KR102064826B1 - Thermal conducting film composition, thermal conducting film produced therefrom and preparing method the same - Google Patents

Thermal conducting film composition, thermal conducting film produced therefrom and preparing method the same Download PDF

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KR102064826B1
KR102064826B1 KR1020170181972A KR20170181972A KR102064826B1 KR 102064826 B1 KR102064826 B1 KR 102064826B1 KR 1020170181972 A KR1020170181972 A KR 1020170181972A KR 20170181972 A KR20170181972 A KR 20170181972A KR 102064826 B1 KR102064826 B1 KR 102064826B1
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oxy
liquid crystal
oxo
propen
ester
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KR1020170181972A
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KR20190079895A (en
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김동균
차은정
김윤호
김병각
유영재
김용석
원종찬
이미혜
김다솜
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한국화학연구원
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
    • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
    • H05K7/20472—Sheet interfaces
    • H05K7/20481—Sheet interfaces characterised by the material composition exhibiting specific thermal properties
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Abstract

본 발명은 아크릴레이트기(acrylate functional group) 함유 로드액정;
하기 화학식 1로 표시되는 디스코틱 액정 화합물; 및
싸이올기(thiol group) 함유 스페이서를 포함하는 방열필름용 조성물을 제공한다.
[화학식 1]

Figure 112017130246334-pat00014

(여기서 상기 R 은
Figure 112017130246334-pat00015
임.)
따라서 기계적 연신에 의하여 액정을 쉽게 배향할 수 있으며, 제조된 방열필름은 유연성을 가지며, 연신 방향으로 높은 열전도도를 나타낼 수 있다. The present invention is a rod liquid crystal containing an acrylate group (acrylate functional group);
A discotic liquid crystal compound represented by Formula 1 below; And
Provided is a composition for a heat radiation film comprising a thiol group-containing spacer.
[Formula 1]
Figure 112017130246334-pat00014

Where R is
Figure 112017130246334-pat00015
being.)
Therefore, the liquid crystal can be easily oriented by mechanical stretching, and the produced heat dissipating film has flexibility and may exhibit high thermal conductivity in the stretching direction.

Description

방열필름용 조성물, 이를 사용하는 방열필름 및 이의 제조방법{Thermal conducting film composition, thermal conducting film produced therefrom and preparing method the same}Heat dissipating film composition, heat dissipating film using same and manufacturing method thereof {Thermal conducting film composition, thermal conducting film produced therefrom and preparing method the same}

본 발명은 액정 화합물을 포함하는 방열필름용 조성물, 이를 사용하는 방열필름 및 이의 제조방법에 관한 것이다. The present invention relates to a heat dissipating film composition comprising a liquid crystal compound, a heat dissipating film using the same and a method for manufacturing the same.

최근 전자기기의 소형화 및 고집적화에 따라, 기기 내부의 열 발생이 증가되고 기기의 수명 및 안전성 측면에서 문제가 야기되고 있다. 효과적인 열 방출 필름의 도입은 전자기기의 수명 및 안전성을 향상시킬 수 있다.With the recent miniaturization and high integration of electronic devices, heat generation inside the device is increased and problems are caused in terms of life and safety of the device. The introduction of an effective heat release film can improve the life and safety of the electronic device.

무겁고 깨지기 쉬운 세라믹 기반의 열 방출 필름에 비해, 고분자 기반의 열 방출 필름은 가볍고 유연하며 다양한 형태로의 가공이 유리한 장점을 가지지만 상대적으로 낮은 열전도도(0.1-0.4 W m-1 K-1) 때문에 그 자체로 응용되기 어려워 열전도도가 높은 무기 필러와의 복합화를 통해 열전도도를 향상시키는 연구가 많이 진행되었다. Compared to the heavy and fragile ceramic based heat dissipating film, the polymer based heat dissipating film has the advantage of being light, flexible and processing in various forms, but with relatively low thermal conductivity (0.1-0.4 W m -1 K -1 ) As a result, many studies have been conducted to improve thermal conductivity through complexation with inorganic fillers having high thermal conductivity.

하지만, 고분자-무기필러의 복합화는 필름의 기계적 강도 감소 및 고분자-무기 필러 계면에서의 큰 포논 산란 등의 문제로 열전도도 향상에 한계가 있어, 매트릭스 고분자 사슬의 배향에 의한 열전도도 향상 연구가 주목을 받고 있다. However, complexation of polymer-inorganic fillers is limited in improving thermal conductivity due to problems such as reduced mechanical strength of the film and large phonon scattering at the polymer-inorganic filler interface. Is getting.

예를 들어, 결정성 고분자인 폴리에틸렌을 연신하면 연신 방향으로 고분자 사슬들이 배향되고, 배향된 고분자의 열전도도는 배향이 되지 않은 고분자보다 100배가량 높은 열전도도를 갖는다.For example, when stretching a crystalline polymer polyethylene, the polymer chains are oriented in the stretching direction, and the thermal conductivity of the oriented polymer has a thermal conductivity about 100 times higher than that of the unoriented polymer.

한편, 액정 분자는 기판 표면 특성, 전기 및 자기장 등 외부 환경에 따라 배향 방향 및 정도를 쉽게 조절할 수 있어, 열 방출 필름으로의 응용 가능성이 제시되어 왔다. On the other hand, the liquid crystal molecules can easily adjust the orientation direction and degree according to the external environment, such as substrate surface properties, electric and magnetic fields, has been proposed to be applied to heat release film.

기존 선형(Rod) 액정, 디스코틱(discotic) 액정 등으로 이루어진 액정 분자를 배향하여 방열 필름을 제조, 배향된 방향으로의 열전도도 향상에 대한 연구는 꾸준히 진행되어 왔다. 예를 들면 최근 디스코틱 액정을 기반으로 하는 조성물을 유리 기판 사이에 도포하여 추가적인 온도 제어를 통한 방열 필름을 제조, 2D 방향으로의 열전도도 향상에 대한 연구는 보고된 바가 있으나 이러한 기존에 보고된 논문들은 배향 공정상의 복잡함, 사슬의 아크릴레이트 구조로 인한 방열 필름의 깨지기 쉬운 문제로 인한 가공의 어려움을 가지고 있다. Researches have been made on improving thermal conductivity in a direction in which a heat-dissipating film is prepared by orienting liquid crystal molecules made of a conventional linear liquid crystal, discotic liquid crystal, or the like. For example, recently, a study on improving thermal conductivity in 2D direction by manufacturing a heat-dissipating film through additional temperature control by applying a composition based on a discotic liquid crystal between glass substrates has been reported. They have difficulty in processing due to the complexity of the alignment process, the fragile problem of the heat radiation film due to the chain acrylate structure.

따라서, 이러한 단점을 극복하고 효과적인 열 방출 필름으로의 응용을 위해서는 플렉서블하며 평면 내 높은 열전도도를 가지는 방열필름과, 기계적으로 쉽게 배향 가능한 액정 기반의 방열 필름 개발이 매우 필요한 실정이다. Therefore, in order to overcome these disadvantages and apply to an effective heat dissipation film, it is very necessary to develop a heat dissipation film having a high thermal conductivity in a plane and a liquid crystal-based heat dissipation film which can be easily oriented mechanically.

이와 관련된 선행문헌으로는 대한민국 특허1334945호(공고일 2013.11.29) 배향막 및 이를 갖는 액정 표시 장치가 있다. Related prior arts include Korean Patent No.1334945 (announced on Nov. 29, 2013) and an LCD and a liquid crystal display having the same.

대한민국 특허1334945호(공고일 2013.11.29)Republic of Korea Patent 1334945 (Notice date 2013.11.29)

따라서, 본 발명은 액정 분자를 포함하되, 방열필름의 깨지지 쉬운 성향(brittle)이 개선되고, 수직 또는 수평 방향의 열확산 능력이 증가된 방열필름용 조성물과 이를 사용한 방열필름을 제공하고자 한다.Accordingly, the present invention is to provide a heat dissipating film composition and a heat dissipating film using the same, including liquid crystal molecules, the brittleness (brittle) of the heat dissipation film is improved, the heat diffusion ability of the vertical or horizontal direction is increased.

또한 기계적 공정을 통하여 제조공정의 효율성을 증가시켜 가공성을 매우 증가시킨 방열필름의 제조방법을 제공하는데 있다. In addition, to provide a method for manufacturing a heat-dissipating film that greatly increases the workability by increasing the efficiency of the manufacturing process through a mechanical process.

본 발명이 해결하고자 하는 과제는 이상에서 언급한 과제(들)로 제한되지 않으며, 언급되지 않은 또 다른 과제(들)는 이하의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The problem to be solved by the present invention is not limited to the problem (s) mentioned above, and other object (s) not mentioned will be clearly understood by those skilled in the art from the following description.

상기 과제를 해결하기 위해, 본 발명의 한 구체예에서 In order to solve the above problems, in one embodiment of the present invention

아크릴레이트기(acrylate functional group) 함유 로드액정;A rod liquid crystal containing an acrylate functional group;

하기 화학식 1로 표시되는 디스코틱 액정 화합물; 및A discotic liquid crystal compound represented by Formula 1 below; And

싸이올기(thiol group) 함유 스페이서를 포함하는 방열필름용 조성물을 제공한다. Provided is a composition for a heat radiation film comprising a thiol group-containing spacer.

[화학식 1] [Formula 1]

Figure 112017130246334-pat00001
Figure 112017130246334-pat00001

(여기서 상기 R 은

Figure 112017130246334-pat00002
임.)Where R is
Figure 112017130246334-pat00002
being.)

또한 상기 로드액정은In addition, the load liquid crystal

4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스터{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나일 수 있다. 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester], 1 , 4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 1 , 4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 4 -[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl-1,4-phenyl Len) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl-1,4- phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester benzo Ic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid}, 4- [[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic acid-4-[[[4-[[6-[(1-oxo -2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6-[(1-Oxo-2-propen-1-yl) oxy] hexyl ] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4- ( (6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1 '-(1,4-phenylene) ester {4-((6- ( (1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4-phenylene) Ester}, 4- [3-[(1-oxo-2- Propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4- [3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro-2,5-bis [4-[[4-[[[4- [(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol {1,4,3,6-Dianhydro-2 , 5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalene carboxylic acid-2- (Methoxycarbonyl) -1,4-phenylene ester {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecarboxylic Acid-2- (methoxycarbonyl ) -1,4-phenylene Ester} may be any one selected from the group consisting of.

또한 상기 스페이서(spacer)는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택될 수 있다. In addition, the spacer has flexibility, 2,2 '-(ethylenedioxy) diethan thiol [2,2'-(Ethylenedioxy) diethanthiol], 1,4-butanedithiol (1,4- Butanedithiol), 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol (1,8-Octanedithiol) , 1,9-nonaneedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, 1,16-Hexadecanedithiol , Tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol].

또한 방열필름용 조성물은 디스코틱 액정 화합물을 21 내지 37 wt%로 함유하고, 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 1.2배(mol%) 과량 첨가될 수 있다. In addition, the heat dissipating film composition may contain 21 to 37 wt% of the discotic liquid crystal compound, and an acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound may be added in an amount of 1.2 times (mol%).

본 발명의 다른 구체예에서, In another embodiment of the invention,

상기 방열필름용 조성물을 도포(casting)하여 제조되는 방열필름을 제공한다. It provides a heat radiation film prepared by coating the composition for the heat radiation film (casting).

또한 상기 방열필름은 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 과량 첨가되어, 결합하지 않은 아크릴레이트기가 광가교(photo cross-linking)될 수 있다. In addition, the heat dissipation film may be excessively added to the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound to the thiol group, and thus the unbonded acrylate group may be photocross-linked.

