르케톤, 폴리에테르술폰, 폴리메틸메타아크릴레이트, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리우레탄 및 에폭시 중에서 선택하여 사용할 수 있으며, 미연신, 1축 또는 2축 연신 필름을 사용할 수 있다.Any transparent plastic film can be used as the transparent substrate. For example, cycloolefin-based derivatives having units of monomers containing cycloolefins such as norbornene or polycyclic norbornene-based monomers, cellulose (diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, isobutyl ester cellulose, Propionylcellulose, butyrylcellulose, acetylpropionylcellulose), ethylene vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, Polymethyl pentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, You can choose from polyethylene naphthalate, polycarbonate, polyurethane, and epoxy, and unstretched, uniaxially or biaxially stretched films can be used.
상기 투명 기재의 두께는 특별히 제한되지 않으나, 8 내지 1000㎛, 구체적으로는 20 내지 150㎛일 수 있다. 상기 투명 기재의 두께가 8㎛ 미만이면 필름의 강도가 저하되어 가공성이 떨어지게 되고, 1000㎛ 초과이면 투명성이 저하되거나 하드코팅 필름의 중량이 커지는 문제가 발생한다.
The thickness of the transparent substrate is not particularly limited, but may be 8 to 1000 μm, specifically 20 to 150 μm. If the thickness of the transparent substrate is less than 8㎛, the strength of the film decreases and processability decreases, and if it exceeds 1000㎛, transparency decreases or the weight of the hard coating film increases.
상기 제1 하드코팅층 내지 제6 하드코팅층을 형성하는 하드코팅 조성물은 광경화형 수지, 광개시제 및 용제를 포함할 수 있으며, 입경이 10 내지 100 nm인 나노실리카를 함유하는 실리카 졸을 추가로 포함할 수 있다.
The hard coating composition forming the first to sixth hard coating layers may include a photocurable resin, a photoinitiator, and a solvent, and may further include a silica sol containing nanosilica with a particle size of 10 to 100 nm. there is.
상기 광경화형 수지는 광경화형 (메타)아크릴레이트 올리고머, 모노머, 아크릴계 덴드리머, 폴리카프로락톤, 폴리로타세인 및 포스파젠 화합물로 구성된 군으로부터 선택된 하나 이상을 포함할 수 있다.The photocurable resin may include one or more selected from the group consisting of photocurable (meth)acrylate oligomers, monomers, acrylic dendrimers, polycaprolactone, polyrotaxane, and phosphazene compounds.
상기 광경화형 (메타)아크릴레이트 올리고머로는 에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트 등을 통상적으로 사용하며, 다관능 우레탄 (메타)아크릴레이트가 보다 바람직하다. 상기 다관능 우레탄 (메타)아크릴레이트는 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트와 이소시아네이트기를 갖는 화합물을 촉매 존재 하에서 반응시켜 제조할 수 있다.As the photocurable (meth)acrylate oligomer, epoxy (meth)acrylate, urethane (meth)acrylate, etc. are commonly used, and polyfunctional urethane (meth)acrylate is more preferable. The multifunctional urethane (meth)acrylate can be produced by reacting a polyfunctional (meth)acrylate having a hydroxy group in the molecule with a compound having an isocyanate group in the presence of a catalyst.
상기 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시이소프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 카프로락톤 개환 히드록시아크릴레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트 혼합물 및 디펜타에리스리톨펜타/헥사(메타)아크릴레이트 혼합물로 이루어진 군으로부터 1종 이상 선택될 수 있다.Polyfunctional (meth)acrylates having a hydroxy group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and caprolactone. One or more types may be selected from the group consisting of ring-opened hydroxyacrylate, pentaerythritol tri/tetra(meth)acrylate mixture, and dipentaerythritol penta/hexa(meth)acrylate mixture.
또한, 상기 이소시아네이트기를 갖는 화합물은 1,4-디이소시아나토부탄, 1,6-디이소시아나토헥산, 1,8-디이소시아나토옥탄, 1,12-디이소시아나토도데칸, 1,5-디이소시아나토-2-메틸펜탄, 트리메틸-1,6-디이소시아나토헥산, 1,3-비스(이소시아나토메틸)시클로헥산, 트랜스-1,4-시클로헥센디이소시아네이트, 4,4'-메틸렌비스(시클로헥실이소시아네이트), 이소포론디이소시아네이트, 톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트, 자일렌-1,4-디이소시아네이트, 테트라메틸자일렌-1,3-디이소시아네이트, 1-클로로메틸-2,4-디이소시아네이트, 4,4'-메틸렌비스(2,6-디메틸페닐이소시아네이트), 4,4'-옥시비스(페닐이소시아네이트), 헥사메틸렌디이소시아네이트로부터 유도되는 3관능성 이소시아네이트, 및 트리메탄프로판올어덕트톨루엔디이소시아네이트로 이루어진 군으로부터 1종 이상 선택될 수 있다.
