KR20130076154A - Polyamic acid composition, polyimide film and substrateused for display device using the same - Google Patents
Polyamic acid composition, polyimide film and substrateused for display device using the same Download PDFInfo
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- KR20130076154A KR20130076154A KR1020110144619A KR20110144619A KR20130076154A KR 20130076154 A KR20130076154 A KR 20130076154A KR 1020110144619 A KR1020110144619 A KR 1020110144619A KR 20110144619 A KR20110144619 A KR 20110144619A KR 20130076154 A KR20130076154 A KR 20130076154A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Abstract
Description
본 발명은 높은 분자량을 유지하면서 낮은 점도를 갖는 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름 및 디스플레이 소자용 기판에 관한 것이다.
The present invention relates to a polyamic acid composition having a low viscosity while maintaining a high molecular weight, a polyimide film and a substrate for a display device using the same.
폴리이미드 필름은 불용, 불융의 초고내열성 수지로 내열산화성, 내열특성, 내방사선성, 저온특성, 내약품성 등이 우수한 특성을 가지고 있고 자동차 재료, 항공소재, 우주선 소재 등의 내열 첨단소재 및 절연코팅제, 절연막, 반도체, TFT-LCD의 전극 보호막 등의 전자재료뿐만 아니라 다양한 분야에 사용되고 있다.Polyimide film is an insoluble and insoluble ultra high heat resistant resin that has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature, and chemical resistance, and heat-resistant advanced materials and insulation coating agents for automobile materials, aeronautical materials, and spacecraft materials. It is used not only in electronic materials such as insulating films, semiconductors, electrode protective films of TFT-LCDs, but also in various fields.
일반적으로 폴리이미드 필름은 방향족 디언하이드라이드와 방향족 디아민의 축중합에 의해 폴리아믹산 조성물을 제조하고, 고온에서 폐환탈수시켜 이미드화하여 제조되는 고내열 필름이다.Generally, a polyimide film is a high heat-resistant film manufactured by producing a polyamic acid composition by polycondensation of an aromatic dianhydride and an aromatic diamine, and imidating by ring-dehydrating at high temperature.
폴리이미드 필름을 제조하는 방법 중 하나로서, 폴리이미드 전구체인 폴리아믹산 조성물을 캐리어 플레이트에 도포하고 경화시켜 폴리이미드 필름을 얻는 캐스트(cast)법이 있다. 상기 캐스트(cast)법은 수지 조성물을 캐리어 플레이트에 도포하는 공정, 도포된 코팅층의 용제를 제거하는 건조공정, 폴리이미드 조성물로부터 폴리이미드로 변환하는 이미드화 공정으로 구성된다.As a method of manufacturing a polyimide film, there exists a cast method which apply | coats and hardens the polyamic-acid composition which is a polyimide precursor to a carrier plate, and obtains a polyimide film. The cast method includes a step of applying a resin composition to a carrier plate, a drying step of removing a solvent of the applied coating layer, and an imidization step of converting the polyimide composition into a polyimide.
이와 같이 폴리이미드 필름을 제조하는데 사용되는 폴리아믹산 조성물은 방향족 디언하이드라이드와 방향족 디아민의 몰비가 1:1이 될 때 폴리아믹산 조성물의 분자량이 급격하게 증가하고, 분자량이 증가함에 따라 열적 안정성이 매우 우수하여 고온에서 필름이 팽창하지 않는다.Thus, the polyamic acid composition used to prepare the polyimide film has a rapid increase in molecular weight of the polyamic acid composition when the molar ratio of aromatic dianhydride and aromatic diamine is 1: 1, and thermal stability is very high as the molecular weight increases. It is excellent so that the film does not expand at high temperatures.
그러나 폴리아믹산 조성물의 분자량이 급격하게 증가하게 되면 분자량의 증가에 따라 점도가 급격하게 증가하게 되고, 점도가 높으면 폴리아믹산 조성물을 도포하기가 어려워 공정상에 문제가 발생한다.However, if the molecular weight of the polyamic acid composition is rapidly increased, the viscosity is rapidly increased as the molecular weight is increased, and if the viscosity is high, it is difficult to apply the polyamic acid composition, causing problems in the process.
따라서 높은 분자량을 유지하면서 낮은 점도를 가져 폴리이미드 필름의 우수한 성질은 유지할 수 있는 폴리아믹산 조성물이 요구된다.
Therefore, there is a need for a polyamic acid composition that has a low viscosity while maintaining a high molecular weight and can maintain the excellent properties of the polyimide film.
본 발명의 목적은 높은 분자량을 유지하면서 낮은 점도를 갖는 폴리아믹산 조성물을 제공하는데 있다.An object of the present invention is to provide a polyamic acid composition having a low viscosity while maintaining a high molecular weight.
또한, 본 발명의 다른 목적은 상기 폴리아믹산 조성물을 이용하여 제조된 폴리이미드 필름을 제공하는데 있다.In addition, another object of the present invention to provide a polyimide film prepared using the polyamic acid composition.
또한, 본 발명의 또 다른 목적은 상기 폴리이미드 필름을 포함하는 디스플레이 소자용 기판을 제공하는데 있다.
In addition, another object of the present invention to provide a substrate for a display device comprising the polyimide film.
