KR20110060038A - Anti static hard coating composition, hard coating film, polarizing plate and display device using the same - Google Patents
Anti static hard coating composition, hard coating film, polarizing plate and display device using the same Download PDFInfo
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- KR20110060038A KR20110060038A KR1020090116506A KR20090116506A KR20110060038A KR 20110060038 A KR20110060038 A KR 20110060038A KR 1020090116506 A KR1020090116506 A KR 1020090116506A KR 20090116506 A KR20090116506 A KR 20090116506A KR 20110060038 A KR20110060038 A KR 20110060038A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
Description
본 발명은 대전방지 하드코팅 조성물, 대전방지 하드코팅 필름, 이를 포함하는 편광판 및 표시장치에 관한 것이다.The present invention relates to an antistatic hard coating composition, an antistatic hard coating film, a polarizing plate and a display device including the same.
일반적으로 CRT(Cathod Ray Tube), LCD(Liquid Crystal Display), PDP(Plasma Display Panel) 등의 표시장치에는 표면 보호재로 기재 필름상에 내긁힘성(anti-scratch)이 뛰어난 하드 코팅층이 형성된 하드코팅 필름을 사용하고 있다. 그러나, 종래의 하드코팅 필름은 표면저항이 1013Ω/sq 이상이기 때문에 주위의 먼지 등이 표면에 부착하기 쉬운 단점이 있다. In general, a hard coating layer having a hard coating layer having excellent anti-scratch on a base film as a surface protective material is used for display devices such as a cathode ray tube (CRT), a liquid crystal display (LCD), and a plasma display panel (PDP). Film is used. However, since the conventional hard coating film has a surface resistance of 10 13 Pa / sq or more, there is a disadvantage that surrounding dust or the like is easily attached to the surface.
그에 따라 하드 코팅층에 대전 방지성을 부여한 대전방지 하드코팅 필름이 사용되고 있다. 하드 코팅층에 대전방지성을 부여하기 위해 일반적으로 대전 방지 제를 첨가하거나, 대전 방지층을 별도로 형성하기도 한다. 최근에 ATO(antimontinoxide), ITO(indiumtinoxide) 등과 같은 금속산화물 계통의 도전성 졸을 이용한 대전방지 하드코팅 조성물이 개발되었다. 이러한 대전방지 하드코팅 조성물은 자유전자 전하이동에 의해 대전방지성의 지속성이 우수하고, 투명도가 대체로 우수한 특성 때문에 상업적 응용이 매우 활발하다. Accordingly, an antistatic hard coating film having imparted antistatic property to a hard coating layer is used. In order to impart antistatic property to the hard coating layer, an antistatic agent is generally added or an antistatic layer may be separately formed. Recently, an antistatic hard coating composition using a metal oxide-based conductive sol such as antimontinoxide (ATO) or indiumtinoxide (ITO) has been developed. Such an antistatic hard coating composition has excellent antistatic persistence by free electron charge transfer and is very active in commercial applications because of its generally excellent transparency.
그러나 상기한 대전방지 하드코팅 조성물은 투명 플라스틱에 코팅했을 때 투과도가 80% 내지 85% 정도로 매우 낮고, 소정의 색상을 가지므로 투명 플라스틱의 외관을 손상시키고, 또한 가격이 매우 고가여서 제품의 단가를 상승시키는 단점이 있다. However, when the antistatic hard coating composition is coated on the transparent plastic, the transmittance is very low, such as 80% to 85%, and has a predetermined color, thereby damaging the appearance of the transparent plastic, and the price is very expensive, thereby reducing the cost of the product. There is a disadvantage to increase.
이에 본 발명의 목적은 대전방지 하드코팅 필름의 제조에 적용 시 대전방지 성능이 탁월하면서도 투과율이 우수한 대전방지 하드코팅 조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide an antistatic hard coating composition excellent in antistatic performance and excellent transmittance when applied to the production of an antistatic hard coating film.
본 발명의 다른 목적은 대전방지 성능 및 투과율이 탁월한 대전방지 하드코팅 필름을 제공하는 것이다. Another object of the present invention is to provide an antistatic hard coating film having excellent antistatic performance and transmittance.
본 발명의 또 다른 목적은 상기 대전방지 하드코팅 필름이 구비된 편광판을 제공하는 것이다. Still another object of the present invention is to provide a polarizing plate provided with the antistatic hard coating film.
본 발명의 또 다른 목적은 상기 대전방지 하드코팅 필름이 구비된 표시 장치 를 제공하는 것이다.Still another object of the present invention is to provide a display device provided with the antistatic hard coating film.
상기한 목적을 달성하기 위한 본 발명은, 하기 화학식 1로 나타내는 (메타)아크릴레이트기를 갖는 이온성 단량체를 포함하는 화합물을 중합시켜 얻어진 중합체를 포함하는 것을 특징으로 하는 대전방지 하드코팅 조성물을 제공한다. The present invention for achieving the above object provides an antistatic hard coating composition comprising a polymer obtained by polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1). .
[화학식 1][Formula 1]
(화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 1 내지 50의 지방족 탄화수소이고, R3는 수소원자 또는 메틸기이고, n은 1 내지 100의 정수이며, X는 1가 음이온으로 사용될 수 있는 원자 또는 화합물이다.)In Formula 1, R 1 and R 2 are each independently an aliphatic hydrocarbon having 1 to 50 carbon atoms, R 3 is a hydrogen atom or a methyl group, n is an integer of 1 to 100, X is a monovalent anion Atoms or compounds.)
상기 중합체는 가교제로 하기 화학식 2 또는 화학식 3으로 나타내는 폴리에틸렌옥사이드 불포화화합물을 사용하여 얻어진 것이 바람직하다. The polymer is preferably obtained by using a polyethylene oxide unsaturated compound represented by the following formula (2) or (3) as a crosslinking agent.
[화학식 2][Formula 2]
(화학식 2에서, m은 1 내지 500의 정수이다.)(In Formula 2, m is an integer of 1 to 500.)
[화학식 3](3)
(화학식 3에서, R4는 서로 독립적으로 수소원자 또는 메틸기이고, p은 1 내지 500의 정수이다.)(In Formula 3, R 4 is independently of each other a hydrogen atom or a methyl group, p is an integer from 1 to 500.)
상기 대전방지 하드코팅 조성물은 우레탄(메타)아크릴레이트, (메타)아크릴레이트 모노머, 광개시제 및 용제를 포함할 수 있다.The antistatic hard coating composition may include a urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator and a solvent.
상기 우레탄(메타)아크릴레이트는 5관능 이상의 우레탄(메타)아크릴레이트를 포함하는 것이 바람직하다. It is preferable that the said urethane (meth) acrylate contains the urethane (meth) acrylate more than 5-functional.
상기 대전방지 하드코팅 조성물 100중량부에 대하여 상기 중합체는 5 내지 45중량부, 상기 우레탄(메타)아크릴레이트는 10 내지 60중량부, 상기 (메타)아크릴레이트 모노머는 5 내지 50중량부, 상기 광개시제는 0.1 내지 10중량부 및 상기 용제는 0.1 내지 75중량부 포함되는 것을 특징으로 하는 대전방지 하드코팅 조성물을 제공한다.5 to 45 parts by weight of the polymer, 10 to 60 parts by weight of the urethane (meth) acrylate, 5 to 50 parts by weight of the (meth) acrylate monomer, and the photoinitiator, based on 100 parts by weight of the antistatic hard coating composition. The 0.1 to 10 parts by weight and the solvent provides an antistatic hard coating composition characterized in that it comprises 0.1 to 75 parts by weight.