In addition, compounds having the isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, and 1,5-diisocyanate. Isocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexenediisocyanate, 4,4'-methylene Bis(cyclohexylisocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-di Isocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenylisocyanate), 4,4'-oxybis(phenylisocyanate), derived from hexamethylene diisocyanate One or more types may be selected from the group consisting of trifunctional isocyanate and trimethane propanol adduct toluene diisocyanate.
상기 모노머는 당해 기술분야에서 사용되는 것일 수 있으며, 구체적으로 광경화형 관능기, 예컨대 (메타)아크릴로일기, 비닐기, 스티릴기, 알릴기 등의 불포화기를 분자내에 갖는 화합물, 바람직하게는 (메타)아크릴로일기를 갖는 화합물이다. The monomer may be used in the art, and specifically, a compound having an unsaturated group such as a photocurable functional group, such as (meth)acryloyl group, vinyl group, styryl group, and allyl group, in the molecule, preferably (meth) It is a compound having an acryloyl group.
상기 (메타)아크릴로일기를 갖는 모노머는 네오펜틸글리콜아크릴레이트, 1,6-헥산디올(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올에탄트리(메타)아크릴레이트, 1,2,4-시클로헥산테트라(메타)아크릴레이트, 펜타글리세롤트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 트리펜타에리스리톨트리(메타)아크릴레이트, 트리펜타에리스리톨헥사(메타)아크릴레이트, 비스(2-하이드록시에틸)이소시아누레이트디(메타)아크릴레이트, 하이드록시에틸(메타)아크릴레이트, 하이드록시프로필(메타)아크릴레이트, 하이드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소덱실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라하이드로퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 및 이소보네올(메타)아크릴레이트로 이루어진 군으로부터 1종 이상 선택될 수 있다.Monomers having the (meth)acryloyl group include neopentyl glycol acrylate, 1,6-hexanediol (meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropylene. Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2 , 4-cyclohexane tetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexa(meth)acrylate, bis. (2-Hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, isooctyl(meth) A group consisting of acrylates, isodexyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and isoborneol (meth)acrylate. One or more types may be selected from.
상기 광경화형 수지는 상기 하드코팅 조성물 전체 100 중량%에 대하여 15 내지 85 중량%, 바람직하게는 25 내지 60 중량%로 포함될 수 있다. 15 중량% 미만인 경우에는 코팅 두께를 올리기 어렵고, 충분한 기계적 특성을 확보하는 것이 어려울 수 있으며, 85 중량% 초과인 경우에는 코팅성이 현저하게 나빠져 외관이 불량하고 두께 균일도를 확보하기 어려울 수 있다.
The photocurable resin may be included in an amount of 15 to 85% by weight, preferably 25 to 60% by weight, based on 100% by weight of the total hard coating composition. If it is less than 15% by weight, it may be difficult to increase the coating thickness and secure sufficient mechanical properties, and if it is more than 85% by weight, coating properties may deteriorate significantly, resulting in poor appearance and difficulty in securing thickness uniformity.
상기 광개시제는 당해 기술분야에서 사용되는 것이라면 제한되지 않고 사용될 수 있다. 구체적으로, 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1, 디페닐케톤 벤질디메틸케탈, 2-히드록시-2-메틸-1-페닐-1-온, 4-히드록시시클로페닐케톤, 디메톡시-2-페닐아세토페논, 안트라퀴논, 플루오렌, 트리페닐아민, 카바졸, 3-메틸아세토페논, 4-클로로아세토페논, 4,4-디메톡시아세토페논, 4,4-디아미노벤조페논, 1-히드록시시클로헥실페닐케톤 및 벤조페논으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다.The photoinitiator may be used without limitation as long as it is used in the art. Specifically, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinepropanone-1, diphenylketone benzyldimethylketal, 2-hydroxy-2-methyl-1-phenyl-1-one , 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyaceto One or more selected from the group consisting of phenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, and benzophenone may be used.