상기한 본 발명의 목적을 달성하기 위하여 본 발명의 폴리아믹산 조성물은 방향족 디아민과 3개의 아민기를 갖는 방향족 트리아민이 70:30 내지 99:1의 몰비로 혼합된 방향족 디/트리아민 화합물 및 방향족 언하이드라이드가 축중합된 것을 특징으로 한다.In order to achieve the above object of the present invention, the polyamic acid composition of the present invention comprises an aromatic di / triamine compound and an aromatic unhydrate in which an aromatic diamine and an aromatic triamine having three amine groups are mixed in a molar ratio of 70:30 to 99: 1. The ride is characterized in that the polycondensation.
상기 방향족 언하이드라이드는 2개의 언하이드라이드기를 갖는 방향족 디언하이드라이드 2종이 10:90 내지 50:50의 몰비로 혼합된다. The aromatic anhydride is mixed with two aromatic dianhydrides having two unhydride groups in a molar ratio of 10:90 to 50:50.
상기 방향족 언하이드라이드는 2개의 언하이드라이드기를 갖는 1종 이상의 방향족 디언하이드라이드와 3개의 언하이드라이드기를 갖는 방향족 트리언하이드라이드가 70:30 내지 99:1의 몰비로 혼합된다.The aromatic anhydride is a mixture of at least one aromatic dianhydride having two unhydride groups and an aromatic trianhydride having three unhydride groups in a molar ratio of 70:30 to 99: 1.
상기 방향족 트리아민은 1,3,5-트리아진-2,4,6-트리아민(1,3,5-triazine-2,4,6-triamine), 1,2,4-페닐렌트리아민(1,2,4-phenylenetriamine), 1,3,5-페닐렌트리아민(1,3,5-phenylenetriamine), 4,5,6-트리아미노-2-메틸피리미딘(4,5,6-triamino-2-methylpyrimidine), 2,4,6-트리메틸벤젠-1,3,5-트리아민(2,4,6-trimethylbenzen-1,3,5-triamine), 4H-1,2,4-트리아졸-3,4,5-트리아민(4H-1,2,4-triazole-3,4,5-triamine)으로 이루어진 군에서 선택된 1종 이상이다.The aromatic triamine is 1,3,5-triazine-2,4,6-triamine (1,3,5-triazine-2,4,6-triamine), 1,2,4-phenylenetriamine (1,2,4-phenylenetriamine), 1,3,5-phenylenetriamine, 4,5,6-triamino-2-methylpyrimidine (4,5,6 -triamino-2-methylpyrimidine), 2,4,6-trimethylbenzene-1,3,5-triamine (2,4,6-trimethylbenzen-1,3,5-triamine), 4H-1,2,4 -Triazole-3,4,5-triamine (4H-1,2,4-triazole-3,4,5-triamine) is one or more selected from the group consisting of.
또한, 상기한 다른 목적을 달성하기 위한 본 발명의 폴리아믹산 조성물은 1종 이상의 방향족 디언하이드라이드와 3개의 언하이드라이드기를 갖는 방향족 트리언하이드라이드가 70:30 내지 99:1의 몰비로 혼합된 방향족 디/트리언하이드라이드 화합물 및 방향족 디아민이 축중합된 것을 특징으로 한다.In addition, the polyamic acid composition of the present invention for achieving the above object is a mixture of at least one aromatic dianhydride and an aromatic trianhydride having three unhydride groups in a molar ratio of 70:30 to 99: 1 It is characterized by the polycondensation of an aromatic di / trianhydride compound and an aromatic diamine.
상기 방향족 디아민은 p-페닐렌디아민(p-PDA), 옥시디아닐린(ODA), p-메틸렌디아민(p-MDA), 4,4'-디아미노디페닐설폰(DDS), 비스트리플루오로메틸벤지딘(TFDB), m-페닐렌디아민(mPDA), 사이클로헥산디아민(13CHD, 14CHD), 비스아미노 페녹시페닐프로판(6HMDA), 비스아미노하이드록시페닐헥사플로오로프로판(DBOH), 비스아미노페녹시디페닐술폰(DBSDA), 디아세틸에틸렌디아민(DAED), 테트라아세틸에틸렌디아민(TAED) 및 톨루일렌디아민(TDA)으로 이루어진 군에서 선택된 1종 이상이다.The aromatic diamine is p-phenylenediamine (p-PDA), oxydianiline (ODA), p-methylenediamine (p-MDA), 4,4'-diaminodiphenylsulfone (DDS), bistrifluoro Methylbenzidine (TFDB), m-phenylenediamine (mPDA), cyclohexanediamine (13CHD, 14CHD), bisamino phenoxyphenylpropane (6HMDA), bisaminohydroxyphenylhexafluoropropane (DBOH), bisaminophenoxy It is at least one selected from the group consisting of cidiphenyl sulfone (DBSDA), diacetylethylenediamine (DAED), tetraacetylethylenediamine (TAED) and toluylenediamine (TDA).
상기 디언하이드라이드는 피로멜리트산디언하이드라이드(PMDA)와 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판디언하이드라이드(6FDA), 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트라하이드로나프탈렌-1,2-디카르복실릭디언하이드라이드(TDA), 벤조페논테트라카르복실릭디언하이드라이드(BTDA), 비페닐테트라카르복실릭디언하이드라이드(s-BPDA), 옥시디프탈릭디언하이드라이드(ODPA), 비스카르복시페닐디메틸실란디언하이드라이드(SiDA), 비스디카르복시페녹시디페닐설파이드디언하이드라이드(BDSDA) 및 사이클로부탄테트라카르복실릭디언하이드라이드(CBDA)로 이루어진 군에서 선택된 1종 이상이다.The dianhydride is pyromellitic acid dianhydride (PMDA), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4- (2,5-dioxo Tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dihydride (TDA), benzophenonetetracarboxylic dihydride (BTDA), non Phenyltetracarboxylic dianhydride (s-BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyldimethylsilanedihydride (SiDA), bisdicarboxyphenoxydiphenylsulfidedihydride (BDSDA) And cyclobutanetetracarboxylic dihydride (CBDA).