본 발명의 다른 목적을 달성하기 위하여 본 발명은 상기한 본 발명에 따른 대전방지 하드코팅 조성물을 이용하여 형성된 하드코팅층을 포함하는 것을 특징으로 하는 대전방지 하드코팅 필름을 제공한다. In order to achieve another object of the present invention, the present invention provides an antistatic hard coating film comprising a hard coating layer formed using the antistatic hard coating composition according to the present invention.
상기 대전방지 하드코팅 필름의 표면저항은 5×1010Ω/sq이하인 것이 바람직하다.The surface resistance of the antistatic hard coating film is preferably 5 × 10 10 Pa / sq or less.
본 발명의 또 다른 목적을 달성하기 위하여 본 발명은 상기한 본 발명에 따른 대전방지 하드코팅 필름을 구비하여 이루어지는 것을 특징으로 하는 편광판을 제공한다.In order to achieve another object of the present invention, the present invention provides a polarizing plate comprising the antistatic hard coating film according to the present invention described above.
본 발명의 또 다른 목적을 달성하기 위하여 본 발명은 상기한 본 발명에 따른 대전방지 하드코팅 필름을 구비하여 이루어지는 것을 특징으로 하는 표시장치를 제공한다.In order to achieve another object of the present invention, the present invention provides a display device comprising the antistatic hard coating film according to the present invention described above.
본 발명에 따른 대전방지 하드코팅 조성물은 하드코팅 필름의 제조에 적용시 뛰어난 대전방지 성능 및 투명성을 나타낸다. 그에 따라 상기 대전방지 하드코팅 조성물은 대전방지 하드코팅 필름, 편광판 및 표시장치에 유용하게 적용할 수 있다.The antistatic hard coating composition according to the present invention exhibits excellent antistatic performance and transparency when applied to the production of hard coating films. Accordingly, the antistatic hard coating composition may be usefully applied to an antistatic hard coating film, a polarizing plate, and a display device.
이하 본 발명을 보다 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명에 따른 대전방지 하드코팅 조성물은 하기 화학식 1로 나타내는 (메타)아크릴레이트기를 갖는 이온성 단량체를 포함하는 화합물을 중합시켜 얻어지는 중합체를 포함한다. The antistatic hard coating composition according to the present invention includes a polymer obtained by polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1).
[화학식 1][Formula 1]
(화학식 1에서, R1 및 R2는 각각 독립적으로 탄소수 1 내지 50의 지방족 탄화수소이고, R3는 수소원자 또는 메틸기이고, n은 1 내지 100의 정수이며, X는 1가 음이온으로 사용될 수 있는 원자 또는 화합물이다.)In Formula 1, R 1 and R 2 are each independently an aliphatic hydrocarbon having 1 to 50 carbon atoms, R 3 is a hydrogen atom or a methyl group, n is an integer of 1 to 100, X is a monovalent anion Atoms or compounds.)
상기 중합체는 하드코팅 조성물에 포함시 기존의 다른 대전방지제에 비하여 우수한 대전방지 특성을 나타낼 뿐만 아니라 높은 투과율을 나타내게 된다. The polymer, when included in the hard coating composition, exhibits excellent antistatic properties as well as high transmittance as compared to other conventional antistatic agents.
상기 화학식 1로 표시되는 단량체는 할로겐알킬알콜과 (메타)아크로일클로라이드를 트리에틸아민과 같은 아민 존재 하에서 반응시켜 할로겐알킬 (메타)아크릴레이트를 제조하고, 이를 N-알킬 이미다졸 화합물과 반응시키면 용이하게 제조할 수 있다.The monomer represented by Formula 1 reacts halogen alkyl alcohol and (meth) acrylochloride in the presence of an amine such as triethylamine to produce a halogen alkyl (meth) acrylate, which is reacted with an N-alkyl imidazole compound. It can be manufactured easily.
상기 할로겐알킬알콜의 구체적인 예로는 2-클로로에탄올, 2-브로모에탄올, 2-요오도에탄올, 3-클로로-1-프로판올, 3-브로모-1-프로판올, 4-클로로-1-부탄올, 6-클로로-1-헥산올, 6-브로모-1-헥산올, 7-브로모-1-헵탄올, 8-클로로-1-옥탄올, 8-브로모-1-옥탄올, 9-브로모-1-노난올, 10-클로로-1-데칸올, 10-브로모-1-데칸올, 11-브로모-1-운데칸올 또는 12-브로모-1-도데칸올 등을 들 수 있다.Specific examples of the halogen alkyl alcohol include 2-chloroethanol, 2-bromoethanol, 2-iodoethanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 4-chloro-1-butanol, 6-chloro-1-hexanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-chloro-1-octanol, 8-bromo-1-octanol, 9- Bromo-1-nonanol, 10-chloro-1-decanol, 10-bromo-1-decanol, 11-bromo-1-undecanol or 12-bromo-1-dodecanol have.
상기 N-알킬이미다졸 화합물의 구체적인 예로는 N-메틸이미다졸, N-에틸-2- 메틸이미다졸, 1,2-디메틸이미다졸, N-데실-2-메틸이미다졸, N-비닐이미다졸, N-아릴이미다졸 또는 N-부틸이미다졸 등을 들 수 있다.Specific examples of the N-alkylimidazole compound include N-methylimidazole, N-ethyl-2-methylimidazole, 1,2-dimethylimidazole, N-decyl-2-methylimidazole, N-vinylimidazole, N-arylimidazole, N-butylimidazole, etc. are mentioned.
상기 화학식 1에서 X는 1가 음이온으로 사용될 수 있는 원자 또는 화합물로서 특별히 한정되지 않는다. 상기 X-는 예컨대 Cl-, Br-, I-, AlCl4 -, Al2Cl7 -, BF4 -, PF6 -, SbF6 -, NO3 -, ClO4 -, CH3COO-, CF3COO-, CH3SO3 -, CF3SO3 -, (CF3SO2)2N-, (C2F5SO2)2N-, C3F7COO-, (CF3SO2)(CF3CO)N- 등일 수 있다.In Formula 1, X is not particularly limited as an atom or a compound that may be used as a monovalent anion. Wherein X - is for example, Cl -, Br -, I - , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, SbF 6 -, NO 3 -, ClO 4 -, CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2 ) (CF 3 CO) N -and the like.
상기 중합체는 하기 화학식 1로 나타내는 (메타)아크릴레이트기를 갖는 이온성 단량체를 포함하는 화합물을 중합시키기 위한 가교제로서 하기 화학식 2 또는 화학식 3으로 표현되는 폴리에틸렌옥사이드 불포화화합물을 사용하는 것이 바람직하다The polymer is preferably a polyethylene oxide unsaturated compound represented by the following formula (2) or (3) as a crosslinking agent for polymerizing a compound containing an ionic monomer having a (meth) acrylate group represented by the following formula (1)
[화학식 2][Formula 2]
(화학식 2에서, m은 1 내지 500의 정수이다.)(In Formula 2, m is an integer of 1 to 500.)
[화학식 3] (3)
(화학식 3에서, R4는 서로 독립적으로 수소원자 또는 메틸기이고, p은 1 내지 500의 정수이다.)(In Formula 3, R 4 is independently of each other a hydrogen atom or a methyl group, p is an integer from 1 to 500.)
가교제로서 상기 화학식 2 또는 화학식 3으로 표시되는 폴리에틸렌옥사이드 불포화 화합물을 사용하게 되면 중합체 내부에 유연성을 부여하여 전기전도도를 향상 시키는 효과를 발휘한다.When the polyethylene oxide unsaturated compound represented by the formula (2) or (3) is used as the crosslinking agent, it provides flexibility to the inside of the polymer to improve the electrical conductivity.