상기 광개시제는 상기 하드코팅 조성물 전체 100 중량%에 대하여 0.1 내지 10 중량%로 포함될 수 있다. 상기 광개시제의 함량이 0.1 중량% 미만이면 경화 속도가 늦고, 10 중량%를 초과하면 과도한 경화로 인해 하드코팅층에 크랙이 발생할 수 있다.
The photoinitiator may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the hard coating composition. If the photoinitiator content is less than 0.1% by weight, the curing speed is slow, and if it exceeds 10% by weight, cracks may occur in the hard coating layer due to excessive curing.
상기 용제는 당해 기술분야에서 사용되는 것이라면 제한되지 않고 사용할 수 있다. 구체적으로, 알코올계(메탄올, 에탄올, 이소프로판올, 부탄올 등), 셀로솔브계(메틸셀로솔브, 에틸셀로솔브 등), 케톤계(메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 디에틸케톤, 디프로필케톤, 시클로헥사논 등), 헥산계(헥산, 헵탄, 옥탄 등), 벤젠계(벤젠, 톨루엔, 자일렌 등) 등이 사용될 수 있다. 상기 용제들은 각각 단독으로 또는 둘 이상을 조합하여 사용할 수 있다.The solvent may be used without limitation as long as it is used in the technical field. Specifically, alcohol-based (methanol, ethanol, isopropanol, butanol, etc.), cellosolve-based (methyl cellosolve, ethyl cellosolve, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl Ketone, dipropyl ketone, cyclohexanone, etc.), hexane-based (hexane, heptane, octane, etc.), benzene-based (benzene, toluene, xylene, etc.) can be used. The above solvents can be used individually or in combination of two or more.
상기 용제는 하드코팅 조성물 전체 100 중량%에 대하여 10 내지 80 중량%, 바람직하게는 20 내지 60 중량%로 포함될 수 있다. 10 중량% 미만인 경우 점도가 높아 작업성이 떨어지고, 80 중량% 초과인 경우에는 건조 및 경화 과정에서 많은 시간이 소요되며, 하드코팅막을 형성할 시에 높은 두께를 형성하기 어렵다는 단점이 있다.
The solvent may be included in an amount of 10 to 80% by weight, preferably 20 to 60% by weight, based on 100% by weight of the total hard coating composition. If it is less than 10% by weight, the viscosity is high and workability is poor, and if it is more than 80% by weight, it takes a lot of time in the drying and curing process, and it is difficult to form a high thickness when forming a hard coating film.
한편, 추가로 사용가능한 상기 실리카 졸은 입경이 10 내지 100 nm인 나노실리카가 유기 용매에 분산되어 있는 콜로이드 형태일 수 있다. 상기 유기 용매로는 메탄올 및 이소프로판올과 같은 알코올류, 메틸에틸케톤 및 메틸이소부틸케톤과 같은 케톤류 등이 사용될 있으며, 이중에서 메틸에틸케톤이 하드코팅 필름의 밀착성을 개선시킬 수 있어 바람직하다. Meanwhile, the additionally usable silica sol may be in the form of a colloid in which nano-silica with a particle size of 10 to 100 nm is dispersed in an organic solvent. The organic solvent may include alcohols such as methanol and isopropanol, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Among these, methyl ethyl ketone is preferred because it can improve the adhesion of the hard coating film.
상기 실리카 졸은 하드코팅 조성물 전체 100 중량%에 대하여 10 내지 60 중량%, 바람직하게는 20 내지 40 중량%로 포함될 수 있다. 10 중량% 미만인 경우에는 내마모성, 내스크래치성, 연필경도 등의 기계적 물성이 충분하지 않을 수 있으며, 60 중량% 초과인 경우에는 외관 불량 및 유연성이 저하될 수 있다.
The silica sol may be included in an amount of 10 to 60% by weight, preferably 20 to 40% by weight, based on 100% by weight of the total hard coating composition. If it is less than 10% by weight, mechanical properties such as wear resistance, scratch resistance, and pencil hardness may not be sufficient, and if it is more than 60% by weight, poor appearance and flexibility may be reduced.
상기 하드코팅 조성물은 상기한 성분들 이외에도, 당해 기술분야에서 일반적으로 사용되는 성분들, 예를 들어 레벨링제, 자외선 안정제, 열 안정제, 항산화제, 계면활성제, 윤활제, 방오제 등이 추가적으로 포함될 수 있다.
In addition to the above-mentioned ingredients, the hard coating composition may additionally contain ingredients commonly used in the art, such as leveling agents, UV stabilizers, heat stabilizers, antioxidants, surfactants, lubricants, and antifouling agents. .