상기 트리언하이드라이드는 벤젠헥사카르복실릭트리언하이드라이드(benzenehexacarboxylic trianhydride)이다.The trianhydride is benzenehexacarboxylic trianhydride.
상기 방향족 아민과 방향족 언하이드라이드를 용해하는 용매는 N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone), N,N`-디메틸포름아미드(N,N`-dimethylformamide), N,N`-디메틸아세트아미드(N,N`-dimethylacetamide), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc) 및 디메틸설폭사이드(DMSO) 로 이루어진 군에서 선택된 1종 이상이다.The solvent dissolving the aromatic amine and the aromatic anhydride is N-methyl-2-pyrrolidone, N, N`-dimethylformamide, N , N′-dimethylacetamide (N, N′-dimethylacetamide), dimethylformamide (DMF), dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).
상기 방향족 아민과 방향족 언하이드라이드가 1:1의 몰비로 축중합한다.The aromatic amine and the aromatic anhydride are polycondensed in a molar ratio of 1: 1.
상기 폴리아믹산 조성물의 분자량은 90,000 내지 120,000 Mw이며, 점도는 10,000 내지 20,000 Cp이다.The polyamic acid composition has a molecular weight of 90,000 to 120,000 Mw and a viscosity of 10,000 to 20,000 Cp.
또한, 상기한 또 다른 목적을 달성하기 위한 본 발명의 폴리이미드 필름은 상기 폴리아믹산 조성물을 이용하여 제조된다.In addition, the polyimide film of the present invention for achieving another object described above is produced using the polyamic acid composition.
또한, 상기한 또 다른 목적을 달성하기 위한 본 발명의 디스플레이 소자용 기판은 상기 폴리이미드 필름을 보호층 또는 기재층으로 포함한다.
In addition, the substrate for a display element of the present invention for achieving the above-mentioned another object includes the polyimide film as a protective layer or a base layer.
본 발명의 폴리아믹산 조성물은 종래와 같이 높은 분자량과 이에 따른 높은 점도를 갖는 폴리아믹산 조성물이 아니라 방향족 아민 및 방향족 언하이드라이드 중 적어도 한 화합물에 2개의 작용기와 3개의 작용기를 갖는 물질을 혼합하여 사용함으로써 종래와 유사한 높은 분자량을 유지하면서 종래와 달리 낮은 점도를 갖는다.The polyamic acid composition of the present invention is not a polyamic acid composition having a high molecular weight and thus a high viscosity as in the prior art, but a mixture of two functional groups and three functional groups in at least one of aromatic amines and aromatic unhydrides. It has a low viscosity unlike the prior art while maintaining a high molecular weight similar to the conventional.
따라서 지지체에 용이하게 도포되어 우수한 품질의 폴리이미드 필름을 제조할 수 있으며, 열적 안정성이 우수하다.
Therefore, it can be easily applied to the support to produce a polyimide film of excellent quality, it is excellent in thermal stability.
본 발명은 높은 분자량을 유지하면서 낮은 점도를 갖는 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름 및 디스플레이 소자용 기판에 관한 것이다.The present invention relates to a polyamic acid composition having a low viscosity while maintaining a high molecular weight, a polyimide film and a substrate for a display device using the same.
폴리아믹산 조성물은 초기 반응물의 종류 및 조성비에 따라 열적 특성 변화가 크기 때문에 초기 반응물의 종류 및 조성비가 중요하다.Since the polyamic acid composition has a large thermal characteristic change depending on the kind and composition ratio of the initial reactant, the kind and composition ratio of the initial reactant are important.
종래의 폴리아믹산 조성물은 선형 폴리머 형태이며 높은 분자량을 가지므로 점도가 높다. Conventional polyamic acid compositions have a high viscosity since they are in the form of linear polymers and have a high molecular weight.
그러므로 본 발명에서는 폴리아믹산 조성물의 높은 분자량은 유지하면서 점도를 낮추기 위하여 3개의 아민기를 가진 방향족 트리아민 및/또는 방향족 트리언하이드라이드를 첨가하여 선형 폴리머 형태를 비선형 폴리머 형태로 변형시킨다.
Therefore, in the present invention, the linear polymer form is transformed into a nonlinear polymer form by adding aromatic triamine and / or aromatic trianhydride having three amine groups in order to lower the viscosity while maintaining the high molecular weight of the polyamic acid composition.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 폴리아믹산 조성물은 방향족 디아민(A)과 3개의 아민기를 갖는 방향족 트리아민(B)이 혼합된 디/트리아민 화합물 및 방향족 언하이드라이드가 축중합되어 얻어진다.The polyamic acid composition of this invention is obtained by condensation polymerization of the di / triamine compound and aromatic unhydride which the aromatic diamine (A) and the aromatic triamine (B) which have three amine groups mixed.