본 발명의 또 다른 구체예에서, In another embodiment of the invention,

아크릴레이트기 함유 로드액정; 싸이올기를 함유하는 스페이서 및 가교제를 포함하되, Acrylate group-containing rod liquid crystals; A spacer containing a thiol group and a crosslinking agent,

상기 로드액정에 함유된 아크릴레이트기가 스페이서 및 가교제에 함유된 싸이올기에 비해 1.2내지 2배(mol%) 과량 첨가된 방열필름용 조성물을 도포하여 제조되며, 액정이 배향되어 수평방향(in-plane) 열확산도가 1.02 내지 1.40 mm2S-1인 것을 특징으로 하는 방열필름을 제공한다. The acrylate group contained in the rod liquid crystal is prepared by applying a composition for heat-dissipating film added 1.2 to 2 times (mol%) excess of the thiol group contained in the spacer and the crosslinking agent, and the liquid crystal is oriented in the horizontal direction (in-plane ) Provides a heat radiation film, characterized in that the thermal diffusivity is 1.02 to 1.40 mm 2 S -1 .

또한 상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나 이고, In addition, the rod liquid crystal 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4- phenylene ester], 1,4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2 -methylbenzene}, 1,4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2 -methylbenzene}, 4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl- 1,4-phenylene) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl -1,4-phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4- Phenylene) ester benzoic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid}, 4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic Seed-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6 -[(1-Oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy ] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4-((6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1 ' -(1,4-phenylene) ester {4-((6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4- phenylene) Ester}, 4- [3-[(1-oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4 -[3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro -2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol {1,4,3,6-Dianhydro-2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naph mask Carboxylic Acid-2- (methoxycarbonyl) -1,4-phenylene S {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2- naphthalenecarboxylic Acid-2- (methoxycarbonyl) -1,4-phenylene Ester}, selected from the group consisting of

상기 스페이서(spacer)는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이고, The spacer is flexible and has 2,2 '-(ethylenedioxy) diethethane thiol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol ), 1,5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1,9-nonaneedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, 1,16-Hexadecanedithiol, Tetra (ethylene glycol) dithiol [tetra (ethylene glycol) dithiol] and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] any one selected from the group consisting of,

상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate)]일 수 있다. The crosslinking agent may be pentaerythritol tetrakis (3-mercaptopropionate).

본 발명의 어느 일 측면에 의하면, According to one aspect of the present invention,

(a) 아크릴레이트기 함유 로드액정, 하기 화학식 1로 표시되는 디스코틱 액정화합물, 싸이올기 함유 스페이서(spacer), 광개시제 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하는 단계;(a) dissolving an acrylate group-containing rod liquid crystal, a discotic liquid crystal compound represented by Chemical Formula 1, a thiol group-containing spacer, a photoinitiator, and a catalyst in toluene to prepare a mixed solution;

(b) 상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하는 단계;(b) applying the mixed solution to a substrate and drying to obtain a liquid crystal film;

(c) 상기 액정필름을 연신하여 액정의 배향을 조절하는 단계; 및(c) stretching the liquid crystal film to adjust alignment of liquid crystals; And

(d) 상기 액정필름에 UV를 조사하여 광가교하는 단계를 포함하는 방열필름 제조방법을 제공한다.(d) it provides a heat radiation film manufacturing method comprising the step of photo-crosslinking by irradiating UV to the liquid crystal film.

[화학식 1] [Formula 1]

Figure 112017130246334-pat00003
Figure 112017130246334-pat00003

(여기서 상기 R 은

Figure 112017130246334-pat00004
임.)Where R is
Figure 112017130246334-pat00004
being.)

또한 상기 혼합용액은 63 내지 79 wt% 로드액정 및 21 내지 37 wt%의 디스코틱 액정 화합물을 포함할 수 있다. In addition, the mixed solution may include 63 to 79 wt% of the load liquid crystal and 21 to 37 wt% of the discotic liquid crystal compound.

또한 상기 스페이서는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이며, In addition, the spacer has flexibility, 2,2 '-(ethylenedioxy) diethanthiol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1,5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1, 9-nonaneedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, tetra (1,16-Hexadecanedithiol) Ethylene glycol) dithiol [Tetra (ethylene glycol) dithiol] and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] any one selected from the group consisting of,

상기 (d) 단계에서, 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 1.2 배(mol%) 과량 첨가되어, 결합하지 않은 아크릴레이트기가 광가교(photo cross-linking)될 수 있다. In the step (d), 1.2 times (mol%) excess of the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound may be added, so that the unbonded acrylate group may be photocross-linked. have.

본 발명의 다른 측면에 의하면, According to another aspect of the present invention,

(i) 아크릴레이트기 함유 로드액정, 광개시제, 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하는 단계;(i) dissolving an acrylate group-containing rod liquid crystal, a photoinitiator, and a catalyst in toluene to prepare a mixed solution;

(ii) 상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하는 단계;(ii) applying the mixed solution to a substrate and drying to obtain a liquid crystal film;

(iii) 상기 액정필름을 연신하여 액정의 배향을 조절하는 단계; 및(iii) stretching the liquid crystal film to adjust alignment of liquid crystals; And

(iv) 상기 액정필름에 UV를 조사하여 광가교하는 단계를 포함하는 방열필름 제조방법을 제공한다.(iv) it provides a heat radiation film manufacturing method comprising the step of photo-crosslinking by irradiating UV to the liquid crystal film.

또한 상기 (i) 단계의 혼합용액은 스페이서(spacer) 및 가교제를 더 포함하며, 상기 스페이서(spacer)는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이며, In addition, the mixed solution of step (i) further comprises a spacer and a crosslinking agent, the spacer has a flexibility, 2,2'- (ethylenedioxy) diethan thiol [2,2 ' -(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1,5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1, 6-Hexanedithiol), 1,8-Octanedithiol, 1,9-Noneindithiol, 1,11-Undicanedithiol (1,11 Undecanedithiol), 1,16-hexadecanedithiol, 1,16-Hexadecanedithiol, tetra (ethylene glycol) dithiol, and hexa (ethylene glycol) dithiol ethylene glycol) dithiol] and any one selected from the group consisting of

상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate)]이고, The crosslinking agent is pentaerythritol tetrakis (3-mercaptobutanoate) [pentaerythritol tetrakis (3-mercaptopropionate)],

상기 로드액정의 아크릴레이트기가 스페이서 및 가교제의 싸이올기(thiol group)에 비해 1.2 내지 2배(mol%) 과량 첨가될 수 있다. The acrylate group of the rod liquid crystal may be added in an amount of 1.2 to 2 times (mol%) in excess of the thiol group of the spacer and the crosslinking agent.

본 발명에 따르면, 디스코틱 액정 화합물을 도입하여 방열필름용 조성물을 제공한다. According to the present invention, a discotic liquid crystal compound is introduced to provide a composition for a heat radiation film.

이를 사용한 방열필름은 수직방향 열확산도(thermal diffusivity)가 증가된 방열필름을 제공한다. The heat dissipation film using the same provides a heat dissipation film with increased vertical thermal diffusivity.

또한 디스코틱 액정을 도입하되 스페이서(spacer)를 삽입하여 유연성을 증가시카고, 열전도를 조절할 수 있다. In addition, a discotic liquid crystal may be introduced, but spacers may be inserted to increase flexibility and control thermal conductivity.

또한 로드액정에 가교제 및 스페이서를 혼합한 방열필름은 매우 유연하여 전자기기, 디스플레이 장치와 같은 열확산이 필요한 장치에 열 방출 필름으로 응용될 수 있다. In addition, the heat-dissipating film mixed with a crosslinking agent and a spacer in the rod liquid crystal is very flexible and can be applied as a heat dissipation film in a device that requires heat diffusion such as an electronic device and a display device.

또한 기계적 연신에 의하여 액정을 쉽게 배향할 수 있으며, 제조된 방열필름은 유연성을 가지며, 연신 방향으로 높은 열전도도를 나타낼 수 있다.In addition, the liquid crystal can be easily oriented by mechanical stretching, and the produced heat dissipation film has flexibility and may exhibit high thermal conductivity in the stretching direction.

도 1은 본 발명의 일 측면에 따른 방열필름의 제조 공정을 나타낸 공정흐름도이다.
도 2는 본 발명의 다른 측면에 따른 방열필름의 제조 공정을 나타낸 공정흐름도이다.
도 3은 본 발명의 일실시예에 따른 방열필름의 제조방법에 있어서 디스코틱 액정 화합물의 NMR 데이터이다.
도 4는 본 발명의 일실시예에 따른 방열필름의 인장률에 따른 연신된 방열필름의 사진이다.
도 5는 본 발명의 다른 실시예에 따른 방열필름의 접힘 사진이다.
도 6은 본 발명의 다른 실시예에 따른 방열필름의 열확산 이미지를 나타낸 것이다.
도 7은 본 발명의 다른 실시예에 따른 방열필름의 열확산 이미지를 나타낸 것이다. 1 is a process flow diagram showing a manufacturing process of a heat radiation film according to an aspect of the present invention.
Figure 2 is a process flow diagram showing a manufacturing process of the heat radiation film according to another aspect of the present invention.
3 is NMR data of a discotic liquid crystal compound in the method of manufacturing a heat radiation film according to an embodiment of the present invention.
Figure 4 is a photograph of the stretched heat radiation film according to the tensile rate of the heat radiation film according to an embodiment of the present invention.
5 is a folded picture of the heat radiation film according to another embodiment of the present invention.
Figure 6 shows a thermal diffusion image of the heat radiation film according to another embodiment of the present invention.
Figure 7 shows a thermal diffusion image of the heat radiation film according to another embodiment of the present invention.

이하 첨부된 도면을 참조하면서 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

본 발명의 이점 및 특징, 그리고 그것을 달성하는 방법은 첨부된 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다.Advantages and features of the present invention, and a method of achieving the same will be apparent with reference to the embodiments described below in detail with reference to the accompanying drawings.

그러나 본 발명은 이하에 개시되는 실시예들에 의해 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.However, the present invention is not limited by the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments make the disclosure of the present invention complete, and those skilled in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims.

또한, 본 발명을 설명함에 있어 관련된 공지 기술 등이 본 발명의 요지를 흐리게 할 수 있다고 판단되는 경우 그에 관한 자세한 설명은 생략하기로 한다.In addition, in the following description of the present invention, if it is determined that related related technologies and the like may obscure the gist of the present invention, detailed description thereof will be omitted.

본 발명자들은 디스코틱 액정 분자 화합물(discotic liquid crystalline)과 로드액정(rod liquid crystalline)분자를 이용한 방열 필름의 열전도를 향상하기 위한 연구를 수행하던 중, 액정의 아크릴레이트(acrylate) 가교 주쇄 구조로 인하여 방열필름이 쉽게 손상되는 것을 확인하여, 스페이서 또는 가교제를 첨가하되, 스페이서 또는 가교제의 싸이오이써기(thio-ether functional group)보다 과량의 아크릴레이트기(acrylate functional group)를 첨가하여 이크릴레이트-싸이올 반응을 이용하여 액정 분자를 고정하고, 기계적 연신으로 액정을 배향한 이후에, 결합하지 않는 잔류 아크릴레이트를 광가교하여 다시 고정함으로써 높은 열확산도를 나타내며, 유연성을 가지는 방열필름을 완성하였다. The inventors of the present invention, while conducting research to improve the thermal conductivity of the heat-dissipating film using discotic liquid crystalline molecules and rod liquid crystalline molecules, due to the acrylate (crosslinked) main chain structure of the liquid crystal Confirm that the heat-dissipating film is easily damaged, add a spacer or a crosslinking agent, and add an acrylate functional group by adding an acrylate functional group in excess of the thio-ether functional group of the spacer or the crosslinking agent. After the liquid crystal molecules were fixed by using all reactions and the liquid crystals were aligned by mechanical stretching, the remaining acrylates not bound were photocrosslinked and fixed again, thereby exhibiting high thermal diffusivity and completing a heat-dissipating film having flexibility.

본 발명의 어느 한 구체예에 따른 방열필름용 조성물은 아크릴레이트기(acrylate functional group) 함유 로드액정, 하기 화학식 1로 표시되는 디스코틱 액정 화합물 및 싸이올기(thiol group) 함유 스페이서를 포함한다.The heat dissipation film composition according to one embodiment of the present invention includes an acrylate-containing (rod) liquid crystal containing a acrylate group, a discotic liquid crystal compound represented by the following Chemical Formula 1, and a thiol group-containing spacer.

