KR102621492B1 - Hard Coating Composition and Hard Coating Film Using the Same - Google Patents
Hard Coating Composition and Hard Coating Film Using the Same Download PDFInfo
- Publication number
- KR102621492B1 KR102621492B1 KR1020160061586A KR20160061586A KR102621492B1 KR 102621492 B1 KR102621492 B1 KR 102621492B1 KR 1020160061586 A KR1020160061586 A KR 1020160061586A KR 20160061586 A KR20160061586 A KR 20160061586A KR 102621492 B1 KR102621492 B1 KR 102621492B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- hard coating
- group
- coating composition
- Prior art date
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- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
Abstract
본 발명은 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치 화합물, 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트, 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트, 광개시제 및 용제를 포함하는 하드코팅 조성물, 이를 이용하여 형성되는 하드코팅 필름 및 상기 하드코팅 필름이 구비된 화상표시장치를 제공한다. 본 발명에 따른 하드코팅 필름은 내찰상성이 높고 경도와 유연성이 우수할 뿐만 아니라 밀착성, 컬 및 크랙 특성이 우수하다.The present invention is a hard coating comprising a hyperbranched compound having a (meth)acrylate terminal group, a polyfunctional urethane (meth)acrylate having a cyclohexyl group, a polyfunctional (meth)acrylate having an ethylene glycol group, a photoinitiator, and a solvent. A composition, a hard coating film formed using the same, and an image display device equipped with the hard coating film are provided. The hard coating film according to the present invention not only has high scratch resistance and excellent hardness and flexibility, but also has excellent adhesion, curl, and crack characteristics.
Description
본 발명은 하드코팅 조성물 및 이를 이용한 하드코팅 필름에 관한 것으로, 보다 상세하게는 경도와 내찰상성이 우수하면서 유연성을 가지는 하드코팅 조성물, 이를 이용하여 형성되는 하드코팅 필름 및 상기 하드코팅 필름이 구비된 화상표시장치에 관한 것이다.The present invention relates to a hard coating composition and a hard coating film using the same, and more specifically, to a hard coating composition having excellent hardness and scratch resistance and flexibility, a hard coating film formed using the same, and a hard coating film provided with the hard coating film. It relates to image display devices.
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.
일본 등록특허 제4966456호에는 다관능성 아크릴레이트 100 중량부, 방사선 경화형 실리콘 수지 0.1 내지 100 중량부 및 구상 필러 0.5 내지 100 중량부를 포함하는 코팅제를 기재 상에 도포 및 경화하여 얻은 하드코팅된 시트가 개선된 슬립성 및 내찰상성을 갖는다고 개시하고 있다.Japanese Patent No. 4966456 discloses an improved hard-coated sheet obtained by applying and curing a coating agent containing 100 parts by weight of a multifunctional acrylate, 0.1 to 100 parts by weight of a radiation-curable silicone resin, and 0.5 to 100 parts by weight of a spherical filler on a substrate. It is disclosed that it has excellent slip properties and scratch resistance.
그러나, 상기 하드코팅된 시트는 플렉서블 표시장치에 적용할 수 있을 만큼 충분한 경도와 유연성을 가지면서 내찰상성을 확보하기 어려운 문제점이 있었다.However, the hard-coated sheet had a problem in that it was difficult to secure scratch resistance while having sufficient hardness and flexibility to be applied to a flexible display device.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 본 발명의 한 목적은 경도와 내찰상성이 우수하면서 유연성을 가지는 하드코팅 필름의 제조에 사용될 수 있는 하드코팅 조성물을 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 composition that can be used in the production of a hard coating film having excellent hardness and scratch resistance and flexibility.
본 발명의 다른 목적은 상기 하드코팅 조성물을 이용하여 형성되는 하드코팅 필름을 제공하는 것이다.Another object of the present invention is to provide a hard coating film formed using the hard coating composition.
본 발명의 또 다른 목적은 상기 하드코팅 필름이 구비된 화상표시장치를 제공하는 것이다.Another object of the present invention is to provide an image display device equipped with the hard coating film.
한편으로, 본 발명은 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치 화합물, 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트, 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트, 광개시제 및 용제를 포함하는 하드코팅 조성물을 제공한다.On the other hand, the present invention includes a hyperbranched compound having a (meth)acrylate end group, a polyfunctional urethane (meth)acrylate having a cyclohexyl group, a polyfunctional (meth)acrylate having an ethylene glycol group, a photoinitiator, and a solvent. A hard coating composition is provided.
본 발명의 일 실시형태에서, 상기 하이퍼브랜치 화합물의 분지화도는 0.05 이상 1 미만일 수 있다.In one embodiment of the present invention, the degree of branching of the hyperbranched compound may be 0.05 or more and less than 1.
본 발명의 일 실시형태에서, 상기 하이퍼브랜치 화합물은 디펜타에리스리톨을 코어로 하는 것일 수 있다.In one embodiment of the present invention, the hyperbranched compound may have dipentaerythritol as its core.
본 발명의 일 실시형태에서, 상기 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트는 시클로헥실기를 갖는 디이소시아네이트와 히드록시기를 갖는 다관능 (메타)아크릴레이트를 축합반응시켜 제조할 수 있다.In one embodiment of the present invention, the polyfunctional urethane (meth)acrylate having a cyclohexyl group can be produced by condensing a diisocyanate having a cyclohexyl group and a polyfunctional (meth)acrylate having a hydroxy group.