상기 방향족 디아민(A)과 방향족 트리아민(B)은 70:30 내지 99:1의 몰비, 바람직하게는 85:15 내지 95:5의 몰비로 혼합된다.The aromatic diamine (A) and aromatic triamine (B) are mixed in a molar ratio of 70:30 to 99: 1, preferably in a molar ratio of 85:15 to 95: 5.
상기 혼합된 디/트리아민 화합물의 몰비가 방향족 디아민(A)을 기준으로 하한값 미만일 경우에는 점도는 낮아지지만 열적 안정성이 낮아질 수 있으며, 몰비가 방향족 디아민(A)을 기준으로 상한값 초과인 경우에는 비선형 폴리머 형태로 변형되지 못하여 점도가 높아질 수 있다.If the molar ratio of the mixed di / triamine compound is less than the lower limit on the basis of the aromatic diamine (A), the viscosity is lower, but the thermal stability may be lower, and when the molar ratio is above the upper limit on the basis of the aromatic diamine (A) is nonlinear It can not be transformed into a polymer form and the viscosity can be high.
상기 방향족 디아민(A)은 p-페닐렌디아민(p-PDA), 옥시디아닐린(ODA), p-메틸렌디아민(p-MDA), 4,4'-디아미노디페닐설폰(DDS), 비스트리플루오로메틸 벤지딘(TFDB), m-페닐렌디아민(mPDA), 사이클로헥산디아민(13CHD, 14CHD), 비스아미노 페녹시페닐프로판(6HMDA), 비스아미노하이드록시페닐헥사플로오로프로판(DBOH), 비스아미노페녹시디페닐술폰(DBSDA), 디아세틸에틸렌디아민(DAED), 테트라아세틸에틸렌디아민(TAED) 및 톨루일렌디아민(TDA)으로 이루어진 군에서 선택된 1종 또는 2종 이상이다. The aromatic diamine (A) is p-phenylenediamine (p-PDA), oxydianiline (ODA), p-methylenediamine (p-MDA), 4,4'-diaminodiphenylsulfone (DDS), bis Trifluoromethyl benzidine (TFDB), m-phenylenediamine (mPDA), cyclohexanediamine (13CHD, 14CHD), bisamino phenoxyphenylpropane (6HMDA), bisaminohydroxyphenylhexafluoropropane (DBOH), Bisaminophenoxydiphenylsulfone (DBSDA), diacetylethylenediamine (DAED), tetraacetylethylenediamine (TAED), and toluylenediamine (TDA).
상기 방향족 트리아민(B)은 1,3,5-트리아진-2,4,6-트리아민(1,3,5-triazine-2,4,6-triamine), 1,2,4-페닐렌트리아민(1,2,4-phenylenetriamine), 1,3,5-페닐렌트리아민(1,3,5-phenylenetriamine), 4,5,6-트리아미노-2-메틸피리미딘(4,5,6-triamino-2-methylpyrimidine), 2,4,6-트리메틸벤젠-1,3,5-트리아민(2,4,6-trimethylbenzen-1,3,5-triamine), 4H-1,2,4-트리아졸-3,4,5-트리아민(4H-1,2,4-triazole-3,4,5-triamine)으로 이루어진 군에서 선택된 1종 또는 2종 이상을 들 수 있다.The aromatic triamine (B) is 1,3,5-triazine-2,4,6-triamine (1,3,5-triazine-2,4,6-triamine), 1,2,4-phenyl Rentriamine (1,2,4-phenylenetriamine), 1,3,5-phenylenetriamine, 4,5,6-triamino-2-methylpyrimidine (4, 5,6-triamino-2-methylpyrimidine), 2,4,6-trimethylbenzene-1,3,5-triamine (2,4,6-trimethylbenzen-1,3,5-triamine), 4H-1, 1 type, or 2 or more types selected from the group which consists of 2, 4- triazole-3, 4, 5- triamine (4H-1, 2, 4-triazole-3, 4, 5-triamine) are mentioned.
상기 방향족 언하이드라이드는 2개의 언하이드라이드기를 갖는 방향족 디언하이드라이드 2종이 10:90 내지 50:50의 몰비로 혼합되거나, 1종 이상의 방향족 디언하이드라이드와 3개의 언하이드라이드기를 갖는 방향족 트리언하이드라이드가 70:30 내지 99:1, 바람직하게는 85:15 내지 95:5의 몰비로 혼합될 수 있다. The aromatic anhydride is a mixture of two aromatic dianhydrides having two unhydride groups in a molar ratio of 10:90 to 50:50, or an aromatic trianion having one or more aromatic dionhydrides and three unhydride groups. The hydrides may be mixed in a molar ratio of 70:30 to 99: 1, preferably 85:15 to 95: 5.
상기 방향족 디/트리 언하이드라이드 혼합물을 제조시 디언하이드라이드를 1종 이상, 바람직하게는 2종 이상으로 사용한다. 상기 2종 이상의 디언하이드라이드를 사용할 경우에는 디언하이드라이드들의 조성비를 조절하여 필름의 열적 안정성을 우수하게 할 수 있다. In preparing the aromatic di / tri anhydride mixture, one or more dianhydrides are used, preferably two or more thereof. In the case of using the two or more dianhydrides, it is possible to improve the thermal stability of the film by adjusting the composition ratio of the dianhydrides.