상기 화학식 2로 표시되는 폴리에틸렌옥사이드비닐에테르 화합물은 구체적으로 에틸렌글리콜디비닐에테르, 디(에틸렌글리콜)디비닐에테르, 트리(에틸렌글리콜)디비닐에테르, 테트라(에틸렌글리콜)디비닐에테르 등으로 이루어진 군으로부터 선택된 적어도 1종을 사용할 수 있다.The polyethylene oxide vinyl ether compound represented by Formula 2 is specifically a group consisting of ethylene glycol divinyl ether, di (ethylene glycol) divinyl ether, tri (ethylene glycol) divinyl ether, tetra (ethylene glycol) divinyl ether, and the like. At least one selected from can be used.
또한, 상기 화학식 3으로 표시되는 폴리에틸렌옥사이드(메타)아크릴레이트 화합물은 구체적으로 에틸렌글리콜디메타아크릴레이트, 에틸렌글리콜디아크릴레이트, 디(에틸렌글리콜)디아크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디메타아크릴레이트 등으로 이루어진 군으로부터 선택된 적어도 1종을 사용할 수 있다.In addition, the polyethylene oxide (meth) acrylate compound represented by the formula (3) is specifically ethylene glycol dimethacrylate, ethylene glycol diacrylate, di (ethylene glycol) diacrylate, polyethylene glycol diacrylate, polyethylene glycol di At least 1 sort (s) chosen from the group which consists of methacrylate etc. can be used.
상기 중합체의 제조방법은 특별히 한정되지는 않으며, 용액중합법, 광중합법, 벌크중합법, 서스펜션중합법 또는 에멀젼 중합법에 의하여 제조될 수 있다. 바람직하게는, 중합체는 용액 중합법을 사용하여 제조하며, 중합온도는 50∼110℃인 것이 바람직하고, 단량체를 균일하게 혼합한 상태에서 중합개시제를 첨가하는 것이 바람직하다. 상기 중합개시제로는 당해 분야에서 사용되는 것을 적용할 수 있으며, 구체적으로는 아조비스이소부티로니트릴, 아조비스이소발레로니트릴 등의 아조계 중합 개시제, 벤조일퍼옥사이드, 디-t-부틸퍼옥사이드, 라우릴퍼옥사이드 등의 퍼옥사이드계 중합 개시제로부터 선택된 적어도 1종을 사용할 수 있다.The production method of the polymer is not particularly limited, and may be prepared by a solution polymerization method, a photopolymerization method, a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method. Preferably, the polymer is prepared using a solution polymerization method, and the polymerization temperature is preferably 50 to 110 ° C, and the polymerization initiator is preferably added in a state where the monomers are uniformly mixed. As the polymerization initiator, those used in the art may be applied. Specifically, azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide And at least one selected from peroxide-based polymerization initiators such as lauryl peroxide.
상기 중합체는 대전방지 하드코팅 조성물 100중량부에 대하여 5 내지 45중량부 포함되는 것이 바람직하다. 상기 중합체의 함량이 5중량부 미만인 경우에는 표면저항이 충분히 향상되지 않아 대전방지 특성이 떨어지는 문제점이 있으며, 45중량부를 초과할 경우에는 상용성이 저하되는 문제점이 있다.The polymer is preferably included 5 to 45 parts by weight based on 100 parts by weight of the antistatic hard coating composition. When the content of the polymer is less than 5 parts by weight, there is a problem that the surface resistance is not sufficiently improved and the antistatic property is lowered, and when it exceeds 45 parts by weight, compatibility is reduced.
본 발명에 따른 대전방지 하드코팅 조성물은 우레탄(메타)아크릴레이트, (메타)아크릴레이트 모노머, 광개시제 및 용제를 포함할 수 있다.The antistatic hard coating composition according to the present invention may include a urethane (meth) acrylate, a (meth) acrylate monomer, a photoinitiator and a solvent.
상기 우레탄(메타)아크릴레이트는 5관능 이상의 우레탄(메타)아크릴레이트를 포함하는 것이 바람직하며, 특히 상기 5관능 이상의 우레탄(메타)아크릴레이트는 하기 화학식 4로 표현되는 것이 더욱 바람직하다.It is preferable that the urethane (meth) acrylate includes a urethane (meth) acrylate of 5 or more functionalities, and particularly, the urethane (meth) acrylate of 5 or more functionalities is more preferably represented by the following formula (4).
[화학식 4] [Formula 4]
(화학식 4에서, Y는 2~20개의 (메타)아크릴레이트 관능기를 포함하는 탄소수 2~80개의 헤테로 원자를 포함하거나 포함하지 않는 지방족 또는 방향족 탄화수소이며, Q는 선형(linear), 가지(branched) 또는 시클릭(cyclic)의 탄소수 3~50개의 헤테로 원자를 포함하거나 포함하지 않는 지방족 또는 방향족 탄화수소이고, q은 1내지 10의 정수이다.)In Formula 4, Y is an aliphatic or aromatic hydrocarbon containing or not containing 2 to 80 heteroatoms including 2 to 20 (meth) acrylate functional groups, and Q is linear or branched. Or an aliphatic or aromatic hydrocarbon containing or without a cyclic C3-C50 hetero atom, and q is an integer of 1 to 10.)
상기 화학식 4로 표시되는 5관능 이상의 우레탄(메타)아크릴레이트는 분자내 2개 이상의 이소시아네이트기를 갖는 화합물에 히드록시기를 포함하는 (메타)아크릴레이트 화합물을 반응시켜 제조할 수 있다.The 5-functional or more urethane (meth) acrylate represented by Formula 4 may be prepared by reacting a (meth) acrylate compound containing a hydroxyl group with a compound having two or more isocyanate groups in a molecule.
상기 이소시아네이트기를 갖는 화합물의 구체적으로 4,4'-디시클로헥실디이소시아네이트, 헥사메틸렌디이소시아네이트 트라이머, 1,4-디이소시아나토부탄, 1,6-디이소시아나토헥산, 1,8-디이소시아나토옥탄, 1,12-디이소시아나토데칸, 1,5-디이소시아나토-2-메틸펜탄, 트리메틸-1,6-디이소시아나토헥산, 1,3-비스(이소시아나토메틸)시클로헥산, 트란스-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'-메틸렌비 스(2,6-디메틸페닐이소시아네이트), 4,4'-옥시비스(페닐이소시아네이트), 헥사메틸렌디이소시아네이트로부터 유도되는 3관능 이소시아네이트, 트리메탄프로판올 어덕트 톨루엔디이소시아네이트 등을 들 수 있다. 이들은 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. Specific examples of the compound having an isocyanate group include 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanate Natooctane, 1,12-diisocyanatodecane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, Trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene- 1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1, -chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (phenylisocyanate), derived from hexamethylene diisocyanate Trifunctional isocyanate, a trimethane propanol adduct toluene diisocyanate, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.
상기 히드록시기를 포함하는 (메타)아크릴레이트 화합물의 구체적인 예로는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시이소프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 카프로락톤 개환 히드록시아크릴레이트, 펜타 에리스리톨트리/테트라(메타)아크릴레이트 혼합물, 디펜타에리스리톨펜타/헥사(메타)아크릴레이트 혼합물 등을 들 수 있으며, 이들은 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Specific examples of the (meth) acrylate compound containing the hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and capro Lactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, dipentaerythritol penta / hexa (meth) acrylate mixture, and the like, and the like, each of which may be used alone or in combination of two or more thereof. have.