[화학식 1] [Formula 1]

Figure 112017130246334-pat00005
Figure 112017130246334-pat00005

(여기서 상기 R 은

Figure 112017130246334-pat00006
임.)Where R is
Figure 112017130246334-pat00006
being.)

상기 로드액정은4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스터{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나 이다. The rod liquid crystal is 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester], 1,4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2- methylbenzene}, 1,4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2- methylbenzene}, 4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl-1 , 4-phenylene) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl- 1,4-phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenyl Ester benzoic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid }, 4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic acid -4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6- [(1-Oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4-((6-((1- (oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1'- (1,4-phenylene) ester {4-((6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4-phenylene ) Ester}, 4- [3-[(1-oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4- [3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro- 2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate]- D-Glycitol {1,4,3,6-Dianhydro-2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy ] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecar Cyclolic acid-2- (methoxycarbonyl) -1,4-phenylene ester {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecarboxylic Acid-2- (methoxycarbonyl) -1,4-phenylene Ester}.

상기 로드액정은 양 말단에 아크릴레이트(acrylate) 또는 메타크릴레이트(methacrylate) 작용기가 포함된 바이펑셔널 모노머(bifunctional monomer)이다. The rod liquid crystal is a bifunctional monomer including an acrylate or methacrylate functional group at both ends.

구체적으로 상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester; 이하 'RM257']이다. Specifically, the rod liquid crystal is 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4 -phenylene ester; 'RM257'].

상기 RM257은 디아크릴레이트 메소겐(diacrylate mesogen)으로 반응성이 높아서 선택되었다. The RM257 was selected because of its high reactivity as a diacrylate mesogen.

상기 RM257의 아크릴레이트기는 싸이올기와 반응하여 결합할 수 있다.The acrylate group of RM257 may react with a thiol group to bond.

상기 RM257의 아크릴레이트는 광선에 조사되어 광가교(photo-crosslink 될 수 있다. The acrylate of the RM257 may be photo-crosslinked by irradiation with light.

상기 화학식 1로 표시되는 디스코틱 액정 화합물은 말단에 불포화탄화수를 포함하여 광선에 조사되는 경우 광중합(photopolymerization)-crosslink)될 수 있으며, 액정 화합물을 배향한 이후에 광선으로 용이하게 고정할 수 있다. The discotic liquid crystal compound represented by Chemical Formula 1 may be photopolymerized-crosslinked when irradiated with light including unsaturated carbonated water at the end thereof, and may be easily fixed with light after the alignment of the liquid crystal compound. .

상기 화학식 1로 표시되는 디스코틱 액정 화합물은 트리페닐렌구조의 코어를 중심으로 치환기에 벤조에이트와 같은 구조를 포함하여 컬럼상(columnar phase)이 아닌 네마틱상(nematic phase)을 갖게 되고, 이로 인해 컬럼상(columnar phase)에 비해 대면적의 수평배향이 용이하다. The discotic liquid crystal compound represented by Chemical Formula 1 has a nematic phase rather than a columnar phase by including a structure such as benzoate in a substituent centered on the core of the triphenylene structure, and thus Compared to the column phase (columnar phase) it is easier to horizontally align the large area.

상기 스페이서(spacer)는 유연성 스페이서(flexible spacer) 이며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나일 수 있다. The spacer is a flexible spacer, 2,2 '-(ethylenedioxy) diethan thiol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1) , 4-Butanedithiol), 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol (1,8 -Octanedithiol), 1,9-Noneindithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol (1,16 -Hexadecanedithiol), tetra (ethylene glycol) dithiol [tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] may be any one selected from the group consisting of.

상기 스페이서는 메소겐(mesogen) 그룹이 사슬 사이에 존재하여 액정분자의 유연성을 결정할 수 있다. The spacer may determine the flexibility of the liquid crystal molecules because mesogen groups exist between the chains.

구체적으로 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol]이며, 2개의 싸이올 작용기를 갖는다.Specifically, it is 2,2 '-(ethylenedioxy) diethan thiol [2,2'-(Ethylenedioxy) diethanethiol], and has two thiol functional groups.

상기 스페이서가 로드액정 및 디스코틱 액정 사이에 결합되어 방열필름의 유연성을 도입하고 열전도를 변화시킬 수 있다. The spacer may be coupled between the rod liquid crystal and the discotic liquid crystal to introduce flexibility of the heat radiating film and to change the thermal conductivity.

따라서 로드액정 및 디스코틱 액정 화합물을 포함하는 방열필름 조성물을 사용하는 방열필름은 유연하고 열확산도가 증가될 수 있다. Therefore, the heat dissipation film using the heat dissipation film composition including the rod liquid crystal and the discotic liquid crystal compound may be flexible and thermal diffusivity may be increased.

상기 방열필름용 조성물은 디스코틱 액정 화합물을 21 내지 37 wt%로 함유하고, 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 1.2배(mol%) 과량 첨가된다. The heat dissipating film composition contains 21 to 37 wt% of the discotic liquid crystal compound, and the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound is added 1.2 times (mol%) in excess of the thiol group.

상기 범위로 디스코틱 액정 화합물을 첨가하여 방열필름용 조성물을 제조하고 이를 이용하여 방열필름을 제조하는 경우에 수직방향의 열확산도가 증가될 수 있다. When the discotic liquid crystal compound is added to the above range to prepare a composition for a heat radiation film, and the heat radiation film is manufactured using the same, the thermal diffusivity in the vertical direction may be increased.

본 발명의 다른 구체예에서 상기 방열필름 조성물을 도포하여 제조하는 방열필름을 제공한다. In another embodiment of the present invention provides a heat radiation film prepared by applying the heat radiation film composition.

상기 방열필름은 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 과량 첨가되어, 결합하지 않은 아크릴레이트기가 광가교(photo cross-linking)될 수 있다.The heat dissipating film may be added in excess of the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound to the thiol group, and thus the unbonded acrylate group may be photocross-linked.

본 발명의 또 다른 구체예에 따른 방열필름은 아크릴레이트기 함유 로드액정, 싸이올기를 함유하는 스페이서 및 가교제를 포함하는 방열필름용 조성물을 도포하여 제조한다. Heat dissipation film according to another embodiment of the present invention is prepared by applying a composition for a heat dissipation film comprising a rod liquid crystal containing an acrylate group, a spacer containing a thiol group and a crosslinking agent.

상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스터{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나 일 수 있다. The rod liquid crystal is 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester], 1,4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2- methylbenzene}, 1,4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2- methylbenzene}, 4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl-1 , 4-phenylene) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl- 1,4-phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenyl Ester benzoic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid }, 4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic ash -4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6- [(1-Oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4-((6-((1- (oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1'- (1,4-phenylene) ester {4-((6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4-phenylene ) Ester}, 4- [3-[(1-oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4- [3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro- 2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate]- D-Glycitol {1,4,3,6-Dianhydro-2,5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy ] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthaleneka Cyclolic acid-2- (methoxycarbonyl) -1,4-phenylene ester {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecarboxylic Acid-2- (methoxycarbonyl) -1,4-phenylene Ester} may be any one selected from the group consisting of.

구제척으로 상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester] 이다. By relief, the rod liquid crystal was 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1, 4-phenylene ester].

상기 RM257은 디아크릴레이트 메소겐(diacrylate mesogen)으로 반응성이 높아서 선택되었다. The RM257 was selected because of its high reactivity as a diacrylate mesogen.

상기 RM257의 아크릴레이트은 싸이올기와 반응하여 결합할 수 있다.The acrylate of RM257 may react with a thiol group to bind.

상기 RM257의 아크릴레이트는 광선에 조사되어 광가교(photo-crosslink 될 수 있다. The acrylate of the RM257 may be photo-crosslinked by irradiation with light.

상기 스페이서(spacer)는 스페이서(spacer)는 유연성 스페이서(flexible spacer) 이며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나일 수 있다. The spacer is a spacer is a flexible spacer, 2,2'- (ethylenedioxy) diethan thiol [2,2'- (Ethylenedioxy) diethanethiol], 1,4-bute Indithiol (1,4-Butanedithiol), 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol 1,8-Octanedithiol, 1,9-Nonanedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol Any selected from the group consisting of all (1,16-Hexadecanedithiol), tetra (ethylene glycol) dithiol, and hexa (ethylene glycol) dithiol; It can be one.

구체적으로 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol]이며 2개의 싸이올 작용기를 갖는다.Specifically, 2,2 '-(ethylenedioxy) diethythiol [2,2'-(Ethylenedioxy) diethanethiol] and has two thiol functional groups.

상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis(3-mercaptopropionate)]이다. The crosslinking agent is pentaerythritol tetrakis (3-mercaptopropionate).

상기 가교제는 4개의 싸이올 작용기를 갖는다. The crosslinker has four thiol functional groups.

따라서 상기 방열필름은 로드액정에 함유된 아크릴레이트기가 스페이서 및 가교제에 함유된 싸이올기에 비해 1.2내지 2배(mol%) 과량 첨가된 방열필름용 조성물을 도포하여 제조되며, 액정이 배향되어 수평방향(in-plane) 열확산도가 1.02 내지 1.40 mm2S-1 이다.Therefore, the heat dissipation film is prepared by applying a composition for heat dissipation film in which 1.2 to 2 times (mol%) excess of the acrylate group contained in the rod liquid crystal is added to the thiol group contained in the spacer and the crosslinking agent. (in-plane) thermal diffusivity is 1.02 to 1.40 mm 2 S -1 .

도 1은 본 발명의 일 측면에 따른 방열필름의 제조 공정을 나타낸 공정흐름도이다. 1 is a process flow diagram showing a manufacturing process of a heat radiation film according to an aspect of the present invention.

도1은 참조하면, 본 발명의 어느 일 측면에 의한 방열필름의 제조방법은 1, a method of manufacturing a heat radiation film according to any aspect of the present invention

아크릴레이트기 함유 로드액정, 하기 화학식 1로 표시되는 디스코틱 액정화합물, 싸이올기 함유 스페이서(spacer), 광개시제 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하고(S10), A mixed solution was prepared by dissolving an acrylate group-containing rod liquid crystal, a discotic liquid crystal compound represented by Formula 1 below, a thiol group-containing spacer, a photoinitiator, and a catalyst in toluene (S10),

상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하며(S20)Applying the mixed solution to the substrate and dried to obtain a liquid crystal film (S20)

상기 액정필름을 연신하여 액정의 배향을 조절하고(S30), Stretching the liquid crystal film to adjust the orientation of the liquid crystal (S30),

상기 액정필름에 UV를 조사하여 광가교할 수 있다(S40).The liquid crystal film may be irradiated with UV to photocrosslink (S40).

[화학식 1][Formula 1]

Figure 112017130246334-pat00007
Figure 112017130246334-pat00007

(여기서 상기 R 은

Figure 112017130246334-pat00008
임.)Where R is
Figure 112017130246334-pat00008
being.)

상기 S10에서 디스코틱 액정화합물, 스페이서(spacer), 광개시제 및 촉매를 톨루엔에 혼합하여 마이클 첨가 반응(Michael addition)을 개시할 수 있다. In S10, a discotic liquid crystal compound, a spacer, a photoinitiator, and a catalyst may be mixed with toluene to initiate a Michael addition reaction.

또한 상기 혼합용액은 63 내지 79 wt% 로드액정 및 21 내지 37 wt%의 디스코틱 액정 화합물을 포함할 수 있다. In addition, the mixed solution may include 63 to 79 wt% of the load liquid crystal and 21 to 37 wt% of the discotic liquid crystal compound.

상기 범위 내로 로드액정 및 디스코틱 액정 화합물을 포함하는 경우에 수직방향 열확산도가 0.113 내지 0.147 mm2S-1로 조절될 수 있다. When the rod liquid crystal and the discotic liquid crystal compound are included in the above range, the vertical thermal diffusivity may be adjusted to 0.113 to 0.147 mm 2 S −1 .