본 발명의 일 실시형태에서, 상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트는 다가 알코올에 에틸렌옥사이드를 부가반응시켜 에틸렌글리콜기를 갖는 다관능 알코올을 수득하고, 상기 다관능 알코올에 (메타)아크릴산을 축합반응시켜 제조할 수 있다.In one embodiment of the present invention, the polyfunctional (meth)acrylate having an ethylene glycol group is obtained by adding ethylene oxide to a polyhydric alcohol to obtain a polyfunctional alcohol having an ethylene glycol group, and (meth)acrylic acid is added to the polyfunctional alcohol. It can be manufactured through a condensation reaction.
본 발명의 일 실시형태에 따른 하드코팅 조성물은 무기 나노입자를 추가로 포함할 수 있다.The hard coating composition according to one embodiment of the present invention may further include inorganic nanoparticles.
다른 한편으로, 본 발명은 상기 하드코팅 조성물을 이용하여 형성되는 하드코팅 필름을 제공한다.On the other hand, the present invention provides a hard coating film formed using the hard coating composition.
또 다른 한편으로, 본 발명은 상기 하드코팅 필름이 구비된 화상표시장치를 제공한다.On the other hand, the present invention provides an image display device equipped with the hard coating film.
본 발명에 따른 하드코팅 조성물을 이용하여 형성되는 하드코팅 필름은 내찰상성이 높고 경도가 우수할 뿐만 아니라, 밀착성, 컬 및 크랙 특성이 우수하므로 플렉서블(flexible) 표시장치의 윈도우에 효과적으로 사용될 수 있다.The hard coating film formed using the hard coating composition according to the present invention not only has high scratch resistance and excellent hardness, but also has excellent adhesion, curl, and crack properties, so it can be effectively used in the window of a flexible display device.
이하, 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치(hyperbranch) 화합물, 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트, 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트, 광개시제 및 용제를 포함하는 하드코팅 조성물에 관한 것이다.
One embodiment of the present invention is a hyperbranched compound having a (meth)acrylate end group, a polyfunctional urethane (meth)acrylate having a cyclohexyl group, a polyfunctional (meth)acrylate having an ethylene glycol group, and a photoinitiator. and a hard coating composition containing a solvent.
본 발명의 일 실시형태에서, 상기 하이퍼브랜치 화합물은 고분자량 고분자로서 수지상 지방족 화합물(dendritic aliphatic compound)로도 불린다. 하이퍼브랜치 화합물 중에서 일반적으로 규칙성이 높은 구조를 덴드리머라고 부르고, 규칙성이 낮은 구조를 하이퍼브랜치 폴리머라고 한다. 상기 하이퍼브랜치 화합물은 복수의 반응 사이트를 갖는 화합물로부터 성장시키는 방법으로 합성된다. 상기 하이퍼브랜치 화합물은 쇄상 고분자와 비교하여 점도의 거동이 다른 특징을 가지게 된다. 이는 쇄상 고분자가 분자끼리 얽혀져 분자의 자유에너지가 억제되기 때문에 쇄의 길이가 길수록 점도가 증대되는 반면, 하이퍼브랜치 화합물은 분자끼리의 얽혀짐이 적기 때문에 같은 분자량의 쇄상 고분자와 비교했을 때 점도가 낮게 되기 때문이다. 이러한 구조적인 특징으로 인해 상기 하이퍼브랜치 화합물은 저점도 코팅이 가능하고 경화속도가 빠르며 경화 수축이 적은 효과를 갖게 된다. 더불어 분자 내 결합밀도 차이로 인해 높은 경도와 유연성을 갖게 한다.In one embodiment of the present invention, the hyperbranched compound is a high molecular weight polymer and is also called a dendritic aliphatic compound. Among hyperbranched compounds, structures with high regularity are generally called dendrimers, and structures with low regularity are called hyperbranched polymers. The hyperbranched compound is synthesized by growing from a compound having a plurality of reaction sites. The hyperbranched compound has different viscosity behavior compared to chain polymers. This is because chain polymers are entangled with each other and the free energy of the molecules is suppressed, so the viscosity increases as the length of the chain increases, whereas hyperbranched compounds have less entanglement between molecules, so their viscosity is lower when compared to chain polymers of the same molecular weight. Because it becomes low. Due to these structural characteristics, the hyperbranched compound enables low-viscosity coating, has a fast curing speed, and has low curing shrinkage. In addition, it has high hardness and flexibility due to the difference in bond density within the molecule.
상기 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치 화합물은 하드코팅 조성물 전체 100중량%에 대하여 10 내지 50중량%, 바람직하게는 15 내지 45 중량%로 포함될 수 있다. 10 중량% 보다 작을 경우에는 굽힘 특성을 나타내기 어려울 수 있고, 50중량% 보다 클 경우에는 입체 저해 효과로 인한 미반응 관능기의 존재로 코팅층에 경도 특성을 부여하기 어려울 수 있다.
The hyperbranched compound having the (meth)acrylate end group may be included in an amount of 10 to 50% by weight, preferably 15 to 45% by weight, based on 100% by weight of the total hard coating composition. If it is less than 10% by weight, it may be difficult to exhibit bending properties, and if it is larger than 50% by weight, it may be difficult to impart hardness properties to the coating layer due to the presence of unreacted functional groups due to the steric inhibition effect.