또한, 상기 방향족 디언하이드라이드와 방향족 트리언하이드라이드의 몰비가 디언하이드라이드를 기준으로 하한값 미만인 경우에는 점도는 낮아지지만 열적 안정성이 낮아질 수 있으며, 몰비가 디아민을 기준으로 상한값 초과인 경우에는 비선형 폴리머 형태로 변형되지 못하여 점도가 높아질 수 있다.In addition, when the molar ratio of the aromatic dianhydride and the aromatic trianhydride is less than the lower limit based on the dianhydride, the viscosity may be lowered but thermal stability may be lowered. When the molar ratio is higher than the upper limit based on the diamine, the nonlinear polymer It may not be deformed into a shape and the viscosity may be high.
상기 방향족 디언하이드라이드는 피로멜리트산디언하이드라이드(PMDA)와 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판디언하이드라이드(6FDA), 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트라하이드로나프탈렌-1,2-디카르복실릭디언하이드라이드(TDA), 벤조페논테트라카르복실릭디언하이드라이드(BTDA), 비페닐테트라카르복실릭디언하이드라이드(s-BPDA), 옥시디프탈릭디언하이드라이드(ODPA), 비스카르복시페닐디메틸실란디언하이드라이드(SiDA), 비스디카르복시페녹시 디페닐설파이드디언하이드라이드(BDSDA) 및 사이클로부탄테트라카르복실릭디언하이드라이드(CBDA)로 이루어진 군에서 선택된 1종 또는 2종 이상을 들 수 있다.The aromatic dianhydrides include pyromellitic acid dianhydride (PMDA), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6FDA), and 4- (2,5-di Oxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dihydride (TDA), benzophenonetetracarboxylic dihydride (BTDA), Biphenyltetracarboxylic dianhydride (s-BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyldimethylsilanedihydride (SiDA), bisdicarboxyphenoxy diphenylsulfidedihydride ( BDSDA) and cyclobutane tetracarboxylic hydride (CBDA) can be mentioned 1 type, or 2 or more types.
또한, 상기 방향족 트리언하이드라이드는 벤젠헥사카르복실릭트리언하이드라이드(benzenehexacarboxylic trianhydride)이다. In addition, the aromatic trianhydride is benzenehexacarboxylic trianhydride.
상기 방향족 언하이드라이드에서 2 종의 방향족 디언하이드라이드를 혼합하여 사용하는 경우에는 피로멜리트산디언하이드라이드(PMDA)와 페닐테트라카르복실릭디언하이드라이드(BPDA)를 혼합하여 사용하는 것이 바람직하다. 상기 피로멜리트산디언하이드라이드(PMDA)와 비페닐테트라카르복실릭디언하이드라이드(BPDA)의 몰비가 PMDA를 기준으로 하한값 미만인 경우에는 1% 무게손실이 일어나는 온도(Td, 1%)가 감소하는 경향을 보이며, 취성(brittle)이 높은 폴리이미드 필름이 제조되어 깨지기 쉽고 필름화가 어려울 수 있고, 몰비가 PMDA를 기준으로 상한값 초과인 경우에는 주쇄가 너무 강직하여 필름의 수축현상이 심하게 될 수 있다.When using two kinds of aromatic dihydrides in the aromatic anhydride, it is preferable to use a mixture of pyromellitic acid dihydride (PMDA) and phenyltetracarboxylic dihydride (BPDA). . When the molar ratio of pyromellitic acid dianhydride (PMDA) and biphenyl tetracarboxylic dianhydride (BPDA) is less than the lower limit based on PMDA, the temperature (Td, 1%) at which 1% weight loss occurs is reduced. The polyimide film having a high brittleness may be manufactured to be fragile and difficult to film, and when the molar ratio is higher than the upper limit based on PMDA, the main chain may be too rigid to cause severe shrinkage of the film. .
상기 디/트리아민 화합물 및 방향족 언하이드라이드는 1:1의 몰비로 하여 축합반응시 아미드계 용매하에서 진행된다. 상기 아미드계 용매는 비양성자성 극성 용매로서, 구체적으로 N-메틸-2-피롤리돈(NMP, N-methyl-2-pyrrolidone), N,N`-디메틸포름아미드(N,N`-dimethylformamide), N,N`-디메틸아세트아미드(N,N`-dimethylacetamide) 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc) 및 디메틸설폭사이드(DMSO) 로 이루어진 군에서 선택된 1종 또는 2종 이상을 들 수 있다.The di / triamine compound and the aromatic anhydride proceed in an amide solvent during the condensation reaction in a molar ratio of 1: 1. The amide solvent is an aprotic polar solvent, specifically N-methyl-2-pyrrolidone (NMP, N-methyl-2-pyrrolidone), N, N`-dimethylformamide ), N, N`-dimethylacetamide One or two or more selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO) Can be mentioned.
상기 디/트리아민 화합물 및 방향족 무수물이 1:1의 몰비를 벗어나는 경우에는 축합반응이 진행되지 않는다.When the di / triamine compound and the aromatic anhydride are out of the molar ratio of 1: 1, the condensation reaction does not proceed.
또한, 본 발명의 폴리아믹산 조성물은 방향족 디언하이드라이드(C)와 3개의 언하이드라이드기를 갖는 방향족 트리언하이드라이드(D)가 혼합된 방향족 디/트리언하이드라이드 화합물 및 방향족 디아민이 축중합되어 얻어진다.In addition, the polyamic acid composition of the present invention is the polycondensation of an aromatic di / trianhydride compound and an aromatic diamine in which an aromatic dianhydride (C) and an aromatic trianhydride (D) having three unhydride groups are mixed. Obtained.