구체적으로 상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester] 이고, 상기 스페이서는 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol]이다.Specifically, the rod liquid crystal is 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4 -phenylene ester], and the spacer is 2,2 '-(ethylenedioxy) diethythiol [2,2'-(Ethylenedioxy) diethanethiol].

상기 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기보다 1.2 ~ 2배(mol%)가 되도록 첨가될 수 있다. The acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound may be added to 1.2 to 2 times (mol%) than the thiol group.

상기 스페이서가 첨가되어 방열필름의 유연성을 부여할 수 있다. The spacer may be added to give flexibility of the heat radiation film.

상기 스페이서가 로드액정 및 디스코틱 액정 사이에 결합되어 필름의 유연성을 도입하고 열전도를 변화시킬 수 있다. The spacer may be coupled between the rod liquid crystal and the discotic liquid crystal to introduce flexibility of the film and to change the thermal conductivity.

상기 범위로 아크릴레이트기와 싸이올기가 조절되는 경우에 반응하지 않고 잔류하는 아크릴레이트기를 광가교(photo-crosslink)하여 고정할 수 있다. When the acrylate group and the thiol group are controlled in the above range, the remaining acrylate group may be fixed by photo-crosslinking without remaining reacting.

따라서 과량의 아크릴레이트기의 존재는 마이클 첨가에 의한 반응을 이끌고, 광가교에 의한 반응에 따른 2단계(2 stage)에서 액정 분자를 고정하여 유연하고 높은 열확산도를 가지는 방열 필름을 제조할 수 있다. Therefore, the presence of excess acrylate group leads to the reaction by the addition of Michael, and can be produced a heat-dissipating film having a flexible and high thermal diffusivity by fixing the liquid crystal molecules in two stages according to the reaction by photocrosslinking. .

상기 S20에서 기판에 혼합용액을 도포한 이후에 상온에서 24시간 동안 건조하고, 다시 30 ℃의 진공오븐에서 5시간 동안 추가 건조할 수 있다. After applying the mixed solution to the substrate in S20 and dried for 24 hours at room temperature, it can be further dried for 5 hours in a vacuum oven at 30 ℃ again.

상기 조건의 건조를 통하여 용매를 완전하게 제거할 수 있다.The solvent can be completely removed by drying the above conditions.

상기 S30에서 연신은 인장기를 이용하여 50 % 내지 200 %에서 인장할 수 있다. Stretching in the S30 can be stretched at 50% to 200% using a tensioner.

상기 범위 내에서 연신하는 경우에 액정 분자인 디스코틱 액정 화합물이 연신 방향으로 일정하게 배향될 수 있다. When extending | stretching within the said range, the discotic liquid crystal compound which is a liquid crystal molecule may be uniformly oriented in a extending direction.

상기 S40에서 5분간 UV를 조사하여 광가교할 수 있다. In the S40 may be irradiated with UV light for 5 minutes to crosslink.

상기 광가교를 통하여 배향된 액정 분자를 고정하여 견고하게 유지할 수 있다. The liquid crystal molecules oriented through the optical crosslinking may be fixed and firmly maintained.

도 2는 본 발명의 다른 측면에 따른 방열필름의 제조 공정을 나타낸 공정흐름도이다. Figure 2 is a process flow diagram showing a manufacturing process of the heat radiation film according to another aspect of the present invention.

도 2를 참조하면, 본 발명의 다른 측면에 의한 방열 필름 제조방법은 2, the heat radiation film manufacturing method according to another aspect of the present invention

아크릴레이트기 함유 로드액정, 광개시제, 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하고(S100),A acrylate group-containing rod liquid crystal, a photoinitiator, and a catalyst were dissolved in toluene to prepare a mixed solution (S100),

상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하며(S200),Applying the mixed solution to the substrate and dried to obtain a liquid crystal film (S200),

상기 액정필름을 연신하여 액정의 배향을 조절하고(S300),Stretching the liquid crystal film to adjust the orientation of the liquid crystal (S300),

상기 액정필름에 UV를 조사하여 광가교할 수 있다(S400).The liquid crystal film may be irradiated with UV to photocrosslink (S400).

또한 상기 S100에서 혼합용액은 스페이서(spacer) 및 가교제를 더 포함한다. In addition, the mixed solution in S100 further includes a spacer and a crosslinking agent.

구체적으로 상기 로드액정은 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester] 이고, 상기 스페이서는 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol]이며, 상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate)]이다.Specifically, the rod liquid crystal is 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4 -phenylene ester], and the spacer is 2,2 '-(ethylenedioxy) diethythiol [2,2'-(Ethylenedioxy) diethanethiol], and the crosslinking agent is pentaerythritol tetrakis (3-mercaptobutano) ) Pentaerythritol tetrakis (3-mercaptopropionate).

상기 스페이서 및 가교제를 첨가하여 로드액적의 아크릴레이트기(acrylate functional group)가 스페이서 및 가교제의 싸이올기(thiol functional group)에 비해 1.2내지 2배(mol%) 과량 첨가될 수 있다. By adding the spacer and the crosslinking agent, an acrylate group of the rod droplet may be added in an amount of 1.2 to 2 times (mol%) in excess of the thiol functional group of the spacer and the crosslinking agent.

상기 S200에서 기판에 혼합용액을 도포한 이후에 상온에서 24시간 동안 건조하고, 다시 30 ℃의 진공오븐에서 5시간 동안 추가 건조할 수 있다. After applying the mixed solution to the substrate in S200 and dried for 24 hours at room temperature, it can be further dried for 5 hours in a vacuum oven at 30 ℃ again.

상기 조건의 건조를 통하여 용매를 완전하게 제거할 수 있다.The solvent can be completely removed by drying the above conditions.

상기 S300에서 연신은 인장기를 이용하여 50 % 내지 200 %에서 인장할 수 있다. Stretching in the S300 may be stretched at 50% to 200% using a tensioner.

상기 범위 내에서 연신하는 경우에 액정 분자인 디스코틱 액정 화합물이 연신 방향으로 일정하게 배향될 수 있다. When extending | stretching within the said range, the discotic liquid crystal compound which is a liquid crystal molecule may be uniformly oriented in a extending direction.

상기 S400에서 5분간 UV를 조사하여 광가교할 수 있다. In the S400 can be photocrosslinked by 5 minutes UV irradiation.

상기 광가교를 통하여 배향된 액정 분자를 고정하여 견고하게 유지할 수 있다. The liquid crystal molecules oriented through the optical crosslinking may be fixed and firmly maintained.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

실시예 1: 디스코틱 액정 화합물(DLC MA 6-0) 의 합성Example 1 Synthesis of Discotic Liquid Crystal Compound (DLC MA 6-0)

4-((6-(아크릴로일옥시)헥실)옥시)벤조익 액시드[4-((6-(acryloyloxy)hexyl)oxy)benzoic acid, 이하 'ABA'] 15 g을 500 mL 2구 둥근바닥 플라스크에 웨잉 후, 마그네틱 스터링바를 넣고 고무 셉텀으로 실링하였다. 500 mL two-neck round 15 g of 4-((6- (acryloyloxy) hexyl) oxy) benzoic acid [4-((6- (acryloyloxy) hexyl) oxy) benzoic acid, hereinafter 'ABA'] After weighing in the bottom flask, a magnetic sterling bar was placed and sealed with a rubber septum.

1,2-디메톡시에탄(DME) 60 mL를 넣고 5분간 교반한 후, 온도를 0 로 감온하였다. 메탄설포닐클로라이드(MsCl) 3.9 mL와 트리에틸아민(TEA) 14.3 mL를 반응기에 차례로 천천히 주입한 후, 1,2-디메톡시에탄(DME) 20 mL를 추가로 주입하였다. 상온에서 2시간 30분간 교반한 후, 다시 0로 감온한 다음, 1,2-디메톡시에탄(DME) 7 mL에 용해시킨 4-디메틸아미노피리딘(DMAP) 0.835 g과 1,2-디메톡시에탄(DME) 13 mL에 용해시킨 헥사하이드록시트리페닐렌(HHTP) 1.848 g을 차례로 반응기에 주입하였다. 상온에 밤새 교반 후, 300mL 메틸렌클로라이드(MC)를 넣고 여과하여 염을 제거하였다. 3M HCl 수용액 400 mL, 3M NaOH 수용액 400 mL로 차례로 워싱하며, 메틸렌클로라이드(MC)로 생성물을 추출하였다. 메틸렌클로라이드(MC)층을 마그네슘설페이트로 건조하고 감압농축한 후, 헥산과 메탄올에 차례로 재침전 및 여과하여 표제화합물(DLC MA 6-0) 7.1 g을 얻었다.60 mL of 1,2-dimethoxyethane (DME) was added thereto, stirred for 5 minutes, and the temperature was reduced to zero. 3.9 mL of methanesulfonylchloride (MsCl) and 14.3 mL of triethylamine (TEA) were slowly injected into the reactor, followed by an additional 20 mL of 1,2-dimethoxyethane (DME). After stirring for 2 hours and 30 minutes at room temperature, the temperature was lowered to 0 again, and 0.835 g of 4-dimethylaminopyridine (DMAP) and 1,2-dimethoxyethane dissolved in 7 mL of 1,2-dimethoxyethane (DME). 1.848 g of hexahydroxytriphenylene (HHTP) dissolved in 13 mL of (DME) was sequentially fed into the reactor. After stirring at room temperature overnight, 300 mL methylene chloride (MC) was added thereto and filtered to remove salts. 400 mL of 3M HCl aqueous solution and 400 mL of 3M NaOH aqueous solution were washed successively, and the product was extracted with methylene chloride (MC). The methylene chloride (MC) layer was dried over magnesium sulfate, concentrated under reduced pressure, and then reprecipitated and filtered in hexane and methanol to obtain 7.1 g of the title compound (DLC MA 6-0).

상기 표제화합물을 디스코틱 액정 화합물로 사용하였다. The title compound was used as a discotic liquid crystal compound.

실시예 2: DLC-EDDET 1 방열필름의 제조Example 2: Preparation of DLC-EDDET 1 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된 상기 실시예 1에서 제조한 화합물(이하 'DLC MA6-0') 0.062g, 유연한 스페이서 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol; 이하 'EDDET'] (EDDET) 0.002ml, 촉매 1,8-Diazabicyclo[5.4.0]undec-7-ene(이하'DBU', 톨루엔에 1/1000로 희석하여 사용) 0.027ml의 혼합 용액을 캐스팅하였다. 0.062 g of the compound prepared in Example 1 (hereinafter 'DLC MA6-0') dissolved in 0.2 ml toluene on a glass substrate (2 × 2 cm 2 ), a flexible spacer 2,2 '-(ethylenedioxy) diene Thiol [2,2 '-(Ethylenedioxy) diethanethiol; Casting a mixture solution of 0.002 ml of 'EDDET' (EDDET) and 0.027 ml of catalyst 1,8-Diazabicyclo [5.4.0] undec-7-ene (hereinafter 'DBU', diluted to 1 000 in toluene) It was.

용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 탈락시켜 DLC-EDDET 1 방열필름을 제조하였다. DLC-EDDET 1 heat-dissipating film was prepared by removing the solvent from the glass substrate after drying at room temperature for 24 hours to remove the solvent.

실시예 3: DLC-EDDET 2 방열필름의 제조Example 3: Preparation of DLC-EDDET 2 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된DLC MA6-0 0.062g, EDDET 0.005ml, DBU 0.055ml의 혼합 용액을 캐스팅하였다. A mixed solution of 0.062 g of DL MA6-0, 0.005 ml of EDDET, and 0.055 ml of DBU was cast on a glass substrate (2 × 2 cm 2 ), dissolved in 0.2 ml toluene.

용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 떼어내어 DLC-EDDET 2 방열필름을 제조하였다. In order to remove the solvent, after drying at room temperature for 24 hours, the glass substrate was removed and a DLC-EDDET 2 heat-dissipating film was prepared.