상기 레벨링제는 상기 하드코팅 조성물을 코팅 시 도막의 평활성 및 코팅성을 부여하기 위해 사용될 수 있다. 상기 레벨링제는 시판되는 실리콘 형태의 레벨링제, 불소 형태의 레벨링제, 아크릴 고분자 형태의 레벨링제 등을 사용할 수 있으며, 예를 들면 비와이케이 케미사의 BYK-3530, BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, 대구사의 TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, 3M사의 FC-4430, FC-4432 등을 사용할 수 있다. 상기 레벨링제는 상기 하드코팅 조성물 전체 100 중량%에 대하여 0.1 내지 1 중량% 범위로 사용하는 것이 좋다.
The leveling agent may be used to provide smoothness and coatability to the coating film when coating the hard coating composition. The leveling agent may be a commercially available silicone type leveling agent, a fluorine type leveling agent, or an acrylic polymer type leveling agent. For example, BYK Chemistry's BYK-3530, BYK-323, BYK-331, BYK -333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, Daegu's TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, 3M's FC-4430, FC-4432, etc. can be used. The leveling agent is preferably used in an amount of 0.1 to 1% by weight based on 100% by weight of the hard coating composition.
상기 하드코팅 조성물은 다이코터, 에어 나이프, 리버스 롤, 스프레이, 블레이드, 캐스팅, 그라비아, 마이크로 그라비아, 스핀코팅 등 공지된 방식을 적절히 사용하여, 투명기재에 도공(Coating Process)이 가능하다.The hard coating composition can be coated on a transparent substrate using known methods such as die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, and spin coating.
상기 하드코팅 조성물을 투명기재에 도포한 후에는, 30 내지 150℃의 온도에서 10초 내지 1시간 동안, 보다 구체적으로는 30초 내지 30분 동안 휘발물을 증발시켜 건조시킨 다음, UV광을 조사하여 경화시킨다. 상기 UV광의 조사량은 구체적으로 약 0.01 내지 10J/㎠일 수 있으며, 보다 구체적으로 0.1 내지 2J/㎠일 수 있다.
After applying the hard coating composition to the transparent substrate, the volatiles are evaporated and dried at a temperature of 30 to 150 ° C. for 10 seconds to 1 hour, more specifically for 30 seconds to 30 minutes, and then irradiated with UV light. and harden. The irradiation amount of the UV light may be specifically about 0.01 to 10 J/cm2, and more specifically may be 0.1 to 2 J/cm2.
본 발명의 일 실시형태는 상술한 하드코팅 필름이 구비된 플렉시블 디스플레이에 관한 것이다. 일례로, 본 발명의 하드코팅 필름은 플렉시블 디스플레이의 윈도우에 부착시킬 수 있다. One embodiment of the present invention relates to a flexible display provided with the above-described hard coating film. For example, the hard coating film of the present invention can be attached to the window of a flexible display.
본 발명의 일 실시형태에 따른 하드코팅 필름은 반사형, 투과형, 반투과형 LCD 또는 TN형, STN형, OCB형, HAN형, VA형, IPS형 등의 각종 구동 방식의 LCD에 사용될 수 있다. 또한, 본 발명의 일 실시형태에 따른 하드코팅 필름은 플라즈마 디스플레이, 필드 에미션 디스플레이, 유기 EL 디스플레이, 무기 EL 디스플레이, 전자 페이퍼 등의 각종 화상표시장치에도 사용될 수 있다.
The hard coating film according to an embodiment of the present invention can be used in LCDs of various driving types such as reflective, transmissive, and transflective LCDs, or TN type, STN type, OCB type, HAN type, VA type, and IPS type. Additionally, the hard coating film according to one embodiment of the present invention can be used in various image display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic papers.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.
Hereinafter, the present invention will be described in more detail through examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are only for illustrating the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.
제조예Manufacturing example 1: 제1 1: 1st 하드코팅층Hard coating layer -형성 조성물의 제조 - Preparation of forming composition
메틸에틸케톤 실리카졸(MEK-AC-2140Z, 닛산화학, 입경 10-15nm) 40 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 15 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 25 중량%를 혼합하여 제1 하드코팅층-형성 조성물을 제조하였다. Methyl ethyl ketone silica sol (MEK-AC-2140Z, Nissan Chemical, particle size 10-15 nm) 40% by weight, 10-functional urethane acrylate oligomer (UV1000, Shina TNC) 15% by weight, tri-functional monomer (M340, MIRAMER) 18.5% by weight %, 1.2% by weight of photoinitiator (I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 25% by weight of methyl ethyl ketone (MEK) were mixed to prepare a first hard coating layer-forming composition.