상기 방향족 디언하이드라이드(C)와 방향족 트리언하이드라이드(D)는 70:30 내지 99:1, 바람직하게는 85:15 내지 95:5의 몰비로 혼합될 수 있다. The aromatic dianhydride (C) and the aromatic trianhydride (D) may be mixed in a molar ratio of 70:30 to 99: 1, preferably 85:15 to 95: 5.
상기 디/트리언하이드라이드 화합물 및 방향족 디아민은 1:1의 몰비로 하여 축합반응시 아미드계 용매하에서 진행되며, 디/트리언하이드라이드 화합물 및 방향족 디아민이 1:1의 몰비를 벗어나는 경우에는 축합반응이 진행되지 않는다.The di / trianhydride compound and the aromatic diamine are carried out in an amide solvent during the condensation reaction at a molar ratio of 1: 1, and when the di / trianhydride compound and the aromatic diamine are out of the molar ratio of 1: 1, the condensation is carried out. The reaction does not proceed.
축합반응시 반응 조건은 특별히 한정되지 않지만, 바람직하게 반응 온도는 -20 내지 80 ℃, 반응 시간은 30분 내지 48시간이다. 또한, 반응시 아르곤, 질소 등의 불활성 분위기에서 수행하는 것이 바람직하다.Although the reaction conditions at the time of condensation reaction are not specifically limited, Preferably reaction temperature is -20-80 degreeC, and reaction time is 30 minutes-48 hours. In addition, the reaction is preferably carried out in an inert atmosphere such as argon, nitrogen.
폴리아믹산 조성물은 폴리이미드 필름으로 제조시 필리이미드 필름의 접동성(유연성), 열전도성, 도전성, 내코로나성과 같은 여러가지 특성을 개선시킬 목적으로 충전제가 더 포함될 수 있다.The polyamic acid composition may further include a filler for the purpose of improving various properties such as the slidability (flexibility), thermal conductivity, conductivity, corona resistance of the filimimide film when manufactured from a polyimide film.
본 발명의 폴리아믹산 조성물은 지지체 위에 도포되어 40 내지 400 ℃의 온도범위에서 서서히 승온시키면서 1분 내지 10시간 동안 가열하여 폴리이미드 필름을 얻는다. 상기 지지체는 당해 분야에서 일반적으로 사용되는 것을 제한 없이 사용할 수 있으나, 바람직하기로는 유리판, 알루미늄박, 스테인레스 벨트 등을 사용하는 것이다.The polyamic acid composition of the present invention is applied on a support and heated for 1 minute to 10 hours while gradually raising the temperature in the temperature range of 40 to 400 ℃ to obtain a polyimide film. The support may be used without limitation, which is generally used in the art, but preferably, a glass plate, an aluminum foil, a stainless belt, or the like is used.
상기 지지체로부터 분리된 폴리이미드 필름은 분자량이 90,000 내지 120,000 Mw이며, 점도는 10,000 내지 20,000 Cp로서, 높은 분자량을 유지하면서 낮은 점도를 갖는다.The polyimide film separated from the support has a molecular weight of 90,000 to 120,000 Mw, a viscosity of 10,000 to 20,000 Cp, and has a low viscosity while maintaining a high molecular weight.
또한, 본 발명은 상기 폴리이미드 필름을 보호층 또는 기재층으로 포함하는 디스플레이 소자용 기판을 제공할 수 있다.
In addition, the present invention can provide a display device substrate comprising the polyimide film as a protective layer or a base layer.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
실시예 1.Example 1.
반응기로서 교반기, 질소주입장치, 적하 깔때기, 온도조절기 및 냉각기를 부착한 1L 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 500ml을 채운 후, 반응기의 온도를 10℃로 맞춘 후 여기에 방향족 디아민인 파라페닐렌디아민(p-PDA) 30.82g(0.285mol)과 방향족 트리아민인 1,3,5-트리아진-2,4,6-트리아민(TTPT) 1.89g(0.015mol)을 첨가하여 용해 시켰다. 이후 피로멜리트산디언하이드라이드(PMDA) 19.63g(0.09mol) 및 3,3',4,4'-비페닐테트라카르복실릭디언하이드라이드(BPDA) 61.79g(0.21mol)을 첨가하여 3시간 동안 교반하고 상기 방향족 디/트리아민과 방향족 디언하이드라이드가 전체적으로 1:1의 몰비로 축합반응이 진행되도록 하여 폴리아믹산 조성물을 제조하였다.After the reactor was filled with 500 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, the temperature of the reactor was adjusted to 10 ° C. Then, here, aromatic diamine paraphenylenediamine (p-PDA) 30.82 g (0.285 mol) and aromatic triamine 1,3,5-triazine-2,4,6-triamine (TTPT) 1.89 g (0.015) mol) was added to dissolve. After adding 19.63 g (0.09 mol) of pyromellitic acid dianhydride (PMDA) and 61.79 g (0.21 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) The polyamic acid composition was prepared by stirring for a period of time and allowing the aromatic di / triamine and the aromatic dianhydride to undergo a condensation reaction at a molar ratio of 1: 1.
반응이 종료된 후 수득된 폴리아믹산 조성물은 브룩필드 점도계를 이용하여 25℃에서 용액점도를 얻었다.The polyamic acid composition obtained after the reaction was completed to obtain a solution viscosity at 25 ℃ using a Brookfield viscometer.