실시예 4: DLC-EDDET 3 방열필름의 제조Example 4 Preparation of DLC-EDDET 3 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된 DLC MA6-0 0.062g, EDDET 0.007ml, DBU 0.082ml의 혼합 용액을 캐스팅하였다. 용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 떼어내어 DLC-EDDET 3 방열필름을 제조하였다. A mixed solution of 0.062 g of DLC MA6-0, 0.007 ml of EDDET, and 0.082 ml of DBU was cast on a glass substrate (2 × 2 cm 2 ), dissolved in 0.2 ml toluene. In order to remove the solvent, after drying at room temperature for 24 hours, the glass substrate was removed and a DLC-EDDET 3 heat-dissipating film was prepared.

실시예 5: DLC-EDDET 4 방열필름의 제조Example 5: Preparation of DLC-EDDET 4 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된 DLC MA6-0 0.062g, EDDET 0.010ml, DBU 0.110ml의 혼합 용액을 캐스팅하였다. 용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 떼어내어 DLC-EDDET 4 방열필름을 제조하였다. A mixed solution of DLC MA6-0 0.062 g, EDDET 0.010 ml, and DBU 0.110 ml was cast on a glass substrate (2 × 2 cm 2 ) in 0.2 ml toluene. To remove the solvent was dried for 24 hours at room temperature and then removed from the glass substrate to prepare a DLC-EDDET 4 heat radiation film.

실시예 6: DLC-EDDET 5 방열필름의 제조Example 6: Preparation of DLC-EDDET 5 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된 DLC MA6-0 0.062g, EDDET 0.012ml, DBU 0.138ml의 혼합 용액을 캐스팅하였다. 용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 떼어내어 DLC-EDDET 5 방열필름을 제조하였다. A mixed solution of 0.062 g DLC MA6-0, 0.012 ml EDDET, and 0.138 ml DBU was cast on a glass substrate (2 × 2 cm 2 ) dissolved in 0.2 ml toluene. To remove the solvent was dried for 24 hours at room temperature and then removed from the glass substrate to prepare a DLC-EDDET 5 heat radiation film.

실시예 7: DLC-EDDET 6 방열필름의 제조Example 7: Preparation of DLC-EDDET 6 Heat Dissipation Film

유리 기판(2×2 cm2) 위에 0.2ml 톨루엔에 용해된 DLC MA6-0 0.062g, EDDET 0.015ml, DBU 0.165ml의 혼합 용액을 캐스팅하였다. 용매를 제거하기 위해 상온에서 24시간 건조 후 유리 기판에서 떼어내어 DLC-EDDET 6 방열필름을 제조하였다.A mixed solution of 0.062 g of DLC MA6-0, 0.015 ml of EDDET, and 0.165 ml of DBU was cast on a glass substrate (2 × 2 cm 2 ) dissolved in 0.2 ml toluene. To remove the solvent was dried for 24 hours at room temperature and then removed from the glass substrate to prepare a DLC-EDDET 6 heat radiation film.

실험예 1: DLC-EDDET 방열필름 Experimental Example 1: DLC-EDDET Heat Dissipation Film

[반응식 1] Scheme 1

Figure 112017130246334-pat00009
Figure 112017130246334-pat00009

상기 반응식 1에 따라 디스코틱 액정 화합물을 제조하였다. A discotic liquid crystal compound was prepared according to Scheme 1.

도 3은 본 발명의 일실시예에 따른 방열필름의 제조방법에 있어서 디스코틱 액정 화합물의 NMR 데이터이다. 3 is NMR data of a discotic liquid crystal compound in the method of manufacturing a heat radiation film according to an embodiment of the present invention.

도 3을 참조하면, 디스코틱 액정 화합물인DLC MA6-0이 생성되었음을 확인하였다. Referring to FIG. 3, it was confirmed that DLC MA6-0, a discotic liquid crystal compound, was produced.

유연성 스페이서 EDDET를 혼합하여 제조된 방열필름을 통하여 유연성 스페이서인 EDDET가 디스코틱 액정 화합물과 결합하여 방열필름을 형성할 수 있는 것을 확인하였다. Flexible spacer through a heat-dissipating film made by mixing the flexible spacer EDDET It was confirmed that EDDET can be combined with the discotic liquid crystal compound to form a heat radiation film.

기존에 상기 디스코틱 액정 화합물만으로 이루어진 방열필름의 경우 깨지지 쉬운 성향(brittle)을 가지고 있었으나 스페이서인 EDDET를 첨가한 방열필름의 경우 유연(flexible)한 특징을 가지는 것을 확인하였다.Conventionally, the heat dissipation film composed of only the discotic liquid crystal compound had a tendency to break (brittle), but it was confirmed that the heat dissipation film added with the spacer EDDET had a flexible feature.

또한, DLC MA 6-0 0.062g 대비 EDDET 함량을 0.002 mL, 0.005 mL, 0.007 mL로 넣은 상기 실시예 2내지 4의 방열필름은 벤딩(bending) 과정을 수 차례 진행하면 깨지는 반면 EDDET 함량을 0.010 mL, 0.012 mL, 0.015 mL로 바꾸어 제조한 상기 실시예 5 내지 7의 방열 필름은 깨지지 않고 물성을 유지, 유연(flexible)한 특징을 가지는 것을 확인하였다. In addition, the heat-dissipating film of Examples 2 to 4 containing EDDET content of 0.002 mL, 0.005 mL, and 0.007 mL compared to 0.062 g of DLC MA 6-0 is broken after several bending processes, while the EDDET content is 0.010 mL. , 0.012 mL, 0.015 mL by replacing the heat-dissipating film of Examples 5 to 7 was confirmed that the physical properties without breaking, having a flexible (flexible) characteristics.

실시예 8: DLC 21wt%-RM257 방열필름의 제조Example 8 Preparation of DLC 21wt% -RM257 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 1.7ml 톨루엔에 용해된 DLC MA6-0 0.086g, 로드액정 4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester, 이하' RM257] 0.31 g, 광개시제 (2-하이드록시에톡시)-2-메틸프로피오페논[(2-hydroxyethoxy)-2-methylpropiophenone; 이하 'HHMP'] 0.0025 g, EDDET 0.090ml, DBU(톨루엔에 1/1000로 희석하여 사용) 0.49ml의 혼합 용액을 캐스팅하였다. 0.086 g of DLC MA6-0 dissolved in 1.7 ml toluene on a glass substrate (5 × 5 cm 2 ), rod liquid crystal 4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenyl 0.31 g of ene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester, hereinafter 'RM257], photoinitiator (2-hydroxyethoxy) -2-methylpropiophenone [(2- hydroxyethoxy) -2-methylpropiophenone; Hereinafter, a mixed solution of 0.0025 g of 'HHMP'], 0.090 ml of EDDET, and 0.49 ml of DBU (using diluted 1/1000 in toluene) was cast.

용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30 에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트기가 1.2배(mol% 기준) 초과된 필름을 제조하였다. After 24 hours of drying at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film having an acrylate group more than 1.2 times (based on mol%) compared to the thiol.

남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 DLC 21wt%-RM257 방열필름을 얻었다.For further crosslinking of the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final DLC 21wt% -RM257 heat dissipation film.

실시예 9: DLC 27wt%-RM257 방열필름의 제조Example 9 Preparation of DLC 27wt% -RM257 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 1.7ml 톨루엔에 용해된 DLC MA6-0 0.11g, RM257 0.29 g, HHMP 0.0025 g, EDDET 0.090ml, DBU 0.49ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트기가 1.2배 초과된 필름을 제조하였다. A mixed solution of DLC MA6-0 0.11 g, RM257 0.29 g, HHMP 0.0025 g, EDDET 0.090 ml, and DBU 0.49 ml was cast on a glass substrate (5 × 5 cm 2 ). After 24 hours of drying at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film having an acrylate group more than 1.2 times compared to the thiol.

남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 DLC 27wt%-RM257 방열필름을 얻었다. For further crosslinking of the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final DLC 27wt% -RM257 heat dissipation film.

실시예 10: DLC 32wt%-RM257 방열필름의 제조Example 10 Preparation of DLC 32wt% -RM257 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 1.7ml 톨루엔에 용해된 DLC MA6-0 0.13g, RM257 0.27 g, HHMP 0.0025 g, EDDET 0.089ml, DBU 0.48ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30 에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 1.2배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 DLC 32wt%-RM257 방열필름을 얻었다. A mixed solution of DLC MA6-0 0.13 g, RM257 0.27 g, HHMP 0.0025 g, EDDET 0.089 ml, DBU 0.48 ml was cast on a glass substrate (5 × 5 cm 2 ). After drying for 24 hours at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than 1.2 times the acrylate compared to the thiol. In order to further crosslink the remaining acrylate, UV irradiation was performed for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final DLC 32wt% -RM257 heat dissipation film.

실시예 11: DLC 37wt%-RM257 방열필름의 제조Example 11 Preparation of DLC 37wt% -RM257 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 1.7ml 톨루엔에 용해된 DLC MA6-0 0.15g, RM257 0.25 g, HHMP 0.0025 g, EDDET 0.089ml, DBU 0.48ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30 에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 1.2배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 DLC 37wt%-RM257 방열필름을 얻었다.A mixed solution of DLC MA6-0 0.15 g, RM257 0.25 g, HHMP 0.0025 g, EDDET 0.089 ml, DBU 0.48 ml, was cast on a glass substrate (5 × 5 cm 2 ) in 1.7 ml toluene. After drying for 24 hours at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than 1.2 times the acrylate compared to the thiol. In order to further crosslink the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final DLC 37wt% -RM257 heat dissipation film.

실험예 2: 방열필름의 조성 Experimental Example 2: Composition of Heat Dissipation Film

하기 표 1은 실시예 8 내지 11에 따른 방열필름의 로드액정과 디스코틱 액정 화합물의 함량을 나타낸 것이다.Table 1 shows the load liquid crystal and the content of the discotic liquid crystal compound of the heat radiation film according to Examples 8 to 11.

RM257(wt%)RM257 (wt%) DLC(wt%)DLC (wt%) 6363 3737 6868 3232 7373 2727 7979 2121

EDDET의 싸이올기는 전체 아크릴레이트기보다 20 mol% 적게 함유되었으며, DBU는 EDDET의 싸이올 반응기[-SH]의 0.25 mol%, HHMP는 DLC, RM257 및 EDDET의 총 함량에 대해 0.5 wt%로 함유하도록 제조하였다.The thiol group of EDDET contains 20 mol% less than the total acrylate group, DBU contains 0.25 mol% of EDDET's thiol reactor [-SH], and HHMP contains 0.5 wt% of the total contents of DLC, RM257 and EDDET. To be prepared.

실험예 3: 디스코틱 액정 화합물 함유 방열필름의 전도도 Experimental Example 3: Conductivity of a Discharging Liquid Crystal Compound-Containing Heat-Resistant Film

실시예 8, 실시예 9, 실시예 10 및 실시예 11 에서 제조된 필름의 평면에 수직 방향(through-plane) 열전도도 분석을 위해 8×8 mm2정사각형 샘플을 컷팅하여 제조하였다. 8 × 8 mm 2 square samples were prepared for cutting through-plane thermal conductivity analysis in the plane of the films prepared in Examples 8, 9, 10 and 11.

필름 양면에 그라파이트를 스프레이코팅 한 후, 레이져 플래쉬 분석 장비(Netzsch, LFA447)를 이용하여 열확산도를 분석하였다. After spray coating graphite on both sides of the film, the thermal diffusivity was analyzed using a laser flash analyzer (Netzsch, LFA447).

실험결과 Experiment result 수직방향의 열확산도 (mm2s-1)Thermal diffusivity in the vertical direction (mm 2 s -1 ) 실시예 8 (DLC 21wt%-RM257)Example 8 (DLC 21wt% -RM257) 0.1130.113 실시예 9 (DLC 27wt%-RM257)Example 9 (DLC 27wt% -RM257) 0.1200.120 실시예 10 (DLC 32wt%-RM257)Example 10 (DLC 32wt% -RM257) 0.1190.119 실시예 11 (DLC 37wt%-RM257)Example 11 (DLC 37wt% -RM257) 0.1470.147

상기 표 2는 제조된 방열필름의 수직방향 열확산도를 나타낸 것이다. Table 2 shows the thermal diffusivity of the produced heat radiation film in the vertical direction.