제조예Manufacturing example 2: 제2 2: second 하드코팅층Hard coating layer -형성 조성물의 제조- Preparation of forming composition
메틸에틸케톤 실리카졸(MEK-AC-2140Z, 닛산화학, 입경 10-15nm) 30 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 25 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 25 중량%를 혼합하여 제2 하드코팅층-형성 조성물을 제조하였다.Methyl ethyl ketone silica sol (MEK-AC-2140Z, Nissan Chemical, particle size 10-15 nm) 30% by weight, 10-functional urethane acrylate oligomer (UV1000, Shina TNC) 25% by weight, 3-functional monomer (M340, MIRAMER) 18.5% by weight %, 1.2% by weight of photoinitiator (I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 25% by weight of methyl ethyl ketone (MEK) were mixed to prepare a second hard coating layer-forming composition.
제조예Manufacturing example 3: 제3 3: third 하드코팅층Hard coating layer -형성 조성물의 제조- Preparation of forming composition
메틸에틸케톤 실리카졸(MEK-AC-2140Z, 닛산화학, 입경 10-15nm) 30 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 15 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 35 중량%를 혼합하여 제3 하드코팅층-형성 조성물을 제조하였다.Methyl ethyl ketone silica sol (MEK-AC-2140Z, Nissan Chemical, particle size 10-15 nm) 30% by weight, 10-functional urethane acrylate oligomer (UV1000, Shina TNC) 15% by weight, tri-functional monomer (M340, MIRAMER) 18.5% by weight %, 1.2% by weight of photoinitiator (I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 35% by weight of methyl ethyl ketone (MEK) were mixed to prepare a third hard coating layer-forming composition.
제조예Manufacturing example 4: 제4 4: 4th 하드코팅층Hard coating layer -형성 조성물의 제조- Preparation of forming composition
메틸에틸케톤 실리카졸(MEK-AC-2140Z, 닛산화학, 입경 10-15nm) 20 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 15 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 45 중량%를 혼합하여 제4 하드코팅층-형성 조성물을 제조하였다.Methyl ethyl ketone silica sol (MEK-AC-2140Z, Nissan Chemical, particle size 10-15 nm) 20% by weight, 10-functional urethane acrylate oligomer (UV1000, Shina TNC) 15% by weight, tri-functional monomer (M340, MIRAMER) 18.5% by weight %, 1.2% by weight of photoinitiator (I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 45% by weight of methyl ethyl ketone (MEK) were mixed to prepare a fourth hard coating layer-forming composition.
제조예Manufacturing example 5: 제5 5: Fifth 하드코팅층Hard coating layer -형성 조성물의 제조- Preparation of forming composition
아이소프로필알콜 실리카졸(ST, 닛산화학, 입경 10-15nm) 30 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 15 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 35 중량%를 혼합하여 제5 하드코팅층-형성 조성물을 제조하였다.Isopropyl alcohol silica sol (ST, Nissan Chemical, particle size 10-15nm) 30% by weight, 10-functional urethane acrylate oligomer (UV1000, Shinart TNC) 15% by weight, tri-functional monomer (M340, MIRAMER) 18.5% by weight, photoinitiator ( A fifth hard coating layer-forming composition was prepared by mixing 1.2% by weight of I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 35% by weight of methyl ethyl ketone (MEK).
제조예Manufacturing example 6: 제6 6: 6th 하드코팅층Hard coating layer -형성 조성물의 제조- Preparation of forming composition
아이소프로필알콜 실리카졸(ST, 닛산화학, 입경 10-15nm) 25 중량%, 10관능 우레탄아크릴레이트 올리고머(UV1000, 신아티앤씨) 10 중량%, 3관능 모노머(M340, MIRAMER) 18.5 중량%, 광개시제(I-184, BASF) 1.2 중량%, 레벨링제(BYK-3530, BYK) 0.3 중량% 및 메틸에틸케톤(MEK) 45 중량%를 혼합하여 제6 하드코팅층-형성 조성물을 제조하였다.
25% by weight of isopropyl alcohol silica sol (ST, Nissan Chemical, particle size 10-15nm), 10% by weight of 10-functional urethane acrylate oligomer (UV1000, Shina T&C), 18.5% by weight of tri-functional monomer (M340, MIRAMER), photoinitiator ( A sixth hard coating layer-forming composition was prepared by mixing 1.2% by weight of I-184, BASF), 0.3% by weight of leveling agent (BYK-3530, BYK), and 45% by weight of methyl ethyl ketone (MEK).