상기 우레탄(메타)아크릴레이트는 제한되지 않으나 대전방지 하드코팅 조성물 100중량부에 대하여 10 내지60중량부 포함되는 것이 바람직하다. 상기 우레탄(메타)아크릴레이트의 함량이 상기의 기준으로 10중량부 미만인 경우 충분한 경도 향상이 어렵고 60중량부를 초과 할 경우 표면 경도 향상으로 크랙이 발생 할 수 있다.The urethane (meth) acrylate is not limited, but is preferably included 10 to 60 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the urethane (meth) acrylate is less than 10 parts by weight based on the above-mentioned, it is difficult to improve the sufficient hardness, and if it exceeds 60 parts by weight, cracks may occur due to surface hardness improvement.
상기 (메타)아크릴레이트 모노머는 상기 우레탄(메타)아크릴레이트의 효과를 극대화 하기 위해 더 첨가될 수 있는 것으로서 수축률이나 경도면에서 바람직하게 사용될 수 있다. 상기 (메타)아크릴레이트 모노머는 구체적으로 디펜타에리스톨헥사(메타)아크릴레이트, 디펜타에리스톨펜타(메타)아크릴레이트, 펜타에리스톨테트 라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, (메타)아크릴릭에스테르, 트리메틸올프로판트리(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트트리(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜(메타)아크릴레이트, 1,3-부탄디올디(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌클리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 비스(2-히드록시에틸)이소시아누레이트디(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 히드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소-덱실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라히드로퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트,이소보네올(메타)아크릴레이트 등을 들 수 있다. 상기의 (메타)아크릴레이트 모노머는 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. The (meth) acrylate monomer may be further added to maximize the effect of the urethane (meth) acrylate and may be preferably used in terms of shrinkage and hardness. Specific examples of the (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth). ) Acrylate, (meth) acrylic ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (Meth) acrylate, propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl Isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (Meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate, etc. are mentioned. Said (meth) acrylate monomers can be used individually or in combination of 2 types or more, respectively.
상기 (메타)아크릴레이트 모노머는 대전방지 하드코팅 조성물 100중량부에 대해 5 내지 50중량부 포함하는 것이 바람직하다. 상기 (메타)아크릴레이트의 함량이 상기의 기준으로 5중량부 미만이면 우레탄(메타)아크릴레이트의 수축율을 조절하기 어렵고 50중량부를 초과 할 경우 경도가 저하되는 문제점이 있다.The (meth) acrylate monomer preferably contains 5 to 50 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the (meth) acrylate is less than 5 parts by weight based on the above criteria, it is difficult to control the shrinkage of the urethane (meth) acrylate, and if the content exceeds 50 parts by weight, there is a problem that the hardness is lowered.
상기 광개시제는 당해 분야에서 일반적으로 사용되는 것이라면 제한 없이 적용할 수 있다. 상기 광개시제는 히드록시케톤류 광개시제 또는 아미노케톤류 광개 시제를 포함할 수 있으며, 보다 구체적으로는 벤조페논, 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1, 디페닐케톤벤질디메틸케탈, 2-히드록시-2-메틸-1-페닐-1-온, 4-히드록시시클로페닐케톤, 디메톡시-2-페닐아테토페논, 안트라퀴논, 플루오렌, 트리페닐아민, 카바졸, 3-메틸아세토페논, 4-크놀로아세토페논, 4,4-디메톡시아세토페논, 4,4-디아미노벤조페논, 1-히드록시시클로헥실페닐케톤으로 이루어진 군으로부터 선택된 적어도 1종의 광개시제를 사용할 수 있다. The photoinitiator may be applied without limitation as long as it is generally used in the art. The photoinitiator may include a hydroxyketone photoinitiator or an amino ketone photoinitiator, more specifically, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, di Phenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine , At least one selected from the group consisting of carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone Species photoinitiators can be used.
바람직 하게 상기 광개시제는 벤조페논과 같은 수소 탈환형 광개시제를 포함하는 것이 바람직하며, 이 경우 표면 경도를 보다 향상 시킬 수 있다. Preferably, the photoinitiator preferably includes a hydrogen-reducing photoinitiator such as benzophenone, and in this case, surface hardness may be further improved.
상기 광개시제는 대전방지 하드코팅 조성물 100중량부에 대하여 0.1 내지 10중량부 포함되는 것이 바람직하다. 상기 광개시제의 함량이 상기의 기준으로 0.1중량부 미만인 경우 경화 속도가 늦고 10중량부를 초과한 경우는 크랙의 문제점이 발생할 수 있다. The photoinitiator is preferably included 0.1 to 10 parts by weight based on 100 parts by weight of the antistatic hard coating composition. When the content of the photoinitiator is less than 0.1 parts by weight based on the above standard, the curing rate may be slow and may exceed 10 parts by weight.
상기 용제는 당해 기술분야에서 알려진 것이라면 제한되지 않고 사용할 수 있다. The solvent can be used without limitation so long as it is known in the art.
상기 용제로는 알코올계(메탄올, 에탄올, 이소프로판올, 부탄올, 메틸셀루소브, 에틸솔루소브 등), 케톤계(메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 디에틸케톤, 디프로필케톤, 사이클로헥사논 등), 헥산계(헥산, 헵탄, 옥탄 등), 벤젠계(벤젠, 톨루엔, 자일렌 등) 등을 예시할 수 있다. 상기 용제는 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. Examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, Cyclohexanone etc.), hexane type (hexane, heptane, octane etc.), benzene type (benzene, toluene, xylene etc.) etc. can be illustrated. The said solvent can be used individually or in combination of 2 or more types, respectively.
상기 용제는 대전방지 하드코팅 조성물 100중량부에 대하여 0.1 내지 75중량부를 첨가할 수 있다. 상기 용제의 함량이 상기의 기준으로 1중량부 미만이면 점도가 높아 작업성이 떨어지고, 75중량부를 초과할 경우에는 경화 과정에서 시간이 많이 소요되고 경제성이 떨어지는 문제가 있다.The solvent may be added 0.1 to 75 parts by weight based on 100 parts by weight of the antistatic hard coating composition. If the content of the solvent is less than 1 part by weight based on the above standard, the viscosity is high, the workability is lowered, and if it exceeds 75 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.
본 발명에 따른 대전방지 하드코팅 조성물에는 상기한 성분들 이외에도 항산화제, UV 흡수제, 광안정제, 열적고분자화 금지제, 레블링제, 계면활성제, 윤활제, 방오제 등이 함께 사용될 수 있다. In addition to the above components, an antistatic hard coating composition according to the present invention may be used with an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a labelling agent, a surfactant, a lubricant, an antifouling agent, and the like.
본 발명에 따른 대전방지 하드코팅 필름은 상기한 본 발명에 따른 대전방지 하드코팅 조성물을 이용하여 형성된 하드코팅층을 포함한다. 즉, 본 발명에 따른 대전방지 하드코팅 필름은 전술한 본 발명에 따른 대전방지 하드코팅 조성물을 기재에 도포하여 형성된 대전방지 하드코팅층을 구비한다.The antistatic hard coating film according to the present invention includes a hard coating layer formed using the antistatic hard coating composition according to the present invention described above. That is, the antistatic hard coating film according to the present invention includes an antistatic hard coating layer formed by applying the antistatic hard coating composition according to the present invention to a substrate.