디스코틱 액정 분자가 많이 포함되어 있는 실시예 11 (DLC 37wt%-RM257) 이 실시예 8 (DLC 21wt%-RM257)보다 열확산도가 1.3 배가량 높았으며, 디스코틱 액정 분자의 함량이 증가할수록 수직방향의 열확산도 또한 증가하는 것을 확인하였다. Example 11 (DLC 37wt% -RM257) containing a lot of discotic liquid crystal molecules The thermal diffusivity was 1.3 times higher than that of Example 8 (DLC 21wt% -RM257), and vertically with increasing content of discotic liquid crystal molecules. It was also found that the thermal diffusion in the direction also increased.

실시예 12: DLC 21wt%-RM257 액정 배향 방열필름의 제조Example 12 Preparation of DLC 21wt% -RM257 Liquid Crystal Alignment Heat Dissipation Film

상기 실시예 8에서 수행했던 실험 과정을 동일하게 진행하되, 필름의 건조 후 광가교 전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 8, but after the drying of the film was carried out for the alignment of the liquid crystal in the entire process of light crosslinking.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate.

이후 인장기를 분리하여 액정이 배향된 DLC 21wt%-RM257 필름을 얻었다. Thereafter, the tensioner was separated to obtain a DLC 21wt% -RM257 film having liquid crystals oriented.

실시예 13: DLC 27wt%-RM257 액정 배향 방열필름의 제조Example 13: Preparation of DLC 27wt% -RM257 Liquid Crystal Alignment Heat Dissipation Film

상기 실시예 9에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교 전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 9, but after the drying of the film was carried out for the alignment of the liquid crystal in the entire process of light crosslinking.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 DLC 27wt%-RM257 필름을 얻었다.  The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain a DLC 27wt% -RM257 film having liquid crystals oriented.

실시예 14: DLC 32wt%-RM257 액정 배향 방열필름의 제조Example 14 Preparation of DLC 32wt% -RM257 Liquid Crystal Alignment Heat Dissipation Film

상기 실시예 10에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교 전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 10, but after the drying of the film was carried out for the alignment of the liquid crystal in the entire process of optical crosslinking.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 DLC 32wt%-RM257 필름을 얻었다. The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain a DLC 32wt% -RM257 film having liquid crystals oriented.

실시예 15: DLC 37wt%-RM257 액정 배향 방열필름의 제조Example 15 Preparation of DLC 37wt% -RM257 Liquid Crystal Alignment Heat Dissipation Film

상기 실시예 11에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 11, but after the drying of the film was carried out for the alignment of the liquid crystal in the photocrosslinking process.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 DLC 37wt%-RM257 필름을 얻었다.  The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain a DLC 37wt% -RM257 film having liquid crystals oriented.

실험예 4: 배향된 필름의 인장률 확인Experimental Example 4: Confirming the Tensile Modulus of the Oriented Film

도 4는 본 발명의 일실시예에 따른 방열필름의 인장률에 따른 연신된 방열필름의 사진이다. Figure 4 is a photograph of the stretched heat radiation film according to the tensile rate of the heat radiation film according to an embodiment of the present invention.

도 4를 참조하면, 인장률이 150%까지 변화되는 동안 방열필름이 연신되었으며, 방열필름은 다양한 인장률로 연신하는 동안 폴리도메인(polydomain)에서 모노도메인(monodomain)으로 변화되었다. Referring to FIG. 4, the heat dissipation film was stretched while the tensile modulus was changed to 150%, and the heat dissipation film was changed from polydomain to monodomain during stretching at various tensile rates.

DLC 21wt%-RM257 방열필름의 인장률은 50%, 100%, 150%, 200 % 로 다양하게 조절하였으며 최대 200 %까지 인장되는 것을 확인하였다.Tensile modulus of DLC 21wt% -RM257 heat dissipation film was variously adjusted to 50%, 100%, 150%, 200% and confirmed to be stretched up to 200%.

DLC 27wt%-RM257 방열필름의 인장률은 50%, 100%, 150% 로 다양하게 조절하였으며 최대 150%까지 인장되는 것을 확인하였다. Tensile modulus of DLC 27wt% -RM257 heat dissipation film was variously adjusted to 50%, 100%, 150% and was confirmed to be stretched up to 150%.

DLC 32wt%-RM257 방열필름의 인장률은 50%, 100%, 150% 로 다양하게 조절하였으며 최대 150%까지 인장되는 것을 확인하였다.Tensile modulus of DLC 32wt% -RM257 heat dissipation film was variously adjusted to 50%, 100%, 150% and confirmed to be stretched up to 150%.

DLC 37wt%-RM257 방열필름의 인장률은 50%, 100%로 다양하게 조절하였으며 최대 100%까지 인장되는 것을 확인하였다.Tensile modulus of DLC 37wt% -RM257 heat dissipation film was variously adjusted to 50%, 100% and confirmed to be stretched up to 100%.

따라서 디스코틱 액정 화합물의 함량이 증가되는 경우, 트리페닐렌 코어의 구조적인 강직성 및 가교밀도 증가 때문에 인장률이 감소되는 경향을 확인하였다. Therefore, when the content of the discotic liquid crystal compound is increased, it was confirmed that the tensile modulus tended to decrease due to the structural rigidity and the crosslinking density of the triphenylene core.

실시예 16: Acryl1.2-PETMP 방열필름의 제조Example 16: Preparation of Acryl1.2-PETMP Heat Dissipation Film

유리 기판(5×5 cm2) 위에 1.7ml 톨루엔에 용해된 RM257 0.39 g, HHMP 0.0025 g, EDDET 0.064ml, PETMP 0.031ml, DBU 0.49ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 1.2배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 Acryl1.2-PETMP 방열필름을 얻었다.A mixed solution of 0.39 g of RM257, 0.0025 g of HHMP, 0.064 ml of EDDET, 0.031 ml of PETMP, and 0.49 ml of DBU was cast on a glass substrate (5 × 5 cm 2 ) in 1.7 ml toluene. After 24 hours of drying at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than 1.2 times the acrylate compared to the thiol. For further crosslinking of the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final Acryl1.2-PETMP heat radiation film.

실시예 17: Acryl1.2-PET2 방열필름의 제조Example 17 Preparation of Acryl1.2-PET2 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 2.5ml 톨루엔에 용해된 RM257 0.34 g, HHMP 0.0018 g, EDDET 0.062ml, PETMP 0.018ml, DBU 0.16ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 1.2배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 Acryl1.2-PET2 방열필름을 얻었다.A mixed solution of 0.34 g of RM257, 0.0018 g of HHMP, 0.062 ml of EDDET, 0.018 ml of PETMP, and 0.16 ml of DBU was cast on a glass substrate (5 × 5 cm 2 ). After 24 hours of drying at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than 1.2 times the acrylate compared to the thiol. For further crosslinking of the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final Acryl1.2-PET2 heat dissipating film.

실시예 18: Acryl1.5-PET6 방열필름의 제조Example 18 Preparation of Acryl1.5-PET6 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 2.5 ml 톨루엔에 용해된 RM257 0.35 g, HHMP 0.0018 g, EDDET 0.025ml, 가교제 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate); 이하 'PETMP'] 0.045ml, DBU 0.13ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30 에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 1.5배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 Acryl1.5-PET6 방열필름을 제 조하였다.0.35 g of RM257 dissolved in 2.5 ml toluene on a glass substrate (5 × 5 cm 2 ), 0.0018 g HHMP, 0.025 ml EDDET, crosslinking agent pentaerythritol tetrakis (3-mercaptobutanoate) [pentaerythritol tetrakis (3-mercaptopropionate) ; Hereinafter, a mixed solution of 0.045 ml of 'PETMP'] and 0.13 ml of DBU was cast. After drying for 24 hours at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than 1.5 times the acrylate compared to the thiol. In order to further crosslink the remaining acrylate, UV irradiation was carried out for 5 minutes to carry out the photocrosslinking reaction, and then separated from the substrate to prepare a final Acryl1.5-PET6 heat dissipating film.

실시예 19: Acryl2-PET10 방열필름의 제조Example 19 Preparation of Acryl2-PET10 Heat Dissipation Film

유리 기판(5×5 cm2) 위에 2.5ml 톨루엔에 용해된 RM257 0.36 g, HHMP 0.0018 g, PETMP 0.058ml, DBU 0.10ml의 혼합 용액을 캐스팅하였다. 용매를 완전히 제거하기 위해 상온에서 24시간 건조 후, 30에서 진공 오븐에서 5시간 추가 건조시켜 싸이올이기에 비해 아크릴레이트가 2배 초과된 필름을 제조하였다. 남아있는 아크릴레이트의 추가적인 가교를 위해 5분간 UV 조사하여 광가교 반응을 진행한 후 기판에서 떼어내어 최종적인 Acryl2-PET10 방열필름을 얻었다.A mixed solution of 0.36 g of RM257, 0.0018 g of HHMP, 0.058 ml of PETMP, and 0.10 ml of DBU was cast on a glass substrate (5 × 5 cm 2 ) in 2.5 ml toluene. After 24 hours of drying at room temperature to completely remove the solvent, and further dried for 5 hours in a vacuum oven at 30 to prepare a film more than twice the acrylate compared to the thiol. For further crosslinking of the remaining acrylate, UV irradiation was carried out for 5 minutes to remove the substrate from the photocrosslinking reaction to obtain a final Acryl2-PET10 heat radiation film.

실시예 20: Acryl1.2-PET2 액정 배향 방열필름의 제조Example 20 Preparation of Acryl1.2-PET2 Liquid Crystal Alignment Heat Dissipation Film

실시예 17에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교 전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 17, but after the drying of the film was carried out for the alignment of the liquid crystal in the entire process of optical crosslinking.

제조된 방열필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 Acryl1.2-PET2 필름을 얻었다. The prepared heat-dissipating film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile rate was fixed to proceed with the photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain an Acryl1.2-PET2 film having liquid crystals oriented.

이 때, 인장률은 100%로 고정하여 제조하였다.At this time, the tensile rate was prepared by fixing to 100%.

실시예 21: Acryl1.5-PET6 액정 배향 방열필름의 제조Example 21 Preparation of Acryl1.5-PET6 Liquid Crystal Alignment Heat Dissipation Film

상기 실시예 18에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교 전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 18, but after the drying of the film was carried out for the alignment of the liquid crystal in the entire process of optical crosslinking.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 Acryl1.5-PET6 필름을 얻었다.  The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain an Acryl1.5-PET6 film having liquid crystals oriented.

이 때, 인장률은 100%로 고정하여 제조하였다.At this time, the tensile rate was prepared by fixing to 100%.

실시예 22: Acryl2-PET10 액정 배향 필름의 제조Example 22 Preparation of Acryl2-PET10 Liquid Crystal Alignment Film

상기 실시예 19에서 수행했던 실험 과정을 동일하게 진행하되 필름의 건조 후 광가교전 과정에서 액정의 배향을 위한 과정을 수행하였다. The experiment was carried out in the same manner as in Example 19, but after the drying of the film was carried out for the alignment of the liquid crystal in the photocrosslinking process.

제조된 필름을 인장기를 사용하여 인장한 다음 인장율이 고정된 상태로 5분간 UV를 조사하여 광가교 반응을 진행, 남아있는 아크릴레이트를 가교시켰다. 이후 인장기를 분리하여 액정이 배향된 Acryl2-PET10 필름을 얻었다.  The prepared film was stretched using a tensioner and then irradiated with UV for 5 minutes in a state where the tensile ratio was fixed to undergo a photocrosslinking reaction to crosslink the remaining acrylate. Thereafter, the tensioner was separated to obtain an Acryl2-PET10 film having liquid crystals oriented.

이 때, 인장률은 100%로 고정하여 제조하였다.At this time, the tensile rate was prepared by fixing to 100%.