본 발명의 일 실시형태에서, 상기 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치 화합물은 분지화도가 0.05 이상 1 미만, 특히 0.1 내지 0.9, 예를 들어 약 0.5일 수 있다.In one embodiment of the present invention, the hyperbranched compound having the (meth)acrylate end group may have a branching degree of 0.05 or more and less than 1, particularly 0.1 to 0.9, for example, about 0.5.
하이퍼브랜치 화합물은 일반적으로 3가지 형태의 반복단위, 즉 덴드리틱 유닛(dendritic unit), 선형 유닛(linear unit) 및 터미널 유닛(terminal unit)을 가지며, 분지화도(degree of branching, DB)는 하기 수학식 1로 정의될 수 있다.Hyperbranched compounds generally have three types of repeating units: dendritic units, linear units, and terminal units, and the degree of branching (DB) is as follows: It can be defined as Equation 1.
[수학식 1][Equation 1]
DB = (D+T)/(D+T+L)DB = (D+T)/(D+T+L)
상기 식에서, In the above equation,
D는 덴드리틱 유닛의 수이고, T는 터미널 유닛의 수이며, L은 선형 유닛의 수이다.D is the number of dendritic units, T is the number of terminal units, and L is the number of linear units.
예를 들어, 만약 분지화도가 0이면 쇄상 고분자, 분지화도가 1이면 덴드리머가 된다. For example, if the degree of branching is 0, it becomes a chain polymer, and if the degree of branching is 1, it becomes a dendrimer.
상기 분지화도는 핵자기공명 스펙트럼에서 덴드리틱 유닛, 선형 유닛, 터미널 유닛에 각각 관련된 피크의 적분치 비로부터 계산가능하다.
The degree of branching can be calculated from the ratio of the integral values of peaks related to dendritic units, linear units, and terminal units in the nuclear magnetic resonance spectrum.
본 발명의 일 실시형태에서, 상기 하이퍼브랜치 화합물의 상업적으로 입수할 수 있는 예로서는 STAR-501(SIRIUS-501, SUBARU-501)(오사카 유키카가쿠고교 주식회사) 등을 들 수 있다. 상기 STAR-501은 디펜타에리스리톨을 코어로 하는 것으로, 말단에 아크릴레이트기를 가지는 다분기(디펜타에리스리톨헥사아크릴레이트(DPHA) 연결형) 폴리아크릴레이트를 주성분으로 하는 것이다. 또, STAR-501의 분자량은 16,000~24,000 정도이다.
In one embodiment of the present invention, commercially available examples of the hyperbranched compounds include STAR-501 (SIRIUS-501, SUBARU-501) (Osaka Yuki Chemical Co., Ltd.). The STAR-501 has dipentaerythritol as its core and is mainly composed of multi-branched (dipentaerythritol hexaacrylate (DPHA) linked) polyacrylate having an acrylate group at the terminal. Additionally, the molecular weight of STAR-501 is approximately 16,000 to 24,000.
본 발명의 일 실시형태에서, 상기 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트는 코팅되는 필름의 기계적 물성, 특히 경도를 개선하기 위한 성분으로서, 하드코팅 조성물 전체 100중량%에 대하여 10 내지 30중량%, 바람직하게는 15 내지 25 중량%로 포함될 수 있다. 10 중량% 보다 적을 경우에는 기계적 물성, 특히 경도의 저하가 있을 수 있고, 30 중량% 보다 클 경우에는 수축력이 커져서 필름의 컬, 파단, 크랙 등이 발생할 수 있다.
In one embodiment of the present invention, the polyfunctional urethane (meth)acrylate having a cyclohexyl group is an ingredient for improving the mechanical properties, especially hardness, of the coated film, and is used in an amount of 10 to 100% by weight of the total hard coating composition. It may be included at 30% by weight, preferably 15 to 25% by weight. If it is less than 10% by weight, there may be a decrease in mechanical properties, especially hardness, and if it is more than 30% by weight, the shrinkage force may increase and curl, breakage, cracks, etc. of the film may occur.
상기 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트는 시클로헥실기를 갖는 디이소시아네이트와 히드록시기를 갖는 다관능 (메타)아크릴레이트를 축합반응시켜 제조할 수 있다.The polyfunctional urethane (meth)acrylate having a cyclohexyl group can be produced by condensing a diisocyanate having a cyclohexyl group and a polyfunctional (meth)acrylate having a hydroxy group.
상기 시클로헥실기를 갖는 디이소시아네이트는 구체적으로 1,4-시클로헥실 디이소시아네이트, 이소포론 디이소시아네이트, 4,4-디시클로헥실메탄 디이소시아네이트 등일 수 있으나, 이에 한정되는 것은 아니다. The diisocyanate having the cyclohexyl group may specifically include 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, etc., but is not limited thereto.
상기 히드록시기를 갖는 다관능 (메타)아크릴레이트는 구체적으로 트리메틸올프로판 디(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트 등일 수 있으나, 이에 한정되는 것은 아니다. The polyfunctional (meth)acrylate having the hydroxy group may specifically include trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate, but is not limited thereto. no.
본 발명의 일 실시형태에서, 상기 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트는 하기 화학식 1 내지 2의 화합물로 구성된 군으로부터 선택된 1종 이상을 포함할 수 있다.In one embodiment of the present invention, the polyfunctional urethane (meth)acrylate having a cyclohexyl group may include at least one selected from the group consisting of compounds of the following formulas 1 and 2.