실시예Example 1 내지 3 및 1 to 3 and 비교예Comparative example 1 내지 3: 1 to 3: 하드코팅hard coating 필름의 제조 Manufacturing of Film
실시예Example 1: One:
상기 제조예 5에서 제조된 제5 하드코팅층-형성 조성물을 폴리이미드(PI) 필름(30㎛)의 일면에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제5 하드코팅층을 형성하고, 상기 제조예 6에서 제조된 제6 하드코팅층-형성 조성물을 상기 폴리이미드(PI) 필름의 다른 일면에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제6 하드코팅층을 형성하였다. 이후, 제조예 3에서 제조된 제3 하드코팅층-형성 조성물을 상기 제5 하드코팅층 상에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제3 하드코팅층을 형성하고, 제조예 4에서 제조된 제4 하드코팅층-형성 조성물을 상기 제6 하드코팅층 상에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제4 하드코팅층을 형성하였다. 이어서, 제조예 1에서 제조된 제1 하드코팅층-형성 조성물을 상기 제3 하드코팅층 상에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제1 하드코팅층을 형성하고, 제조예 2에서 제조된 제2 하드코팅층-형성 조성물을 상기 제4 하드코팅층 상에 5㎛의 두께로 코팅하고 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에서 350mJ/㎠의 광량으로 경화하여 제2 하드코팅층을 형성함으로써 하드코팅필름을 제조하였다.
The fifth hard coating layer-forming composition prepared in Preparation Example 5 was coated to a thickness of 5㎛ on one side of a polyimide (PI) film (30㎛), dried in an oven at 80°C for 2 minutes, and then heated at 350mJ/cm2 in a high-pressure mercury lamp. A fifth hard coating layer was formed by curing with an amount of light, and the sixth hard coating layer-forming composition prepared in Preparation Example 6 was coated on the other side of the polyimide (PI) film to a thickness of 5㎛ and placed in an oven at 80°C. After drying for 2 minutes, it was cured in a high-pressure mercury lamp with a light intensity of 350 mJ/cm2 to form a sixth hard coating layer. Thereafter, the third hard coating layer-forming composition prepared in Preparation Example 3 was coated on the fifth hard coating layer to a thickness of 5㎛, dried in an oven at 80°C for 2 minutes, and then cured in a high pressure mercury lamp with a light amount of 350mJ/cm2. A third hard coating layer was formed, and the fourth hard coating layer-forming composition prepared in Preparation Example 4 was coated on the sixth hard coating layer to a thickness of 5㎛, dried in an oven at 80°C for 2 minutes, and then heated in a high-pressure mercury lamp at 350mJ/min. The fourth hard coating layer was formed by curing with a light quantity of cm2. Next, the first hard coating layer-forming composition prepared in Preparation Example 1 was coated on the third hard coating layer to a thickness of 5㎛, dried in an oven at 80°C for 2 minutes, and then cured in a high pressure mercury lamp with a light amount of 350mJ/cm2. A first hard coating layer was formed, and the second hard coating layer-forming composition prepared in Preparation Example 2 was coated on the fourth hard coating layer to a thickness of 5㎛, dried in an oven at 80°C for 2 minutes, and then heated at 350mJ/min in a high-pressure mercury lamp. A hard coating film was manufactured by curing with a light quantity of cm2 to form a second hard coating layer.
실시예Example 2: 2:
상기 하드코팅층-형성 조성물을 각각 10㎛의 두께로 코팅하는 것을 제외하고는 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was prepared in the same process as Example 1, except that the hard coating layer-forming composition was coated to a thickness of 10 μm.
실시예Example 3: 3:
상기 하드코팅층-형성 조성물을 각각 15㎛ 의 두께로 코팅하는 것을 제외하고는 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was prepared in the same manner as in Example 1, except that the hard coating layer-forming composition was coated to a thickness of 15 μm.
비교예Comparative example 1: One:
상기 제1 내지 2 하드코팅층을 형성하지 않는 것을 제외하고는, 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was manufactured in the same process as Example 1, except that the first to second hard coating layers were not formed.
비교예Comparative example 2: 2:
상기 제3 내지 4 하드코팅층을 형성하지 않는 것을 제외하고는, 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was manufactured in the same process as Example 1, except that the third to fourth hard coating layers were not formed.
비교예Comparative example 3: 3:
상기 제5 내지 6 하드코팅층을 형성하지 않는 것을 제외하고는, 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was manufactured in the same process as Example 1, except that the fifth to sixth hard coating layers were not formed.