실험예 5: 가교제를 함유하는 방열필름의 유연성 Experimental Example 5: Flexibility of the heat-dissipating film containing a crosslinking agent

도 5는 본 발명의 다른 실시예에 따른 방열필름의 접힘 사진이다. 5 is a folded picture of the heat radiation film according to another embodiment of the present invention.

도 5를 참조하면, 인장기를 통하여 연신한 이후에도 유연성을 유지하여 접힘이 가능한 것을 확인하였다. Referring to Figure 5, even after stretching through the tensioner was confirmed that the folding is possible to maintain the flexibility.

또한, 방열필름의 양 끝을 잡고, 곡률반경 5 mm 이하로 100회 이상 벤딩(bending) 테스트를 실시하여도 크랙(crack)이나 깨짐 현상 없이 필름의 유연성이 유지되는 것을 확인하였다.In addition, it was confirmed that the flexibility of the film is maintained without cracking or cracking even when holding both ends of the heat dissipating film and performing a bending test more than 100 times at a radius of curvature of 5 mm or less.

실험예 6: 가교제를 함유하는 방열필름의 열전도도 측정Experimental Example 6: Measurement of thermal conductivity of a heat-dissipating film containing a crosslinking agent

실시예 17, 실시예 18, 및 실시예 19에서 제조된 필름의 평면 내 (in-plane) 열확산도 분석을 위해 지름 2.54 cm의 원형 샘플을 컷팅하여 제조하였다. Circular samples of diameter 2.54 cm were cut for in-plane thermal diffusivity analysis of the films prepared in Examples 17, 18, and 19.

필름 양면에 그라파이트를 스프레이코팅 한 후, 레이져 플래쉬 분석 장비(Netzsch, LFA447)를 이용하여 열확산도를 분석하였다.After spray coating graphite on both sides of the film, the thermal diffusivity was analyzed using a laser flash analyzer (Netzsch, LFA447).

수평방향의 열확산도(mm2s-1)Thermal diffusivity in the horizontal direction (mm 2 s -1 ) 실시예 17(Acryl1.2-PET2)Example 17 (Acryl1.2-PET2) 1.171.17 실시예 18(Acryl1.5-PET6)Example 18 (Acryl1.5-PET6) 1.021.02 실시예 19(Acryl2-PET10)Example 19 (Acryl2-PET10) 1.401.40

상기 표3은 가교제를 함유하는 방열필름의 열전도도를 측정한 결과이다. Table 3 shows the results of measuring the thermal conductivity of the heat radiation film containing a crosslinking agent.

수평방향의 열확산도를 측정한 결과 싸이올 반응기 대비 아크릴레이트 반응기를 2배 과량 넣어 제조한 실시예 19(Acryl2-PET10)에 따른 방열필름이 가장 우수한 수평방향 열확산도를 가지는 것으로 확인하였다. As a result of measuring the thermal diffusivity in the horizontal direction, the heat dissipation film according to Example 19 (Acryl2-PET10) prepared by doubling the acrylate reactor compared to the thiol reactor was confirmed to have the best horizontal thermal diffusivity.

이는 과량 첨가한 아크릴레이트의 추가적인 가교로 인한 것으로 액정 배향을 견고하고 유지시켜줌과 동시에 가교 밀도의 증가로 인한 높은 열확산도를 가지는 것으로 확인하였다.This is due to the additional crosslinking of the added acrylate, it was confirmed that it has a high thermal diffusivity due to an increase in the crosslink density while maintaining and maintaining the liquid crystal alignment.

실험예 7: 가교제를 함유하는 방열필름의 열확산 이미지Experimental Example 7: Thermal Diffusion Image of Heat Dissipating Film Containing Crosslinking Agent

실시예 17, 실시예 18, 실시예 19에 따라 제조된 방열필름을 준비하고, 실시예 17, 실시예 20, 실시예 19, 실시예 22에 따라 제조된 방열필름을 준비하였다. The heat dissipation films prepared according to Examples 17, 18, and 19 were prepared, and the heat dissipation films prepared according to Examples 17, 20, 19, and 22 were prepared.

준비된 방열필름의 열 확산 이미지 촬영을 위해, 직사각형 샘플로 컷팅 하였다. 직사각형의 아랫부분과 핫플레이트(hot plate)를 구리 테이프로 고정시킨 후, 30 로 핫플레이트의 온도를 안정화 시켰다. 온도가 안정화된 후, 100로 핫플레이트의 온도를 셋팅하고, 시간에 따른 승온 과정에서의 필름 내 열 확산 이미지를 적외선 카메라를 이용해 관찰하였다. For thermal diffusion image photographing of the prepared heat-dissipating film, it was cut into rectangular samples. After fixing the bottom of the rectangle and the hot plate (hot plate) with copper tape, the temperature of the hot plate was stabilized to 30. After the temperature was stabilized, the temperature of the hot plate was set to 100, and the thermal diffusion image in the film was observed using an infrared camera during the temperature rising process over time.

도 6, 7은 본 발명의 다른 구체예에 따른 방열필름의 열확산 이미지를 나타낸 것이다. 6 and 7 show thermal diffusion images of the heat radiation film according to another embodiment of the present invention.

도 6, 7을 참조하면, 실시예 19 (Acryl2-PET10)과 실시예 22(Acryl2-PET10의 배향 필름)이 가장 열 확산이 잘 일어나는 것을 확인 하였다. 6 and 7, it was confirmed that Example 19 (Acryl2-PET10) and Example 22 (alignment film of Acryl2-PET10) were the most thermal diffusion occurs.

상대적으로 실시예19에 비해서 실시예 22가 우수한 열 확산도를 가지는 것으로 확인하였다. 이는 과량 첨가한 아크릴레이트가 액정 배향을 더욱 견고하게 유지시켜 준다는 사실을 보여준다.It was confirmed that Example 22 had an excellent thermal diffusivity relative to Example 19. This shows that the excessively added acrylate maintains the liquid crystal alignment more firmly.

또한 열확산 이미지 분석을 통해 실시예 22(Acryl2-PET10 액정배향 필름)는 상기 표3에서 실시예 19(Acryl2-PET10)의 기록된 1.40mm2s-1 열확산도의 값보다 더 큰 열확산도 값을 갖는 것으로 확인되었다.Thermal diffusive image analysis also showed that Example 22 (Acryl2-PET10 liquid crystal alignment film) exhibited a thermal diffusivity value greater than the recorded 1.40 mm 2 s -1 thermal diffusivity value of Example 19 (Acryl2-PET10) in Table 3 above. It was confirmed to have.

지금까지 본 발명에 따른 방열필름 및 이의 제조방법에 관한 구체적인 실시예에 관하여 설명하였으나, 본 발명의 범위에서 벗어나지 않는 한도 내에서는 여러 가지 실시 변형이 가능함은 자명하다.So far it has been described with respect to specific embodiments of the heat dissipation film and a method for manufacturing the same, it is obvious that various embodiments can be modified within the scope of the present invention.

그러므로 본 발명의 범위에는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등한 것들에 의해 정해져야 한다.Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims below and equivalents thereof.

즉, 전술된 실시예는 모든 면에서 예시적인 것이며, 한정적인 것이 아닌 것으로 이해되어야 하며, 본 발명의 범위는 상세한 설명보다는 후술될 특허청구범위에 의하여 나타내어지며, 그 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.In other words, the foregoing embodiments are to be understood in all respects as illustrative and not restrictive, the scope of the invention being indicated by the following claims rather than the detailed description, and the meaning and scope of the claims and All changes or modifications derived from the equivalent concept should be construed as being included in the scope of the present invention.

Claims (13)

아크릴레이트기(acrylate functional group) 함유 로드액정;
하기 화학식 1로 표시되는 디스코틱 액정 화합물; 및
싸이올기(thiol group) 함유 스페이서를 포함하는 방열필름용 조성물:
[화학식 1]
Figure 112017130246334-pat00010

(여기서 상기 R 은
Figure 112017130246334-pat00011
임.)

A rod liquid crystal containing an acrylate functional group;
A discotic liquid crystal compound represented by Formula 1 below; And
Composition for a heat radiation film comprising a thiol group-containing spacer:
[Formula 1]
Figure 112017130246334-pat00010

Where R is
Figure 112017130246334-pat00011
being.)