또한, 폴리아믹산 조성물을 글라스에 도포한 후 40㎛로 캐스팅하고 150℃의 열풍으로 1시간 동안 건조한 후 필름을 글라스 기판에서 박리하여 프레임에 핀으로 고정하였다.In addition, the polyamic acid composition was applied to the glass, cast at 40 μm, dried for 1 hour with hot air at 150 ° C., and then the film was peeled off the glass substrate to be fixed to the frame with a pin.
필름이 고정된 프레임을 진공오븐에 넣고 80부터 400℃까지 8시간 동안 천천히 가열한 후 서서히 냉각해 프레임으로부터 분리하여 폴리이미드 필름을 수득하였으며 폴리이미드 필름의 두께는 20㎛이었다.The film on which the film was fixed was put in a vacuum oven, heated slowly from 80 to 400 ° C. for 8 hours, and then slowly cooled to separate from the frame to obtain a polyimide film. The thickness of the polyimide film was 20 μm.
이때, 파라페닐렌디아민(p-PDA)과 1,3,5-트리아진-2,4,6-트리아민(TTPT)은 95:5의 몰비로 혼합되었으며, 방향족 디언하이드라이드인 피로멜리트산디언하이드라이드(PMDA)와 비페닐테트라카르복실릭디언하이드라이드(BPDA)는 30:70의 몰비로 혼합되었다.
At this time, paraphenylenediamine (p-PDA) and 1,3,5-triazine-2,4,6-triamine (TTPT) were mixed in a molar ratio of 95: 5, and an aromatic dianhydride pyromellitate Sandian hydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) were mixed in a molar ratio of 30:70.
실시예 2.Example 2.
상기 실시예 1과 동일하게 실시하되, 상기 95:5의 몰비로 혼합된 파라페닐렌디아민(p-PDA)과 1,3,5-트리아진-2,4,6-트리아민(melamine) 대신에 파라페닐렌디아민(p-PDA)과 1,2,4-페닐렌트리아민(PTA)을 85:15의 몰비로 하여 폴리아믹산 조성물을 제조하였다.
In the same manner as in Example 1, but instead of paraphenylenediamine (p-PDA) and 1,3,5-triazine-2,4,6-triamine (melamine) mixed in a molar ratio of 95: 5 Polyamic acid composition was prepared using paraphenylenediamine (p-PDA) and 1,2,4-phenylenetriamine (PTA) in a molar ratio of 85:15.
실시예 3.Example 3.
상기 실시예 1과 동일하게 실시하되, 상기 상기 95:5의 몰비로 혼합된 파라페닐렌디아민(p-PDA)과 1,3,5-트리아진-2,4,6-트리아민(TTPT) 대신에 옥시디아닐린(ODA)과 트리아미노-2-메틸피리미딘(TAMP)을 95:5 의 몰비로 하여 폴리아믹산 조성물을 제조하였다.
In the same manner as in Example 1, the paraphenylenediamine (p-PDA) and 1,3,5-triazine-2,4,6-triamine (TTPT) mixed in the molar ratio of 95: 5 Instead oxydianiline (ODA) and triamino-2-methylpyrimidine (TAMP) in a molar ratio of 95: 5 To prepare a polyamic acid composition.
실시예 4.Example 4.
상기 실시예 1과 동일하게 실시하되, 상기 30:70의 몰비로 혼합된 피로멜리트산디언하이드라이드(PMDA)과 비페닐테트라카르복실릭디언하이드라이드(BPDA)를 혼합하는 대신에 피로멜리트산디언하이드라이드(PMDA)와 벤조페논테트라카르복실릭디언하이드라이드(BTDA)를 20:80 의 몰비로 하여 폴리아믹산 조성물을 제조하였다.
The same process as in Example 1, but instead of mixing pyromellitic acid hydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) mixed in a molar ratio of 30:70, pyromellitic Sandian hydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA) in a molar ratio of 20:80 To prepare a polyamic acid composition.
실시예 5.Example 5.
상기 실시예 1과 동일하게 실시하되, 상기 피로멜리트산디언하이드라이드(PMDA)과 비페닐테트라카르복실릭디언하이드라이드(BPDA) 대신에 피로멜리트산디언하이드라이드(PMDA) 및 비페닐테트라카르복실릭디언하이드라이드(BPDA)와 벤젠헥사카르복실릭트리언하이드라이드(BHTA)를 95:5의 몰비(디언하이드라이드와 트리언하이드라이드의 몰비)로 혼합하여 폴리아믹산 조성물을 제조하였다. 이때 PMDA와 BPDA의 몰비는 30:70이다.
The same procedure as in Example 1, except that pyromellitic acid hydride (PMDA) and biphenyl tetracarboxylic hydride (BPDA) are substituted with pyromellitic acid hydride (PMDA) and biphenyl tetra Carboxylician hydride (BPDA) and benzenehexacarboxylic trianhydride (BHTA) were mixed in a molar ratio of 95: 5 (molar ratio of dione hydride and trianhydride) to prepare a polyamic acid composition. At this time, the molar ratio of PMDA and BPDA is 30:70.
실시예 6.Example 6.