상기 기재로는 투명필름이 바람직하며, 예를 들면 노르보르넨이나 다환 노르보르넨계 단량체와 같은 시클로올레핀을 포함하는 단량체의 단위를 갖는 시클로올레핀계 유도체, 디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부틸레이트, 프로피오닐셀룰오로스, 부티릴셀룰로오스, 아세틸프로피오닐셀룰로오스 등에서 선택되는 셀룰로오스, 에틸렌-아세트산비닐공중합체, 폴리에스테르, 폴리스티렌, 폴리아미드, 폴리에테르이미드, 폴리아크릴, 폴리이미드, 폴리에테르술폰, 폴리술폰, 폴리에틸렌, 폴리프로필렌, 폴리메틸펜텐, 폴리염화비닐, 폴리염화비닐리 덴, 폴리비닐알콜, 폴리비닐아세탈, 폴리에테르케톤, 폴리에테르에테르케톤, 폴리에테르술폰, 폴리메틸메타아크릴레이트, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리우레탄에서 선택된 것을 사용할 수 있으며, 미연신, 1축 또는 2축 연신 필름을 사용할 수 있다. 이 중에서 바람직하게는 투명성 및 내열성이 우수한 1축 또는 2축 연신 폴리에스테르 필름이나, 투명성 및 광학적으로 이방성이 없다는 점에서 트리아세틸 셀룰로오스 필름이 적합하게 사용된다. The substrate is preferably a transparent film, and for example, cycloolefin derivatives having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyl Cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, Polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene Terephthalate, Polybutylene Terephthalate , Polyethylene naphthalate, polycarbonate, polyurethane may be used, and an unoriented, uniaxial or biaxially oriented film may be used. Among them, preferably, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a triacetyl cellulose film is suitably used in view of transparency and optical anisotropy.
상기 기재의 두께는 제한되지 않으나 8~1000㎛가 바람직하고, 보다 바람직하게는 40~100㎛이다.Although the thickness of the said base material is not restrict | limited, 8-1000 micrometers is preferable, More preferably, it is 40-100 micrometers.
상기 기재에 대전방지 하드코팅 조성물을 도포하는 방법은 당해분야에서 일반적으로 사용되는 방법이 적용될 수 있으며, 예를 들어 다이코터, 에어 나이프, 리버스 롤, 스프레이, 블레이드, 캐스팅, 그라비아 및 스핀코팅 등에서 선택된 적당한 방식으로 실시할 수 있다. The method of applying the antistatic hard coating composition to the substrate may be a method generally used in the art, for example, selected from die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating, etc. It may be carried out in a suitable manner.
상기 대전방지 하드코팅 조성물의 도포두께는 0.1 내지 200㎛이며, 바람직하게는 2 내지 30㎛이고, 보다 바람직하게는 4 내지 25㎛이다. 대전방지 하드코팅 조성물을 도포한 후 30 내지 150℃의 온도에서 1초 내지 30분, 바람직하게는 10초 내지 10분 동안 휘발물을 증발시켜 건조한다. 이후 UV광을 조사하여 경화시킨다. 상기 UV광의 조사량은 약 0.01 내지 10J/㎠이 바람직하고, 보다 바람직하게는 0.1 내지 2J/㎠이다.The coating thickness of the antistatic hard coating composition is 0.1 to 200 µm, preferably 2 to 30 µm, and more preferably 4 to 25 µm. After applying the antistatic hard coating composition, the volatiles are dried by evaporation at a temperature of 30 to 150 ° C. for 1 second to 30 minutes, preferably 10 seconds to 10 minutes. After curing by irradiation with UV light. The irradiation amount of the UV light is preferably about 0.01 to 10 J / cm 2, more preferably 0.1 to 2 J / cm 2.
상기 하드코팅층의 두께는 제한되지 않으나 1 내지 30㎛ 범위가 바람직하고, 5 내지 15㎛ 범위가 보다 바람직하다. 하드코팅층의 두께가 상기 범위일 경우 컬링 특성이 15mm 이하로 조정 가능한 대전방지 하드코팅 필름을 얻을 수 있다.The thickness of the hard coating layer is not limited, but is preferably in the range of 1 to 30 μm, more preferably in the range of 5 to 15 μm. When the thickness of the hard coating layer is within the above range, it is possible to obtain an antistatic hard coating film having a curling property of 15 mm or less.
상기와 같이 제조된 대전방지 하드코팅 필름은 우수한 표면저항, 광학적 고투명성을 가지며, 제조 시에 경화속도가 빨라 생산성이 우수하며, 경화한 후 제조된 필름은 컬링 현상이 발생하지 않는 이점이 있다. 특히 본 발명에서 제조된 대전방지 하드코팅 필름은 표면저항이 1010 이하로 우수한 특성을 나타낸다. The antistatic hard coating film manufactured as described above has excellent surface resistance and optical high transparency, and has a high curing speed at the time of manufacture, and thus has high productivity, and the film produced after curing has an advantage of not causing a curling phenomenon. In particular, the antistatic hard coating film produced in the present invention exhibits excellent surface resistance of 10 10 or less.
본 발명에 따른 편광판은 전술한 대전방지 하드코팅 필름을 적어도 한면에 적층하여 형성된다. The polarizing plate according to the present invention is formed by laminating the aforementioned antistatic hard coating film on at least one surface.
상기 편광판은 특별하게 제한되지 않지만, 다양한 종류가 사용될 수 있다. 상기 편광판은 예를 들면, 폴리비닐 알코올계 필름, 에틸렌-비닐 아세테이트 공중합체계 부분 비누화 필름, 요오드 또는 2색성 염료 등의 2색성 물질을 흡착시켜 1축 연신한 필름, 폴리비닐 알코올의 탈수처리물 또는 폴리염화비닐의 탈염산처리물 등의 폴리엔계 배향 필름 등이 사용될 수 있다. 이 중에서도, 폴리비닐 알코올계 필름 또는 요오드 등의 2색성 물질로 이루어지는 편광판이 바람직하다. 이들 편광판의 두께는 특별히 제한되지는 않지만 일반적으로 5 내지 80㎛ 정도이다.The polarizing plate is not particularly limited, but various kinds may be used. The polarizing plate may be, for example, a film uniaxially stretched by adsorbing a dichroic substance such as a polyvinyl alcohol film, an ethylene-vinyl acetate copolymerized partial saponified film, iodine or a dichroic dye, a dehydrated product of polyvinyl alcohol, or Polyene type orientation films, such as the dehydrochlorination material of polyvinyl chloride, etc. can be used. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film or iodine, is preferable. Although the thickness in particular of these polarizing plates is not restrict | limited, Usually, it is about 5-80 micrometers.
본 발명에 따른 표시장치는 전술한 대전방지 하드코팅 필름을 구비한다 즉, 본 발명의 대전방지 하드코팅 필름이 적층된 편광판을 표시장치에 내장함으로써, 대전방지성이 우수한 표시장치를 제조할 수 있다. 특히 본 발명의 대전방지 하드코팅 필름은 반사형, 투과형, 반투과형 LCD 또는 TN형, STN형, OCB형, HAN형, VA형, IPS형 등의 각종 구동 방식의 LCD에 바람직하게 이용될 수 있다. 또한, 본 발명의 대전방지 하드코팅 필름은 내마모성 및 방오성이 우수하여 플라즈마 디스플레이, 필드 에미션 디스플레이, 유기 EL 디스플레이, 무기 EL 디스플레이, 전자 페이퍼 등의 각종 표시장치에도 바람직하게 이용될 수 있다.The display device according to the present invention includes the antistatic hard coating film described above. That is, the display device having excellent antistatic property can be manufactured by embedding a polarizing plate on which the antistatic hard coating film of the present invention is laminated. . In particular, the antistatic hard coating film of the present invention can be preferably used in reflective, transmissive, transflective LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. . In addition, the antistatic hard coating film of the present invention is excellent in wear resistance and antifouling property, and can be preferably used in various display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.