제1항에 있어서,
상기 로드액정은
4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스터{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나 인 것을 특징으로 하는 방열필름용 조성물.
The method of claim 1,
The load liquid crystal
4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester], 1 , 4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 1 , 4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 4 -[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl-1,4-phenyl Len) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl-1,4- phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester benzo Ic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid}, 4- [[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic acid-4-[[[4-[[6-[(1-oxo -2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6-[(1-Oxo-2-propen-1-yl) oxy] hexyl ] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4- ( (6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1 '-(1,4-phenylene) ester {4-((6- ( (1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4-phenylene) Ester}, 4- [3-[(1-oxo-2- Propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4- [3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro-2,5-bis [4-[[4-[[[4- [(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol {1,4,3,6-Dianhydro-2 , 5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalene carboxylic acid-2- (Methoxycarbonyl) -1,4-phenylene ester {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecarboxylic Acid-2- (methoxycarbonyl ) -1,4-phenylene Ester} composition for a heat radiation film, characterized in that any one selected from the group consisting of.
제1항에 있어서,
상기 스페이서(spacer)는
유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나인 것을 특징으로 하는 방열필름용 조성물.
The method of claim 1,
The spacer is
Flexible, 2,2 '-(ethylenedioxy) diethanthiol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1,5- Pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1,9-nonanedydi Thiol (1,9-Nonanedithiol), 1,11-Undecanedithiol, 1,16-hexadecanedithiol (1,16-Hexadecanedithiol), tetra (ethylene glycol) di Thiol [Tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] A composition for a heat radiation film, characterized in that any one selected from the group consisting of.
제1항에 있어서,
상기 방열필름용 조성물은
디스코틱 액정 화합물을 21 내지 37 wt%로 함유하고, 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 1.2배(mol%) 과량 첨가된 것을 특징으로 하는 방열필름용 조성물.
The method of claim 1,
The heat dissipation film composition
21 to 37 wt% of a discotic liquid crystal compound, and a heat dissipating film composition, characterized in that 1.2 times (mol%) excess of the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound is added to the thiol group.
제1항 내지 제4항 중 어느 한 항의 방열필름용 조성물을 도포하여 제조되는 방열필름.
A heat radiation film produced by applying the composition for heat radiation film of any one of claims 1 to 4.
제5항에 있어서,
상기 방열필름은
로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 과량 첨가되어, 결합하지 않은 아크릴레이트기가 광가교(photo cross-linking)된 것을 특징으로 하는 방열필름.
The method of claim 5,
The heat dissipation film is
An acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound is excessively added compared to the thiol group, the heat-dissipating film, characterized in that the non-bonded acrylate group is photocross-linked.
아크릴레이트기 함유 로드액정; 싸이올기를 함유하는 스페이서 및 가교제를 포함하되,
상기 로드액정에 함유된 아크릴레이트기가 스페이서 및 가교제에 함유된 싸이올기에 비해 1.2내지 2배(mol%) 과량 첨가된 방열필름용 조성물을 도포하여 제조되며, 액정이 배향되어 수평방향(in-plane) 열확산도가 1.02 내지 1.40 mm2S-1인 것을 특징으로 하는 방열필름.
Acrylate group-containing rod liquid crystals; A spacer containing a thiol group and a crosslinking agent,
The acrylate group contained in the rod liquid crystal is prepared by applying a composition for heat-dissipating film added 1.2 to 2 times (mol%) excess of the thiol group contained in the spacer and the crosslinking agent, and the liquid crystal is oriented in the horizontal direction (in-plane Heat dissipation film, characterized in that the thermal diffusivity is 1.02 to 1.40 mm 2 S -1 .
제7항에 있어서,
상기 로드액정은
4-(3-아크릴로일옥시프로필옥시)-벤조익애시드 2-메틸-1, 4-페닐렌 에스터[4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester], 1,4-비스-[4-(3-아크릴로일옥시프로필옥시)벤조일옥시]-2-메틸벤젠{1,4-Bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 1,4-비스-[4-(6- 아크릴로일옥시프로필옥시)벤조일옥시]-2- 메틸벤젠{1,4-Bis-[4-(6-acryloyloxypropyloxy)benzoyloxy]-2-methylbenzene}, 4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조익 애시드-1,1'-(2-메틸-1,4-페닐렌)에스터{4-[[[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoic Acid-1,1'-(2-methyl-1,4-phenylene) Ester}, 4-[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]-1,1'-(2-메틸-1,4-페닐렌)에스터 벤조익 애시드{4-[4-[(1-Oxo-2-propen-1-yl)oxy]butoxy]-1,1'-(2-methyl-1,4-phenylene)ester Benzoic Acid}, 4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]벤조익 애시드-4-[[[4-[[6-[(1-옥소-2-프로펜-1-일)옥시]헥실]옥시]시클로헥실]카보닐]옥시]페닐 에스터{4-[[6-[(1-Oxo-2-propen-1-yl)oxy]hexyl]oxy]benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl)oxy]hexyl]oxy]cyclohexyl]carbonyl]oxy]phenyl Ester}, 4-((6-((1-옥소-2-프로펜-1-일)옥시)헥실)옥시)벤조익 애시드-1,1'-(1,4-페닐렌)에스터{4-((6-((1-oxo-2-propen-1-yl)oxy)hexyl)oxy)benzoic Acid-1,1'-(1,4-phenylene) Ester}, 4-[3-[(1-옥소-2-프로펜-1-일)옥시]프로폭시]-1,1'-(1,4-페닐렌)에스터 벤조익 애시드{4-[3-[(1-Oxo-2-propen-1-yl)oxy]propoxy]-1,1'-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-디안하이드로-2,5-비스[4-[[4-[[[4-[(1-옥소-2-프로펜-1-일)옥시]부톡시]카보닐]옥시]벤조일]옥시]벤조에이트]-D-글루시톨{1,4,3,6-Dianhydro-2,5-bis[4-[[4-[[[4-[(1-oxo-2-propen-1-yl)oxy]butoxy]carbonyl]oxy]benzoyl]oxy]benzoate]-D-glucitol} 및 6-[[[4-[(1-옥소-2-프로페닐)옥시]부톡시]카보닐]옥시]-2-나프탈렌카르복실릭 애시드-2-(메톡시카보닐)-1,4-페닐렌 에스터{6-[[[4-[(1-Oxo-2-propenyl)oxy]butoxy]carbonyl]oxy]-2-naphthalenecarboxylic Acid-2-(methoxycarbonyl)-1,4-phenylene Ester}로 이루어진 군에서 선택된 어느 하나 이고,
상기 스페이서는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이며,
상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate)] 인 것을 특징으로 하는 방열필름.
The method of claim 7, wherein
The load liquid crystal
4- (3-acryloyloxypropyloxy) -benzoic acid 2-methyl-1, 4-phenylene ester [4- (3-Acryloyloxypropyloxy) benzoic acid 2-methyl-1,4-phenylene ester], 1 , 4-bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (3-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 1 , 4-bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene {1,4-Bis- [4- (6-acryloyloxypropyloxy) benzoyloxy] -2-methylbenzene}, 4 -[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic acid-1,1 '-(2-methyl-1,4-phenyl Len) ester {4-[[[4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoic Acid-1,1 '-(2-methyl-1,4- phenylene) Ester}, 4- [4-[(1-oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester benzo Ic acid {4- [4-[(1-Oxo-2-propen-1-yl) oxy] butoxy] -1,1 '-(2-methyl-1,4-phenylene) ester Benzoic Acid}, 4- [[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] benzoic acid-4-[[[4-[[6-[(1-oxo -2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl ester {4-[[6-[(1-Oxo-2-propen-1-yl) oxy] hexyl ] oxy] benzoic Acid-4-[[[4-[[6-[(1-oxo-2-propen-1-yl) oxy] hexyl] oxy] cyclohexyl] carbonyl] oxy] phenyl Ester}, 4- ( (6-((1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic acid-1,1 '-(1,4-phenylene) ester {4-((6- ( (1-oxo-2-propen-1-yl) oxy) hexyl) oxy) benzoic Acid-1,1 '-(1,4-phenylene) Ester}, 4- [3-[(1-oxo-2- Propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) ester benzoic acid {4- [3-[(1-Oxo-2-propen-1-yl) oxy] propoxy] -1,1 '-(1,4-phenylene) Ester Benzoic Acid}, 1,4,3,6-dianhydro-2,5-bis [4-[[4-[[[4- [(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol {1,4,3,6-Dianhydro-2 , 5-bis [4-[[4-[[[4-[(1-oxo-2-propen-1-yl) oxy] butoxy] carbonyl] oxy] benzoyl] oxy] benzoate] -D-glucitol} and 6-[[[4-[(1-oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalene carboxylic acid-2- (Methoxycarbonyl) -1,4-phenylene ester {6-[[[4-[(1-Oxo-2-propenyl) oxy] butoxy] carbonyl] oxy] -2-naphthalenecarboxylic Acid-2- (methoxycarbonyl ) -1,4-phenylene Ester}, selected from the group consisting of
The spacer is flexible and has 2,2 '-(ethylenedioxy) diethinol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1 , 5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1,9 Nonanedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, tetra (ethylene Glycol) dithiol [Tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] is any one selected from the group consisting of,
The crosslinking agent is a pentaerythritol tetrakis (3-mercaptobutanoate) [pentaerythritol tetrakis (3-mercaptopropionate)] heat radiation film, characterized in that.
(a) 아크릴레이트기 함유 로드액정, 하기 화학식 1로 표시되는 디스코틱 액정화합물, 싸이올기 함유 스페이서(spacer), 광개시제 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하는 단계;
(b) 상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하는 단계;
(c) 상기 액정필름을 연신하여 액정의 배향을 조절하는 단계; 및
(d) 상기 액정필름에 UV를 조사하여 광가교하는 단계를 포함하는 방열필름 제조방법:
[화학식 1]
Figure 112019088743510-pat00012

(여기서 상기 R 은
Figure 112019088743510-pat00013
임.)
(a) dissolving an acrylate group-containing rod liquid crystal, a discotic liquid crystal compound represented by Chemical Formula 1, a thiol group-containing spacer, a photoinitiator, and a catalyst in toluene to prepare a mixed solution;
(b) applying the mixed solution to a substrate and drying to obtain a liquid crystal film;
(c) stretching the liquid crystal film to adjust alignment of liquid crystals; And
(D) a heat radiation film manufacturing method comprising the step of photo-crosslinking by irradiating UV to the liquid crystal film:
[Formula 1]
Figure 112019088743510-pat00012

Where R is
Figure 112019088743510-pat00013
being.)
제9항에 있어서,
상기 혼합용액은
63 내지 79 wt% 로드액정 및 21 내지 37 wt%의 디스코틱 액정 화합물을 포함하는 방열필름 제조방법.
The method of claim 9,
The mixed solution is
A heat dissipation film production method comprising 63 to 79 wt% load liquid crystal and 21 to 37 wt% of a discotic liquid crystal compound.
제9항에 있어서,
상기 스페이서는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이며,
상기 (d) 단계에서, 로드액정 및 디스코틱 액정 화합물에 함유된 아크릴레이트기가 싸이올기에 비해 1.2 배(mol%) 과량 첨가되어, 결합하지 않은 아크릴레이트기가 광가교(photo cross-linking)된 것을 특징으로 하는 방열필름 제조방법.
The method of claim 9,
The spacer is flexible and has 2,2 '-(ethylenedioxy) diethinol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1 , 5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1,9 Nonanedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, and tetra (ethylene Glycol) dithiol [Tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] is any one selected from the group consisting of,
In the step (d), 1.2 times (mol%) excess of the acrylate group contained in the rod liquid crystal and the discotic liquid crystal compound is added, so that the unbonded acrylate group is photocross-linked. Heat radiation film manufacturing method characterized in that.
(i) 아크릴레이트기 함유 로드액정, 광개시제, 및 촉매를 톨루엔(toluene)에 용해시켜 혼합용액을 제조하는 단계;
(ii) 상기 혼합용액을 기판에 도포하고 건조하여 액정필름을 수득하는 단계;
(iii) 상기 액정필름을 연신하여 액정의 배향을 조절하는 단계; 및
(iv) 상기 액정필름에 UV를 조사하여 광가교하는 단계를 포함하는 방열필름 제조방법.
(i) dissolving an acrylate group-containing rod liquid crystal, a photoinitiator, and a catalyst in toluene to prepare a mixed solution;
(ii) applying the mixed solution to a substrate and drying to obtain a liquid crystal film;
(iii) stretching the liquid crystal film to adjust alignment of liquid crystals; And
(iv) a heat radiation film manufacturing method comprising the step of photo-crosslinking by irradiating UV to the liquid crystal film.
제12항에 있어서,
상기 (i) 단계의 혼합용액은 스페이서(spacer) 및 가교제를 더 포함하며,
상기 스페이서는 유연성을 가지며, 2,2'-(에틸렌디옥시)디에테인싸이올[2,2'-(Ethylenedioxy)diethanethiol], 1,4-뷰테인디싸이올(1,4-Butanedithiol), 1,5-펜테인디싸이올(1,5-Pentanedithiol), 1,6-헥세인디싸이올(1,6-Hexanedithiol), 1,8-옥테인디싸이올(1,8-Octanedithiol), 1,9-노네인디싸이올(1,9-Nonanedithiol), 1,11-언디케인디싸이올(1,11-Undecanedithiol), 1,16-헥사디케인디싸이올(1,16-Hexadecanedithiol), 테트라(에틸렌 글리콜)디싸이올[Tetra(ethylene glycol)dithiol], 및 헥사(에틸렌 글리콜)디싸이올[Hexa(ethylene glycol)dithiol]로 이루어지는 군에서 선택되는 어느 하나이며,
상기 가교제는 펜타에리스리톨 테트라키스(3-메르캅토부타노에이트) [pentaerythritol tetrakis (3-mercaptopropionate)]이고,
상기 로드액정의 아크릴레이트기가 스페이서 및 가교제의 싸이올기(thiol group)에 비해 1.2 내지 2배(mol%) 과량 첨가되는 것을 특징으로 하는 방열필름 제조방법.


The method of claim 12,
The mixed solution of step (i) further comprises a spacer and a crosslinking agent,
The spacer is flexible and has 2,2 '-(ethylenedioxy) diethinol [2,2'-(Ethylenedioxy) diethanethiol], 1,4-butanedithiol (1,4-Butanedithiol), 1 , 5-pentanedithiol (1,5-Pentanedithiol), 1,6-hexanedithiol (1,6-Hexanedithiol), 1,8-octanedithiol (1,8-Octanedithiol), 1,9 Nonanedithiol, 1,11-Undecanedithiol, 1,16-hexadecanedithiol, and tetra (ethylene Glycol) dithiol [Tetra (ethylene glycol) dithiol], and hexa (ethylene glycol) dithiol [Hexa (ethylene glycol) dithiol] is any one selected from the group consisting of,
The crosslinking agent is pentaerythritol tetrakis (3-mercaptobutanoate) [pentaerythritol tetrakis (3-mercaptopropionate)],
Method of producing a heat-radiating film, characterized in that the acrylate group of the load liquid crystal is added in excess of 1.2 to 2 times (mol%) compared to the thiol group of the spacer and the crosslinking agent.


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KR101060829B1 (en) 2003-08-08 2011-08-30 코닌클리즈케 필립스 일렉트로닉스 엔.브이. Alignment layer with reactive mesogens to align the liquid crystal molecules
KR101124834B1 (en) 2003-07-12 2012-03-26 메르크 파텐트 게엠베하 Polymerised liquid crystal film with improved adhesion

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KR101124834B1 (en) 2003-07-12 2012-03-26 메르크 파텐트 게엠베하 Polymerised liquid crystal film with improved adhesion
KR101060829B1 (en) 2003-08-08 2011-08-30 코닌클리즈케 필립스 일렉트로닉스 엔.브이. Alignment layer with reactive mesogens to align the liquid crystal molecules
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