[화학식 1] [Formula 1]
[화학식 2] [Formula 2]
본 발명의 일 실시형태에서, 상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트는 코팅되는 필름에 유연성을 부여하기 위한 성분으로서, 하드코팅 조성물 전체 100 중량%에 대하여 5 내지 30 중량%, 바람직하게는 10 내지 25 중량%로 포함될 수 있다. 5 중량% 보다 적을 경우에는 유연성이 부족하여 코팅 필름의 파단이나 크랙이 발생할 수 있고, 30 중량% 보다 클 경우에는 기계적인 물성이 저하되어 표면 스크래치나 연필경도 저하 현상이 발생할 수 있다.
In one embodiment of the present invention, the polyfunctional (meth)acrylate having an ethylene glycol group is a component for providing flexibility to the coated film, and is preferably contained in an amount of 5 to 30% by weight based on 100% by weight of the total hard coating composition. May be included in 10 to 25% by weight. If it is less than 5% by weight, the coating film may break or crack due to lack of flexibility, and if it is more than 30% by weight, mechanical properties may deteriorate, resulting in surface scratches or a decrease in pencil hardness.
상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트는 다가 알코올에 에틸렌옥사이드를 부가반응시켜 에틸렌글리콜기를 갖는 다관능 알코올을 수득하고, 상기 다관능 알코올에 (메타)아크릴산을 축합반응시켜 제조할 수 있다.The polyfunctional (meth)acrylate having an ethylene glycol group can be prepared by adding ethylene oxide to a polyhydric alcohol to obtain a polyfunctional alcohol having an ethylene glycol group, and then condensing (meth)acrylic acid with the polyfunctional alcohol. .
상기 다가 알코올은 구체적으로 글리세롤, 트리메틸올프로판, 펜타에리스리톨, 디펜타에리스리톨 등일 수 있으나, 이에 한정되는 것은 아니다.The polyhydric alcohol may specifically be glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc., but is not limited thereto.
상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트의 구체적인 예로는, 트리메틸올프로판(EO)3 트리(메타)아크릴레이트, 트리메틸올프로판(EO)6 트리(메타)아크릴레이트, 트리메틸올프로판(EO)9 트리(메타)아크릴레이트, 글리세린(EO)3 트리(메타)아크릴레이트, 글리세린(EO)6 트리(메타)아크릴레이트, 글리세린(EO)9 트리(메타)아크릴레이트, 펜타에리스리톨(EO)4 테트라(메타)아크릴레이트, 펜타에리스리톨(EO)8 테트라(메타)아크릴레이트, 펜타에리스리톨(EO)12 테트라(메타)아크릴레이트, 디펜타에리스리톨(EO)6 헥사(메타)아크릴레이트, 디펜타에리스리톨(EO)12 헥사(메타)아크릴레이트, 디펜타에리스리톨(EO)18 헥사(메타)아크릴레이트 등이 있다.Specific examples of the polyfunctional (meth)acrylate having an ethylene glycol group include trimethylolpropane (EO) 3 Tri(meth)acrylate, trimethylolpropane (EO) 6 Tri(meth)acrylate, trimethylolpropane (EO) 9 Tri(meth)acrylate, glycerin (EO) 3 Tri(meth)acrylate, glycerin (EO) 6 Tri(meth)acrylate, glycerin (EO) 9 Tri(meth)acrylate, pentaerythritol (EO) 4 Tetra(meth)acrylate, pentaerythritol (EO) 8 Tetra(meth)acrylate, pentaerythritol (EO) 12 Tetra(meth)acrylate, dipentaerythritol (EO) 6 hexa(meth)acrylate, dipentaerythritol (EO) 12 hexa(meth)acrylate, dipentaerythritol (EO) 18 hexa(meth)acrylate, etc. there is.
본 발명의 일 실시형태에서, 상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트는 하기 화학식 3 내지 4의 화합물로 구성된 군으로부터 선택된 1종 이상을 포함할 수 있다.In one embodiment of the present invention, the polyfunctional (meth)acrylate having an ethylene glycol group may include at least one selected from the group consisting of compounds of the following formulas 3 to 4.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
본 발명의 일 실시형태에서, 상기 광개시제는 당해 기술분야에서 사용되는 것이라면 제한되지 않고 사용될 수 있다. 화학구조 또는 분자결합 에너지의 차에 의해 분자의 분해로 라디칼이 생성되는 Type 1형 광개시제와 3차 아민과 공존하여 수소 탈환형의 Type 2형 광개시제가 있다. Type 1형 광개시제의 구체적인 예로는 4-페녹시디클로로아세트페논, 4-t-부틸디클로로아세트페논, 4-t-부틸트리클로로아세트페논, 디에톡시아세트페논, 2-히드록시-2-메틸-l-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-l-온, 1-(4-도데실페닐)-2-히드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실페닐케톤 등의 아세트페논류, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤질디메틸케탈 등의 벤조인류, 아실포스핀옥사이드류, 티타노센 화합물 등을 들 수 있다. Type 2형 광개시제의 구체적인 예로는 벤조페논, 벤조일벤조익에시드, 벤조일벤조익에시드메틸에테르, 4-페닐벤조페논, 히드록시벤조페논, 4-벤졸-4'-메틸디페닐설파이드, 3,3'-메틸-4-메톡시벤조페논 등의 벤조페논류, 티옥산톤, 2-클로로티옥산톤, 2-메틸티옥산톤, 2,4-디메틸티옥산톤, 이소프로필티옥산톤 등의 티옥산톤 등을 들 수 있다. 이들은 각각 단독으로 또는 둘 이상을 조합하여 사용할 수 있다. 또한 Type 1형 광개시제와 Type 2형 광개시제를 단독으로 또는 병용하여 사용할 수도 있다.In one embodiment of the present invention, the photoinitiator may be used without limitation as long as it is used in the relevant technical field. There are Type 1 photoinitiators, which generate radicals by decomposition of molecules due to differences in chemical structure or molecular bond energy, and Type 2 photoinitiators, which coexist with tertiary amines and produce hydrogen recapture. Specific examples of type 1 photoinitiators include 4-phenoxydichloroacetphenone, 4-t-butyldichloroacetphenone, 4-t-butyltrichloroacetphenone, diethoxyacetphenone, and 2-hydroxy-2-methyl-l. -Phenylpropan-l-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl Acetophenones such as propan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, benzoin, benzoinmethyl Benzoins such as ether, benzoin ethyl ether, and benzyl dimethyl ketal, acylphosphine oxides, and titanocene compounds can be mentioned. Specific examples of type 2 photoinitiators include benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzole-4'-methyldiphenyl sulfide, 3,3' -Benzophenones such as methyl-4-methoxybenzophenone, teas such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and isopropylthioxanthone Oxanthone, etc. can be mentioned. These can be used individually or in combination of two or more. Additionally, Type 1 photoinitiator and Type 2 photoinitiator can be used alone or in combination.