본 발명은 하기의 실시예에 의하여 보다 구체화될 것이며, 하기의 실시예는 본 발명의 구체적인 예시에 불과하며 본 발명의 보호범위를 한정하거나 제한하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.
[할로알킬(메타)아크릴레이트 합성][Haloalkyl (meth) acrylate synthesis]
[합성예 1] Synthesis Example 1
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 메틸렌클로라이드 250중량부, 2-브로모에탄올(알드리치사) 50중량부, 트리에틸아민 15중량부를 첨가하고 반응기 온도를 0℃로 낮춘 후 아크로일클로라이드 25중량부를 메틸렌클로라이드 25중량부에 희석하여 천천히 적가 투입하였다. 적가 종료 후 상온으로 승온 시킨 후 1시간 동안 교반하였다. 반응 종료는 가스크로마토그래피를 이용하여 확인하고 반응 종료 후 물 250중량부를 투입하여 교반 후 정치하여 물층을 제거하는 공 정을 3회 반복 실시하였다. 용제층은 감압장치를 이용하여 용제를 제거하고 순도 95%의 2-브로모에틸아크릴레이트를 얻었다.250 parts by weight of methylene chloride, 50 parts by weight of 2-bromoethanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the reactor temperature was lowered to 0 ° C. 25 parts by weight of acroyl chloride was diluted with 25 parts by weight of methylene chloride and slowly added dropwise thereto. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left to stand. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 2-bromoethyl acrylate of purity 95%.
[합성예 2]Synthesis Example 2
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 메틸렌클로라이드 250중량부, 6-브로모-1-헥산올(알드리치사) 65중량부, 트리에틸아민 15중량부를 첨가하고 반응기 온도를 0℃로 낮춘 후 아크로일클로라이드 23중량부를 메틸렌클로라이드 23중량부에 희석하여 천천히 적가 투입하였다. 적가 종료 후 상온으로 승온 시킨 후 1시간 동안 교반하였다. 반응 종료는 가스크로마토그래피를 이용하여 확인하고 반응 종료 후 물 250중량부를 투입하여 교반 후 정치하여 물층을 제거하는 공정을 3회 반복 실시하였다. 용제층은 감압장치를 이용하여 용제를 제거하고 순도 96%의 6-브로모헥실아크릴레이트를 얻었다.250 parts by weight of methylene chloride, 65 parts by weight of 6-bromo-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller. After lowering to ℃ ℃ 23 parts by weight of acroyl chloride diluted to 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left standing to remove the water layer. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-bromohexyl acrylate of purity 96%.
[합성예 3]Synthesis Example 3
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 메틸렌클로라이드 250중량부, 6-브로모-1-헥산올(알드리치사) 65중량부, 트리에틸아민 15중량부를 첨가하고 반응기 온도를 0℃로 낮춘 후 메타아크로일클로라이드 23중량부를 메틸렌클로라이드 23중량부에 희석하여 천천히 적가 투입하였다. 적가 종료 후 상온으로 승온 시킨 후 1시간 동안 교반하였다. 반응 종료는 가스크로마토그래피를 이용하여 확인하고 반응 종료 후 물 250중량부를 투입하여 교반 후 정치하여 물층을 제거하 는 공정을 3회 반복 실시하였다. 용제층은 감압장치를 이용하여 용제를 제거하고 순도 94%의 6-브로모헥실메타아크릴레이트를 얻었다.250 parts by weight of methylene chloride, 65 parts by weight of 6-bromo-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller. After lowering to ℃ ℃ 23 parts by weight of methacroyl chloride was diluted with 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, followed by stirring. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-bromohexyl methacrylate of 94% purity.
[합성예 4]Synthesis Example 4
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 메틸렌클로라이드 250중량부, 6-클로로-1-헥산올(알드리치사) 60중량부, 트리에틸아민 15중량부를 첨가하고 반응기 온도를 0℃로 낮춘 후 메타아크로일클로라이드 23중량부를 메틸렌클로라이드 23중량부에 희석하여 천천히 적가 투입하였다. 적가 종료 후 상온으로 승온 시킨 후 1시간 동안 교반하였다. 반응 종료는 가스크로마토그래피를 이용하여 확인하고 반응 종료 후 물 250중량부를 투입하여 교반 후 정치하여 물층을 제거하는 공정을 3회 반복 실시하였다. 용제층은 감압장치를 이용하여 용제를 제거하고 순도 94%의 6-클로로헥실메타아크릴레이트를 얻었다.250 parts by weight of methylene chloride, 60 parts by weight of 6-chloro-1-hexanol (Aldrich) and 15 parts by weight of triethylamine were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the reactor temperature was 0 ° C. After lowering to 23 parts by weight of methacroyl chloride diluted to 23 parts by weight of methylene chloride was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature, followed by stirring for 1 hour. After completion of the reaction, the reaction was confirmed using gas chromatography. After completion of the reaction, 250 parts by weight of water was added thereto, stirred, and left standing to remove the water layer. The solvent layer removed the solvent using the pressure reduction apparatus, and obtained 6-chlorohexyl methacrylate of 94% purity.
[(메타)아크릴레이트를 갖는 이온성 화합물 합성(음이온 : BrSynthesis of Ionic Compounds Having [(meth) acrylate (Anion: Br -- 또는or ClCl -- )])]
[합성예 5] Synthesis Example 5
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 2-브로모에틸아크릴레이트(합성예 1에서 제조된 것임) 30중량부, N-에틸이미다졸 70중량부를 첨가하고 80℃에서 24시간 동안 교반 하였다. 가스크로마토그래피로 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 헥산 100중량부를 투입하여 교반 후 용제 층을 제거하 는 공정을 5회 반복하여 잔량의 N-에틸이미다졸을 제거한 후 감압으로 잔류 용제를 제거하여 1-에틸-3-아크로일에틸이미다졸륨브로마이드를 얻었다.30 parts by weight of 2-bromoethyl acrylate (as prepared in Synthesis Example 1) and 70 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the resultant was stirred at 80 ° C. for 24 hours. Stirred. After confirming the completion of the reaction by gas chromatography, lowering the temperature to room temperature, adding 100 parts by weight of hexane, stirring and removing the solvent layer five times to remove the residual amount of N-ethylimidazole and remaining under reduced pressure. The solvent was removed to obtain 1-ethyl-3-acroylethylimidazolium bromide.
[합성예 6] [Synthesis Example 6]
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 6-브로모헥실아크릴레이트(합성예 2에서 제조된 것임) 30중량부, N-에틸이미다졸 80중량부를 첨가하고 80℃에서 24시간 동안 교반 하였다. 가스크로마토그래피로 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 헥산 100중량부를 투입하여 교반 후 용제 층을 제거하는 공정을 5회 반복하여 과량의 N-에틸이미다졸을 제거한 후 감압으로 잔류 용제를 제거하여 1-에틸-3-아크로일헥실이미다졸륨브로마이드를 얻었다.30 parts by weight of 6-bromohexyl acrylate (prepared in Synthesis Example 2) and 80 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller for 24 hours at 80 ° C. Stirred. After confirming the completion of the reaction by gas chromatography, lowering the temperature to room temperature, adding 100 parts by weight of hexane, stirring and removing the solvent layer five times to remove excess N-ethylimidazole, and then remaining solvent under reduced pressure. Was removed to obtain 1-ethyl-3-acroylhexylimidazolium bromide.