비교예Comparative example 4: 4:
각 하드코팅층의 형성시에 고압 수은램프의 광량을 1500mJ/㎠로 증가시켜 경화를 수행하는 하는 것을 제외하고는, 실시예 1과 동일한 과정으로 하드코팅 필름을 제조하였다.
A hard coating film was manufactured in the same manner as in Example 1, except that when forming each hard coating layer, the amount of light from the high-pressure mercury lamp was increased to 1500 mJ/cm2 to perform curing.
실험예Experiment example 1: One:
상기에서 제조된 하드코팅 필름의 물성을 후술하는 방법으로 측정하고, 그 결과를 하기 표 1에 나타내었다.
The physical properties of the hard coating film prepared above were measured by the method described below, and the results are shown in Table 1 below.
(1) (One) 압축탄성율Compression modulus
각 하드코팅층의 표면 중앙을 피코덴터 HM-500((주)피셔 인스트루먼츠)을 사용해서 나노 인덴테이션법에 의해 압축 탄성율을 측정하였다. 상기 측정은 온도 25℃, 습도 50％에서 수행되었으며, 각 하드코팅층에 대해서 5회 측정한 후 평균값을 도출하였다.
The compressive elastic modulus of the center of the surface of each hard coating layer was measured by nano-indentation using a picodenter HM-500 (Fisher Instruments, Inc.). The measurement was performed at a temperature of 25°C and a humidity of 50%, and each hard coating layer was measured five times and the average value was derived.
(2) (2) 가교밀도crosslink density
각 하드코팅층을 15ml 테트라하이드로퓨란(THF) 용액 내에서 상온 조건하에 24시간 동안 보관하여 여과한 후, 녹지 않는 부분을 100℃에서 3시간 동안 건조 후 다시 50℃에서 15시간 동안 건조하였다. 이때, 각 하드코팅층에 대한 THF 용액에 담지시키기 전의 중량(W0) 및 THF 용액에 담지시킨 후의 중량(Wt)을 측정하여, 하기 식에 따라 가교밀도를 계산하였다.Each hard coating layer was stored in 15 ml of tetrahydrofuran (THF) solution at room temperature for 24 hours and filtered. The insoluble portion was dried at 100°C for 3 hours and then dried again at 50°C for 15 hours. At this time, the weight (W 0 ) of each hard coating layer before being supported in the THF solution and the weight (W t ) after being supported in the THF solution were measured, and the crosslinking density was calculated according to the following formula.
가교밀도 = Wt/W0
Crosslink density = W t /W 0
(3) (3) 가교강직성Cross-linking rigidity
상기 측정된 압축탄성율 및 가교밀도를 이용하여 하기 수학식 1에 따라 가교강직성을 계산하였다.Using the measured compressive modulus and crosslink density, crosslink stiffness was calculated according to Equation 1 below.
[수학식 1][Equation 1]
가교강직성(kPa·m) = 압축 탄성율(GPa)×층 두께(㎛)×가교밀도
Crosslink stiffness (kPa·m) = Compressive modulus (GPa) × Layer thickness (㎛) × Crosslink density
(4) 연필경도(4) Pencil hardness
유리 기판 상에 하드코팅 필름을 놓고, 연필경도 시험기(PHT, 한국 석보과학사)를 이용하여 1000g 하중을 걸고 제1 하드코팅층에 대한 연필경도를 측정하였다. 연필은 미쯔비시 제품을 사용하고, 한 연필경도당 5회 실시하였다. A hard coating film was placed on a glass substrate, and a 1000 g load was applied using a pencil hardness tester (PHT, Korea Seokbo Science Co., Ltd.) to measure the pencil hardness of the first hard coating layer. The pencil was a Mitsubishi product, and the test was conducted 5 times per pencil hardness.
점착제 연필경도는 유리 기판 상에 50㎛ 두께의 점착제층을 형성시키고, 상기 점착제층 상에 하드코팅 필름을 이의 제2 하드코팅층이 점착제층과 접하도록 부착하여(위부터 제1 하드코팅층/제3 하드코팅층/제5 하드코팅층/기재/제6 하드코팅층/제4 하드코팅층/제2 하드코팅층/점착제/유리 기판의 순서) 평가하였다.