상기 광개시제는 상기 하드코팅 조성물 전체 100 중량%에 대하여 0.1 내지 10 중량%, 바람직하게는 1 내지 5 중량%로 포함될 수 있다. 0.1 중량% 미만인 경우 경화가 충분히 진행되지 않아 최종 얻어진 도막의 기계적 물성이나 밀착력이 저하될 수 있으며, 10 중량% 초과인 경우 경화 수축으로 인한 크랙 및 컬 현상이 발생할 수 있다.
The photoinitiator may be included in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on 100% by weight of the total hard coating composition. If it is less than 0.1% by weight, curing may not proceed sufficiently and the mechanical properties or adhesion of the final coating film may be reduced, and if it is more than 10% by weight, cracks and curls may occur due to curing shrinkage.
본 발명의 일 실시형태에서, 상기 용제는 당해 기술분야에서 사용되는 것이라면 제한되지 않고 사용할 수 있다. 구체적으로, 알코올계(메탄올, 에탄올, 이소프로판올, 부탄올, 프로필렌글리콜 메톡시 알코올 등), 케톤계(메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 디에틸케톤, 디프로필케톤 등), 아세테이트계(메틸 아세테이트, 에틸 아세테이트, 부틸 아세테이트, 프로필렌글리콜 메톡시 아세테이트 등), 셀로솔브계(메틸 셀로솔브, 에틸 셀로솔브, 프로필 셀로솔브 등), 탄화수소계(노말 헥산, 노말 헵탄, 벤젠, 톨루엔, 자일렌 등) 등을 들 수 있다. 상기 용제들은 각각 단독으로 또는 둘 이상을 조합하여 사용할 수 있다.In one embodiment of the present invention, the solvent may be used without limitation as long as it is used in the technical field. Specifically, alcohol-based (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.), acetate-based (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc.), cellosolve type (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbon type (normal hexane, normal heptane, benzene, toluene, xyl Ren, etc.), etc. may be mentioned. The above solvents can be used individually or in combination of two or more.
상기 용제는 상기 하드코팅 조성물 전체 100 중량%에 대하여 5 내지 90 중량%, 바람직하게는 20 내지 70 중량%로 포함될 수 있다. 5 중량% 미만인 경우 점도가 높아 작업성이 떨어지고, 90 중량% 초과인 경우에는 코팅막 두께 조정이 어렵고 건조얼룩이 발생하여 외관불량이 생기는 단점이 있다.
The solvent may be included in an amount of 5 to 90 wt%, preferably 20 to 70 wt%, based on 100 wt% of the total hard coating composition. If it is less than 5% by weight, the viscosity is high and workability is poor, and if it is more than 90% by weight, it is difficult to adjust the thickness of the coating film and dry stains occur, resulting in poor appearance.
본 발명의 일 실시형태에 따른 하드코팅 조성물은 기계적 특성을 보다 더 개선하기 위하여 무기 나노입자를 추가로 포함할 수 있다.The hard coating composition according to one embodiment of the present invention may further include inorganic nanoparticles to further improve mechanical properties.
상기 무기 나노입자는 평균 입경이 1 내지 100㎚, 바람직하게는 5 내지 50㎚인 것을 사용할 수 있다. 이러한 무기 나노입자는 도막 내에 균일하게 형성되어 내마모성, 내스크래치성, 연필경도 등의 기계적 물성을 향상시킬 수 있다. 만약, 입자 크기가 상기 범위 미만이면 조성물 내에서 응집이 발생하여 균일한 도막을 형성할 수 없으며 상기 효과를 기대할 수 없고, 이와 반대로 상기 범위를 초과하면 최종 얻어진 도막의 광학 특성이 저하될 뿐만 아니라, 오히려 기계적 물성이 저하되는 문제가 발생할 수 있다. The inorganic nanoparticles may have an average particle diameter of 1 to 100 nm, preferably 5 to 50 nm. These inorganic nanoparticles are uniformly formed within the coating film and can improve mechanical properties such as wear resistance, scratch resistance, and pencil hardness. If the particle size is less than the above range, agglomeration may occur within the composition, making it impossible to form a uniform coating film, and the above effect cannot be expected. Conversely, if the particle size exceeds the above range, not only will the optical properties of the final coating film obtained deteriorate, Rather, a problem of deterioration of mechanical properties may occur.