[합성예 7][Synthesis Example 7]
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 6-브로모헥실메타아크릴레이트(합성예 3에서 제조된 것임) 30중량부, N-에틸이미다졸 75중량부를 첨가하고 80℃에서 24시간 동안 교반 하였다. 가스크로마토그래피로 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 헥산 100중량부를 투입하여 교반 후 용제 층을 제거하는 공정을 5회 반복하여 잔량의 N-에틸이미다졸을 제거한 후 감압으로 잔류 용제를 제거하여 1-에틸-3-메타아크로일헥실이미다졸륨브로마이드를 얻었다.30 parts by weight of 6-bromohexyl methacrylate (manufactured in Synthesis Example 3) and 75 parts by weight of N-ethylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature controller, and the result was 24 hours at 80 ° C. Was stirred. After confirming the completion of the reaction by gas chromatography and lowering the temperature to room temperature, 100 parts by weight of hexane was added thereto, followed by stirring five times to remove the solvent layer, to remove residual N-ethylimidazole. Was removed to obtain 1-ethyl-3-methacrylohexylimidazolium bromide.
[합성예 8][Synthesis Example 8]
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 6-클로로헥실메타아크릴레이트(합성예 4에서 제조된 것임) 30중량부, N-부틸이미다졸 84중량부를 첨가하고 80℃에서 24시간 동안 교반 하였다. 가스크로마토그래피로 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 헥산 100중량부를 투입하여 교반 후 용제 층을 제거하는 공정을 5회 반복하여 과량의 N-부틸이미다졸을 제거한 후 감압으로 잔류 용제를 제거하여 1-부틸-3-메타아크로일에틸이미다졸륨클로라이드를 얻었다.30 parts by weight of 6-chlorohexyl methacrylate (prepared in Synthesis Example 4) and 84 parts by weight of N-butylimidazole were added to a reactor equipped with a condenser, a stirring device, and a temperature control unit at 80 ° C. for 24 hours. Stirred. After confirming the completion of the reaction by gas chromatography and lowering the temperature to room temperature, 100 parts by weight of hexane was added and stirred to remove the solvent layer five times to remove excess N-butylimidazole, and then residual solvent under reduced pressure. Was removed to give 1-butyl-3-methacryloylethylimidazolium chloride.
[(메타)아크릴레이트를 갖는 이온성 화합물 합성(음이온 : NTfSynthesis of Ionic Compounds Having [(meth) acrylate (Anion: NTf 22 -- 또는 PF Or PF 66 -- ]]
[합성예 9]Synthesis Example 9
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 아세토니트릴 200중량부, 1-에틸-3-아크로일에틸이미다졸륨브로마이드(합성예 5에서 제조된 것임) 20중량부, 니튬비스(트리플루오로메탄셀폰닐)이미드(알드리치사) 25중량부를 첨가하고 80℃에서 48시간 동안 교반 하였다. 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 실리카겔(400mesh, 머크사)를 충진한 컬럼를 통과 시켜 니튬브로마이드 고체를 제거하여 1-에틸-3-아크로일에틸이미다졸륨비스(트리플루오로메탄셀폰닐)이미드를 얻었다.200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-acroylethylimidazolium bromide (manufactured in Synthesis Example 5) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat 25 parts by weight of trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-acryloylethylimidazolium bis (trifluoromethane cell phone). Nil) imide was obtained.
[합성예 10]Synthesis Example 10
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 아세토니트릴 200중량부, 1-에틸-3-아크로일헥실이미다졸륨브로마이드(합성예 6에서 제조된 것임) 20중량부, 니튬비스(트리플루오로메탄셀폰닐)이미드(알드리치사) 40중량부를 첨가하고 80℃에서 48시간 동안 교반 하였다. 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 실리카겔(400mesh, 머크사)를 충진한 컬럼를 통과 시켜 니튬브로마이드 고체를 제거하여 1-에틸-3-아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드를 얻었다.200 parts by weight of acetonitrile, 1-ethyl-3-acylhexylimidazolium bromide (manufactured in Synthesis Example 6) as a solvent in a reactor equipped with a condenser, a stirring device, and a temperature controller, and a lithium bis ( 40 parts by weight of trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-acrylohexylimidazolium bis (trifluoromethane cell phone). Nil) imide was obtained.
[합성예 11]Synthesis Example 11
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 아세토니트릴 200중량부, 1-에틸-3-메타아크로일헥실이미다졸륨브로마이드(합성예 7에서 제조된 것임) 20중량부, 니튬비스(트리플루오로메탄셀폰닐)이미드(알드리치사) 40중량부를 첨가하고 80℃에서 48시간 동안 교반 하였다. 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 실리카겔(400mesh, 머크사)를 충진한 컬럼를 통과 시켜 니튬브로마이드 고체를 제거하여 1-에틸-3-메타아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드를 얻었다.200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-methacrohexylimidazolium bromide (manufactured in Synthesis Example 7) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat 40 parts by weight of (trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature and passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-methacroylhexylimidazolium bis (trifluoromethane). Celfonyl) imide was obtained.
[합성예 12]Synthesis Example 12
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 아세토니트릴 200중량부, 1-부틸-3-메타아크로일에틸이미다졸륨클로라이드(합성예 8에서 제조된 것임) 20중량부, 니튬비스(트리플루오로메탄셀폰닐)이미드(알드리치사) 40중량부를 첨가하고 80℃에서 48시간 동안 교반 하였다. 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 실리카겔(400mesh, 머크사)를 충진한 컬럼를 통과 시켜 니튬클로라이드 고체를 제거하여 1-부틸-3-메타아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드를 얻었다.200 parts by weight of acetonitrile, 20 parts by weight of 1-butyl-3-methacroylethylimidazolium chloride (manufactured in Synthesis Example 8) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat, lithium bis 40 parts by weight of (trifluoromethanecellfonyl) imide (Aldrich) was added and stirred at 80 ° C for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature and passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium chloride solid, thereby removing 1-butyl-3-methacrylohexylimidazolium bis (trifluoromethane). Celfonyl) imide was obtained.
[합성예 13][Synthesis Example 13]
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 아세토니트릴 200중량부, 1-에틸-3-메타아크로일헥실이미다졸륨브로마이드(합성예 7에서 제조된 것임) 20중량부, 소듐헥사플루오로포스핀(알드리치사) 30중량부를 첨가하고 80℃에서 48시간 동안 교반 하였다. 반응 종결을 확인 하고 상온으로 온도를 저하시킨 후 실리카겔(400mesh, 머크사)를 충진한 컬럼를 통과 시켜 니튬브로마이드 고체를 제거하여 1-에틸-3-메타아크로일헥실이미다졸륨헥사플루오로포스핀을 얻었다.200 parts by weight of acetonitrile, 20 parts by weight of 1-ethyl-3-methacrylohexylimidazolium bromide (prepared in Synthesis Example 7) as a solvent in a reactor equipped with a condenser, a stirring device, and a thermostat, sodium hexa 30 parts by weight of fluorophosphine (Aldrich) was added and stirred at 80 ° C. for 48 hours. After confirming the completion of the reaction, the temperature was lowered to room temperature, and then passed through a column filled with silica gel (400 mesh, Merck) to remove the lithium bromide solid to remove 1-ethyl-3-methacroylhexylimidazolium hexafluorophosphine. Got it.
[중합체 합성][Polymer synthesis]
[합성예 14][Synthesis Example 14]
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-아크로일에틸이미다졸륨비스(트리플루오로메탄셀폰닐)이미드(합성예 9에서 제조된 것임) 25중량부, 테트라(에틸렌글리콜)디비닐에테르 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-acryloethylimidazolium bis (trifluoromethaneselfonyl) imide (manufactured in Synthesis Example 9) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.