The pencil hardness of the adhesive is obtained by forming a 50㎛ thick adhesive layer on a glass substrate and attaching a hard coating film on the adhesive layer so that its second hard coating layer is in contact with the adhesive layer (from the top, first hard coating layer/third The order of hard coating layer/fifth hard coating layer/substrate/sixth hard coating layer/fourth hard coating layer/second hard coating layer/adhesive/glass substrate) was evaluated.
(5) (5) 굴곡성flexibility
지름 4mm 및 6mm의 굽힘 테스트 기기(㈜ 코보텍)에 하드코팅 필름의 제1 하드코팅층이 안쪽으로 향하게 하여 굽혔을 때 필름에 파단(크랙)이 발생하는지 여부를 확인하였으며, 굽힘 과정을 20만회 반복하였다. 상기 테스트 기기에 굽힘 횟수를 입력한 후 실시간 카메라를 통해 크랙이 발생한 위치 및 굽힘 횟수를 확인하였다. 각 평가는 n=3으로 진행하였다.
We checked whether fractures (cracks) occurred in the film when the first hard coating layer of the hard coating film was bent inward on a bending test device (Kobotech Co., Ltd.) with a diameter of 4 mm and 6 mm, and the bending process was repeated 200,000 times. did. After inputting the number of bending into the test device, the location of the crack and the number of bending were confirmed through a real-time camera. Each evaluation was conducted with n=3.
제1 하드코팅층
1st hard coating layer
제2 하드코팅층
Second hard coating layer
제3 하드코팅층
Third hard coating layer
제4 하드코팅층
Fourth hard coating layer
제5 하드코팅층
Fifth hard coating layer
제6 하드코팅층
6th hard coating layer
상기 표 1에서 볼 수 있는 바와 같이, 6개의 하드코팅층을 구비하면서 각 층의 두께가 5 내지 50㎛이고 각층의 가교강직성 값이 1.2 내지 15 kPa·m의 범위를 동시에 만족하는 실시예 1 내지 3의 하드코팅 필름은 이러한 조건을 만족하지 못하는 비교예 1 내지 4의 경우에 비해 연필경도가 높고 우수한 굽힘 결과를 나타내었다.
As can be seen in Table 1, Examples 1 to 3 have six hard coating layers, each layer has a thickness of 5 to 50 μm, and each layer has a crosslinking stiffness value of 1.2 to 15 kPa·m. The hard coating film showed higher pencil hardness and excellent bending results compared to Comparative Examples 1 to 4, which did not meet these conditions.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. do. Anyone skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (11)
상기 제1 하드코팅층 내지 제6 하드코팅층은 각각 두께가 5 내지 50 ㎛ 이고, 하기 수학식 1로 정의되는 가교강직성 값의 범위가 1.2 내지 15 kPa·m인 플렉시블 디스플레이용 하드코팅 필름:
[수학식 1]
가교강직성(kPa·m) = 압축 탄성율(GPa)×층 두께(㎛)×가교밀도.transparent substrate; A first hard coating layer formed on one side of the transparent substrate; a second hard coating layer formed on the other side of the transparent substrate; A third hard coating layer located between the transparent substrate and the first hard coating layer; A fourth hard coating layer located between the transparent substrate and the second hard coating layer; A fifth hard coating layer located between the transparent substrate and the third hard coating layer; And a sixth hard coating layer located between the transparent substrate and the fourth hard coating layer,
The first to sixth hard coating layers each have a thickness of 5 to 50 ㎛, and have a crosslinking stiffness value in the range of 1.2 to 15 kPa·m, defined by Equation 1 below: A hard coating film for a flexible display:
[Equation 1]
Crosslink stiffness (kPa·m) = compressive modulus (GPa) × layer thickness (㎛) × crosslink density.
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| KR101415838B1 (en) | 2012-08-23 | 2014-07-09 | 주식회사 엘지화학 | Composition for hard coating |
| KR101959474B1 (en) * | 2012-12-13 | 2019-03-18 | 동우 화인켐 주식회사 | Organic-inorganic hybrid hard coating film and polarizing plate using the same |
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| JP2000214791A (en) | 1998-11-17 | 2000-08-04 | Dainippon Printing Co Ltd | Hard coat film and antireflection film |
| WO2013125235A1 (en) | 2012-02-24 | 2013-08-29 | 三井化学株式会社 | Optical-device surface-sealing composition, optical-device surface-sealing sheet, display, and display manufacturing method |
| JP2015151472A (en) | 2014-02-14 | 2015-08-24 | 株式会社巴川製紙所 | Adhesive composition for hard coat film, adhesive type hard coat film, and curable hard coat film |
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| KR20170075663A (en) | 2017-07-03 |
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