이러한 무기 나노입자의 재질은 금속 산화물일 수 있으며, Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, ITO, IZO, ATO, ZnO-Al, Nb2O3, SnO, MgO 및 이들의 조합으로 이루어진 군에서 선택된 1종을 사용할 수 있으며, 바람직하게는 Al2O3, SiO2, ZrO2 등을 사용할 수 있다. 상기 무기 나노입자는 직접 제조하거나 시판되는 것을 구입하여 사용할 수 있다. 시판되는 제품의 경우 유기 용매에 10 내지 80 중량%의 농도로 분산된 것을 사용할 수 있다.The material of these inorganic nanoparticles may be metal oxide, 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- One type selected from the group consisting of Al, Nb 2 O 3 , SnO, MgO, and combinations thereof may be used, and preferably Al 2 O 3 , SiO 2 , ZrO 2 , etc. may be used. The inorganic nanoparticles can be manufactured directly or purchased commercially. In the case of commercially available products, they can be used dispersed in an organic solvent at a concentration of 10 to 80% by weight.
상기 무기 나노입자는 상기 하드코팅 조성물 전체 100 중량%에 대하여 5 내지 40 중량%로 포함될 수 있다. 5 중량% 미만인 경우에는 내마모성, 내스크래치성, 연필경도 등의 기계적 물성이 충분하지 않을 수 있으며, 40 중량% 초과인 경우에는 경화성을 방해하여 오히려 기계적 물성이 저하되고, 외관이 불량해질 수 있다.
The inorganic nanoparticles may be included in an amount of 5 to 40% by weight based on 100% by weight of the total hard coating composition. If it is less than 5% by weight, mechanical properties such as wear resistance, scratch resistance, and pencil hardness may not be sufficient, and if it is more than 40% by weight, it may interfere with hardenability, which may result in lower mechanical properties and poor appearance.
본 발명의 일 실시형태에 따른 하드코팅 조성물은 상기한 성분들 이외에도, 당해 기술분야에서 일반적으로 사용되는 성분들, 예를 들어 레벨링제, 자외선 안정제, 열 안정제, 항산화제, UV 흡수제, 계면활성제, 윤활제, 방오제 등이 추가적으로 포함될 수 있다.
In addition to the above-described ingredients, the hard coating composition according to an embodiment of the present invention includes ingredients commonly used in the art, such as leveling agents, UV stabilizers, heat stabilizers, antioxidants, UV absorbers, surfactants, Lubricants, anti-fouling agents, etc. may be additionally included.
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-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-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 자외선 안정제는 경화된 도막의 표면이 지속적인 자외선 노출에 의해 분해를 일으켜 변색되고 잘 부스러지게 되므로, 이러한 자외선을 차단하거나 흡수하여 도막을 보호할 목적으로 첨가되는 첨가제이다. 상기 자외선 안정제는 작용 기구에 따라 흡수제, 소광제(Quencher), 힌더드 아민 광안정제(HALS, Hindered Amine Light Stabilizer)로 구분한다. 또한, 화학구조에 따라 페닐 살리실레이트(Phenyl Salicylate, 흡수제), 벤조페논(Benzophenone, 흡수제), 벤조트리아졸(Benzotriazole, 흡수제), 니켈유도체(소광제), 라디칼 스캐빈저(Radical Scavenger)로 구분할 수 있다. 상기 자외선 안정제는 도막의 초기 색상을 크게 변화시키지 않는 것이라면 특별히 한정되지 않는다.The UV stabilizer is an additive added to protect the coating film by blocking or absorbing UV rays because the surface of the cured coating film is decomposed by continuous exposure to UV rays, causing discoloration and brittleness. The UV stabilizers are classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) depending on their mechanism of action. In addition, depending on the chemical structure, it is classified into Phenyl Salicylate (absorbent), Benzophenone (absorbent), Benzotriazole (absorbent), Nickel Derivative (quencher), and Radical Scavenger. can be distinguished. The UV stabilizer is not particularly limited as long as it does not significantly change the initial color of the coating film.
상기 열 안정제는 상업적으로 적용할 수 있는 제품으로 1차 열 안정제인 폴리페놀계, 2차 열 안정제인 포스파이트계 및 락톤계를 각각 단독 또는 혼용하여 사용할 수 있다.The heat stabilizer is a commercially applicable product, and polyphenol-based primary heat stabilizers, phosphite-based and lactone-based secondary heat stabilizers can be used alone or in combination.
상기 자외선 안정제와 열 안정제는 자외선 경화성에 영향이 없는 수준에서 적절히 함량을 조절하여 사용할 수 있다.
The UV stabilizer and heat stabilizer can be used by appropriately adjusting the content to a level that does not affect UV curing properties.