[합성예 15]Synthesis Example 15
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드(합성예 10에서 제조된 것임) 25중량부, 테트라(에틸렌글리콜)디비닐에테르 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-acroylhexylimidazolium bis (trifluoromethaneselfonyl) imide (manufactured in Synthesis Example 10) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.
[합성예 16]Synthesis Example 16
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-메타아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드(합성예 11에서 제조된 것임) 25중량부, 테트라(에틸렌글리콜)디비닐에테르 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrylohexyl imidazolium bis (trifluoromethanecellfonyl) imide (in Synthesis Example 11) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether is added, and the temperature is raised to 70 ° C, 0.1 part by weight of azobisisobutyronitrile is dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.
[합성예 17]Synthesis Example 17
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-부틸-3-메타아크로일헥실이미다졸륨비스(트리플루오로메탄셀폰닐)이미드(합성예 12에서 제조된 것임) 25중량부, 테트라(에틸렌글리콜)디비닐 에테르 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-butyl-3-methacroylheximidazolium bis (trifluoromethanecellfonyl) imide (in Synthesis Example 12) in a reactor equipped with a condenser, a stirring device, and a temperature controller. 25 parts by weight, 1 part by weight of tetra (ethylene glycol) divinyl ether was added and the temperature was raised to 70 ° C, and 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.
[합성예 18]Synthesis Example 18
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-메타아크로일헥실이미다졸륨헥사플루오로포스핀 (합성예 13에서 제조된 것임) 25중량부, 테트라(에틸렌글리콜)디비닐 에테르 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) 1 part by weight of tetra (ethylene glycol) divinyl ether was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto, followed by stirring for 8 hours. To obtain a polymer having a solid content of 50% by weight.
[합성예 19]Synthesis Example 19
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-메타아크로일헥실이미다졸륨헥사플루오로포스핀 (합성예 13에서 제조된 것임) 25중량부, 디(에틸렌글리콜)디아크릴레이트 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) 1 part by weight of di (ethylene glycol) diacrylate was added and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added thereto, followed by stirring for 8 hours. To obtain a polymer having a solid content of 50% by weight.
[합성예 20]Synthesis Example 20
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-메타아크로일헥실이미다졸륨헥사플루오로포스핀 (합성예 13에서 제조된 것임) 25중량부, 폴리(에틸렌글리콜)디메타아크릴레이트(p=6) 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) Then, 1 part by weight of poly (ethylene glycol) dimethacrylate (p = 6) was added, and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added. Stirring was performed for 8 hours to obtain a polymer having a solid content of 50% by weight.
[합성예 21]Synthesis Example 21
콘덴서, 교반장치, 온도조절장치가 장착된 반응기에 용제로 에틸아세테이트 50중량부, 1-에틸-3-메타아크로일헥실이미다졸륨헥사플루오로포스핀 (합성예 13에서 제조된 것임) 25중량부, 폴리(에틸렌글리콜)디아크릴레이트(p=12) 1중량부를 첨가하고 온도를 70℃로 승온 후 개시제로 아조비스이소부티로니트릴 0.1중량부를 에틸아세테이트 10중량부에 용해시켜 천천히 투입하고 8시간 동안 교반을 진행 하여 고형분 함량이 50중량%인 중합체를 얻었다.50 parts by weight of ethyl acetate as a solvent, 1-ethyl-3-methacrohexyl imidazolium hexafluorophosphine (manufactured in Synthesis Example 13) in a reactor equipped with a condenser, a stirring device, and a temperature controller (25 parts) Then, 1 part by weight of poly (ethylene glycol) diacrylate (p = 12) was added and the temperature was raised to 70 ° C., 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of ethyl acetate as an initiator, and slowly added 8 Stirring was performed for a time to obtain a polymer having a solid content of 50% by weight.
[실시예 1 내지 14 및 비교예 1 내지 3][Examples 1 to 14 and Comparative Examples 1 to 3]
하기 표 1에 나타난 바와 같은 성분들을 혼합하여 대전방지 하드코팅 조성물 제조하였다. To prepare the antistatic hard coating composition by mixing the components as shown in Table 1.
우레탄 아크릴레이트: 10관능 우레탄 아크릴레이트(SUO-1700B, 신아티엔씨)Urethane acrylate: 10 functional urethane acrylate (SUO-1700B, Shin ArtenC)
아크릴레이트 모노머 : 펜타에리스리톨트리/펜타아크릴레이트(M340, 미원상사)Acrylate monomer: pentaerythritol tree / pentaacrylate (M340, Miwon Corporation)
대전방지제 : ATO(Antimony Tin Oxide 30% in 2-메톡시에탄올, 에스켐텍)Antistatic Agent: ATO (Antimony Tin Oxide 30% in 2-methoxyethanol, Schemtech)
대전방지제 : 4급암모늄(1-메틸-3-부틸이미다졸늄테트라플루오로보레이트, 씨트리)Antistatic agent: quaternary ammonium (1-methyl-3-butylimidazonium tetrafluoroborate, sea tree)
I-184 : 1-히드록시시클로헥실페닐케톤(시바사)I-184: 1-hydroxycyclohexylphenyl ketone (Shiba Corporation)
I-907 : 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1(시바사)I-907: 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (Shiba Corporation)
MEK : 메틸에틸케톤(대정화금)MEK: methyl ethyl ketone
MIBK : 메틸이소부틸케톤(대정화금)MIBK: methyl isobutyl ketone
BYK-378 : 실리콘변성오일(BYK사)BYK-378: Silicone Modified Oil (BYK)
<실험예>Experimental Example
상기 실시예 및 비교예에서 제조된 대전방지 하드코팅 조성물을 두께 80㎛의 트리아세틸셀룰로오스필름으로 된 투명기재의 한쪽 위에 도포한 후 가열건조하고 자외선 경화시켜 두께 5㎛의 하드코팅층을 형성하였다. 이렇게 제조된 필름에 대하여 하기와 같이 물성을 측정하였으며, 그 결과는 하기 표 2에 나타내었다. The antistatic hard coating composition prepared in Examples and Comparative Examples was applied on one side of a transparent substrate made of a triacetyl cellulose film having a thickness of 80 μm, and then dried by heating and UV cured to form a hard coating layer having a thickness of 5 μm. The physical properties of the thus prepared film were measured as follows, and the results are shown in Table 2 below.
(1) 투과율 및 헤이즈(1) transmittance and haze
분광광도계(HZ-1, 일본 스가사)를 이용하여 전광선투과율(Total Transmittance)과 헤이즈(Haze)를 측정하였다. Total transmittance and haze were measured using a spectrophotometer (HZ-1, Suga, Japan).
(2) 표면저항율(2) surface resistivity
Hiresta의 MCP-HT450을 사용하여 전기 저항을 측정하였다.Electrical resistance was measured using Hiresta's MCP-HT450.
상기 표 2에서 보는 바와 같이 본 발명에 따른 이온성 단량체를 포함하는 화합물의 중합체를 포함하는 실시예 1 내지 14의 경우 이를 포함하지 않는 비교예 1 내지 3에 비하여 대전방지성능이 좋으면서도 투과율이 매우 높음을 확인 할 수 있다. As shown in Table 2, in Examples 1 to 14 including the polymer of the compound containing the ionic monomer according to the present invention, the antistatic performance is very good and the transmittance is very high compared to Comparative Examples 1 to 3 not including the same. You can see the high.
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