본 발명의 일 실시형태는 상술한 하드코팅 조성물을 이용하여 형성되는 하드코팅 필름에 관한 것이다. 본 발명의 일 실시형태에 따른 하드코팅 필름은 투명기재의 한면 또는 양면에 상술한 하드코팅 조성물의 경화물을 포함하는 코팅층이 형성되어 있는 것을 특징으로 한다.One embodiment of the present invention relates to a hard coating film formed using the above-described hard coating composition. The hard coating film according to one embodiment of the present invention is characterized in that a coating layer containing a cured product of the above-described hard coating composition is formed on one or both sides of a transparent substrate.
상기 투명기재로는 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 oriented films can be used.
상기 투명기재의 두께는 특별히 제한되지 않으나, 8 내지 1000㎛, 구체적으로는 20 내지 150㎛일 수 있다. 상기 투명기재의 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 ㎛, specifically 20 to 150 ㎛. If the thickness of the transparent substrate is less than 8㎛, the strength of the film is lowered and processability is lowered, and if it is more than 1000㎛, transparency is reduced or the weight of the hard coating film increases.
본 발명의 일 실시형태에 따른 하드코팅 필름은 투명기재의 한면 또는 양면에 본 발명의 하드코팅 조성물을 도포하고 경화시켜 코팅층을 형성시킴으로써 제조할 수 있다.The hard coating film according to one embodiment of the present invention can be manufactured by applying the hard coating composition of the present invention to one or both sides of a transparent substrate and curing it to form a coating layer.
본 발명의 일 실시형태에 따른 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 according to one embodiment of the present invention is 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. ) is possible.
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.
이때, 형성되는 코팅층의 두께는 구체적으로 2 내지 30㎛, 보다 구체적으로 3 내지 20㎛일 수 있다. 상기 코팅층의 두께가 상기 범위 내에 포함될 경우 우수한 경도 효과를 얻을 수 있다.
At this time, the thickness of the coating layer formed may be specifically 2 to 30 μm, and more specifically, 3 to 20 μm. When the thickness of the coating layer is within the above range, an excellent hardness effect can be obtained.
본 발명의 일 실시형태는 상술한 하드코팅 필름이 구비된 화상표시장치에 관한 것이다. 일례로, 본 발명의 하드코팅 필름은 화상표시장치, 특히 플렉서블(flexible) 표시장치의 윈도우에 부착시킬 수 있다. 또한, 본 발명의 하드코팅 필름은 편광판, 터치 센서 등에 부착하여 사용할 수도 있다.One embodiment of the present invention relates to an image display device equipped with the above-described hard coating film. For example, the hard coating film of the present invention can be attached to the window of an image display device, especially a flexible display device. Additionally, the hard coating film of the present invention can also be used by attaching it to a polarizing plate, touch sensor, etc.
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.
실시예Example 1 내지 4 및 1 to 4 and 비교예Comparative example 1 내지 3: 1 to 3: 하드코팅hard coating 조성물의 제조 Preparation of composition
하기 표 1의 조성으로 하드코팅 조성물을 제조하였다(단위: 중량%).A hard coating composition was prepared with the composition shown in Table 1 below (unit: weight %).
하이퍼브랜치 화합물: SIRIUS-501(오사카 유키카가쿠고교 주식회사)Hyperbranch compound: SIRIUS-501 (Osaka Yuki Kagaku Kogyo Co., Ltd.)
화학식1의 화합물 (신아 T&C SOU-1700B)Compound of Formula 1 (Shinah T&C SOU-1700B)
화학식4의 화합물 (DPEA-126, 일본화약)Compound of formula 4 (DPEA-126, Japanese gunpowder)
무기 나노입자: MEK-AC-2140Z (Nissan chemical사)Inorganic nanoparticles: MEK-AC-2140Z (Nissan chemicals)
광개시제: CP-4 (미원스폐셜티케미칼사)Photoinitiator: CP-4 (Miwon Specialty Chemicals)
용제: 메틸에틸케톤
Solvent: Methyl ethyl ketone
실험예Experiment example 1: One:
상기 실시예 및 비교예에서 제조된 하드코팅 조성물을 광학용 폴리이미드 필름(미츠비시 가스케미칼, 100㎛, L-3430)의 일면에 건조 후 두께가 20㎛가 되도록 코팅하고, 80℃ 오븐에서 2분간 건조한 후 고압 수은램프에 400mJ의 광량으로 경화하여 하드코팅 필름을 제조하였다.
The hard coating composition prepared in the above examples and comparative examples was coated on one side of an optical polyimide film (Mitsubishi Gas Chemical, 100㎛, L-3430) to a thickness of 20㎛ after drying, and placed in an oven at 80°C for 2 minutes. After drying, a hard coating film was prepared by curing in a high-pressure mercury lamp with a light dose of 400 mJ.
제조된 하드코팅 필름의 물성을 후술하는 방법으로 측정하고, 그 결과를 하기 표 2 및 표 3에 나타내었다.
The physical properties of the manufactured hard coating film were measured by the method described below, and the results are shown in Tables 2 and 3 below.
(1) 연필경도(1) Pencil hardness
연필경도 시험기(PHT, 한국 석보과학사)를 이용하여 500g 하중을 걸고 연필경도를 측정하였다. 연필은 미쯔비시 제품을 사용하고 한 연필경도당 5회 실시하였다.
The pencil hardness was measured using a pencil hardness tester (PHT, Seokbo Science, Korea) with a 500g load. The pencil was a Mitsubishi product, and the test was conducted 5 times per pencil hardness.
(2) (2) 내찰상성scratch resistance
스틸울테스트기(WT-LCM100, 한국 프로텍사)를 이용하여 1㎏/(2㎝×2㎝)하에서 10회 왕복 운동시켜 내찰상성을 시험하였다.Scratch resistance was tested by reciprocating 10 times under 1kg/(2cm×2cm) using a steel wool tester (WT-LCM100, Korea Protex).
스틸울은 #0000을 사용하였다.#0000 steel wool was used.
S: 스크래치가 0개S: 0 scratches
A: 스크래치가 1~10개A: 1 to 10 scratches
B: 스크래치가 11~20개B: 11 to 20 scratches
C: 스크래치가 21~30개C: 21 to 30 scratches
D: 스크래치가 31개 이상
D: 31 or more scratches
(3) 밀착성(3) Adhesion
필름의 도포된 면에 1㎜ 간격으로 가로 세로 각각 11개의 직선을 그어 100개의 정사각형을 만든 후, 테이프(CT-24, 일본 니치방사)을 이용하여 3회 박리 테스트를 진행하였다. 100개의 사각형 3개를 테스트하여 평균치를 기록하였다.Eleven straight lines were drawn horizontally and vertically at 1 mm intervals on the coated surface of the film to create 100 squares, and then a peeling test was performed three times using tape (CT-24, Nichibang Corporation, Japan). Three 100 squares were tested and the average value was recorded.
밀착성은 다음과 같이 기록하였다.Adhesion was recorded as follows.
밀착성 = n/100Adhesion = n/100
n : 전체 사각형 중 박리되지 않는 사각형 수n: Number of squares that are not peeled out of all squares
100 : 전체 사각형의 개수100: Total number of squares
따라서 하나도 박리되지 않았을 시 100/100으로 기록하였다.
Therefore, when no peeling occurred, it was recorded as 100/100.
(4) 컬(4) Curl
A4 사이즈(29.7×21.0㎝)의 정방형 형상으로 절단한 시료를 평탄한 글라스 판 위에, 필름의 도포된 면을 위로해서 두고, 4각의 글라스 판으로부터 떨어진 거리를 25℃, 50%RH에서 측정하여 평균값을 측정값으로 하였다.
A sample cut into a square shape of A4 size (29.7 was taken as the measured value.
(5) (5) 내크랙성Crack resistance
크랙성을 평가하기 위하여 1㎝×10㎝의 크기로 절단한 코팅된 필름 시료를 각각의 지름 (2φ ~ 20 φ)의 쇠 막대 위에 놓고 코팅층을 위로 하여 손으로 꺾어 표면이 크랙이 생기지 않는 가장 작은 지름을 표시하였다.
To evaluate cracking properties, a coated film sample cut to a size of 1cm The diameter is indicated.
상기 표 2 및 표 3에서 보듯이, 본 발명에 따른 실시예 1 내지 4의 하드코팅 조성물을 사용하여 제조되는 하드코팅 필름은 경도, 내찰상성, 밀착성, 컬 특성과 내크랙성이 모두 우수하였다. 반면, 비교예 1 내지 3의 하드코팅 조성물을 사용하여 제조되는 하드코팅 필름은 경도, 내찰상성, 밀착성, 컬 특성 또는 내크랙성이 저하되는 것을 확인하였다. 특히, 비교예 1 내지 3의 하드코팅 조성물을 사용하여 제조되는 하드코팅 필름은 내찰상성과 경도를 동시에 충족하지 않는 것으로 확인되었다.
As shown in Tables 2 and 3, the hard coating films manufactured using the hard coating compositions of Examples 1 to 4 according to the present invention were all excellent in hardness, scratch resistance, adhesion, curl characteristics, and crack resistance. On the other hand, it was confirmed that the hardness, scratch resistance, adhesion, curl characteristics, or crack resistance of the hard coating films manufactured using the hard coating compositions of Comparative Examples 1 to 3 were reduced. In particular, it was confirmed that the hard coating films manufactured using the hard coating compositions of Comparative Examples 1 to 3 did not meet both scratch resistance and hardness.
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 (17)
상기 하이퍼브랜치 화합물의 분지화도는 0.05 이상 1 미만이며,
하드코팅 조성물 전체 100중량%에 대하여 상기 (메타)아크릴레이트 말단기를 갖는 하이퍼브랜치 화합물은 10 내지 50중량%, 상기 시클로헥실기를 갖는 다관능 우레탄 (메타)아크릴레이트는 10 내지 30중량%, 상기 에틸렌글리콜기를 갖는 다관능 (메타)아크릴레이트는 5 내지 30 중량%로 포함되는 하드코팅 조성물.It includes a hyperbranched compound having a (meth)acrylate terminal group, a polyfunctional urethane (meth)acrylate having a cyclohexyl group, a polyfunctional (meth)acrylate having an ethylene glycol group, a photoinitiator, and a solvent,
The degree of branching of the hyperbranched compound is 0.05 or more and less than 1,
Based on 100% by weight of the total hard coating composition, the hyperbranched compound having the (meth)acrylate end group is 10 to 50% by weight, the polyfunctional urethane (meth)acrylate having the cyclohexyl group is 10 to 30% by weight, A hard coating composition containing 5 to 30% by weight of the polyfunctional (meth)acrylate having an ethylene glycol group.
[화학식 1]
[화학식 2]
[Formula 1]
[Formula 2]
[화학식 3]
[화학식 4]
[Formula 3]
[Formula 4]
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