반응기로서 교반기, 질소주입장치, 적하 깔때기, 온도조절기 및 냉각기를 부착한 1L 반응기에 질소를 통과시키면서 N-메틸-2-피롤리돈(NMP) 500ml을 채운 후, 반응기의 온도를 10℃로 맞춘 후 여기에 방향족 디아민인 파라페닐렌디아민(p-PDA) 32.44g(0.3mol)을 첨가하여 용해시켰다. 이후 피로멜리트산디언하이드라이드(PMDA) 18.54g(0.085mol), 3,3',4,4'-비페닐테트라카르복실릭디언하이드라이드(BPDA) 58.84g(0.2mol) 및 벤젠헥사카르복실릭트리언하이드라이드 4.46g(0.015mol)을 첨가하여 3시간 동안 교반하고 상기 방향족 디아민과 방향족 디/트리언하이드라이드가 전체적으로 1:1의 몰비로 축합반응이 진행되도록 하여 폴리아믹산 조성물을 제조하였다.After the reactor was filled with 500 ml of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, the temperature of the reactor was adjusted to 10 ° C. Thereafter, 32.44 g (0.3 mol) of paraphenylenediamine (p-PDA) which is an aromatic diamine was added thereto and dissolved. Pyromellitic acid hydride (PMDA) 18.54 g (0.085 mol), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) 58.84 g (0.2 mol) and benzenehexacar 4.46 g (0.015 mol) of cyclic trianhydride was added thereto, stirred for 3 hours, and the polyamic acid composition was prepared by allowing the aromatic diamine and the aromatic di / trianhydride to undergo a condensation reaction at a total molar ratio of 1: 1. It was.
반응이 종료된 후 수득된 폴리아믹산 조성물은 브룩필드 점도계를 이용하여 25℃에서 용액점도를 얻었다.The polyamic acid composition obtained after the reaction was completed to obtain a solution viscosity at 25 ℃ using a Brookfield viscometer.
또한, 폴리아믹산 조성물을 글라스에 도포한 후 40㎛로 캐스팅하고 150℃의 열풍으로 1시간 동안 건조한 후 필름을 글라스 기판에서 박리하여 프레임에 핀으로 고정하였다.In addition, the polyamic acid composition was applied to the glass, cast at 40 μm, dried for 1 hour with hot air at 150 ° C., and then the film was peeled off the glass substrate to be fixed to the frame with a pin.
필름이 고정된 프레임을 진공오븐에 넣고 80부터 400℃까지 8시간 동안 천천히 가열한 후 서서히 냉각해 프레임으로부터 분리하여 폴리이미드 필름을 수득하였으며 폴리이미드 필름의 두께는 20㎛이었다.The film on which the film was fixed was put in a vacuum oven, heated slowly from 80 to 400 ° C. for 8 hours, and then slowly cooled to separate from the frame to obtain a polyimide film. The thickness of the polyimide film was 20 μm.
이때, 피로멜리트산디언하이드라이드(PMDA) 및 3,3',4,4'-비페닐테트라카르복실릭디언하이드라이드(BPDA)와 벤젠헥사카르복실릭트리언하이드라이드는 95:5의 몰비(디언하이드라이드와 트리언하이드라이드의 몰비)로 혼합되었다.
In this case, pyromellitic acid hydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and benzenehexacarboxylic trianhydride are 95: 5 It was mixed in a molar ratio (molar ratio of dianhydride and trianhydride).
비교예 1.Comparative Example 1
상기 실시예 1과 동일하게 실시하되, 상기 파라페닐렌디아민(p-PDA) 과 1,3,5-트리아진-2,4,6-트리아민(melamine)을 혼합하여 사용하는 대신에 1,3,5-트리아진-2,4,6-트리아민을 사용하지 않고 파라페닐렌디아민(p-PDA)만을 단독으로 사용하여 폴리아믹산 조성물을 제조하였다.
The same procedure as in Example 1, except that 1,3,5-triazine-2,4,6-triamine (melamine) is mixed with the paraphenylenediamine (p-PDA) 1, A polyamic acid composition was prepared using only paraphenylenediamine (p-PDA) alone without using 3,5-triazine-2,4,6-triamine.
비교예 2.Comparative Example 2
상기 실시예 1과 동일하게 실시하되, 상기 파라페닐렌디아민(p-PDA)과 1,3,5-트리아진-2,4,6-트리아민(TTPT)을 95:5의 몰비 대신에 30:70의 몰비로 하여 폴리아믹산 조성물을 제조하였다.
The same procedure as in Example 1, except that paraphenylenediamine (p-PDA) and 1,3,5-triazine-2,4,6-triamine (TTPT) were substituted in a molar ratio of 95: 5. A polyamic acid composition was prepared in a molar ratio of 70.
비교예 3.Comparative Example 3
상기 실시예 1과 동일하게 실시하되, 상기 피로멜리트산디언하이드라이드(PMDA)과 비페닐테트라카르복실릭디언하이드라이드(BPDA)을 30:70의 몰비 대신에 70:30의 몰비로 하여 폴리아믹산 조성물을 제조하였다.
The same process as in Example 1, except that the pyromellitic acid hydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) were used in a molar ratio of 70:30 instead of 30:70. The mixed acid composition was prepared.
비교예 4.Comparative Example 4
상기 실시예 6과 동일하게 실시하되, 상기 피로멜리트산디언하이드라이드(PMDA) 및 3,3',4,4'-비페닐테트라카르복실릭디언하이드라이드(BPDA)와 벤젠헥사카르복실릭트리언하이드라이드(BHTA)를 70:30의 몰비로 혼합하는 대신에 30:70으로 하여 폴리아믹산 조성물을 제조하였다.
In the same manner as in Example 6, the pyromellitic acid hydride (PMDA) and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and benzenehexacarboxylic Instead of mixing trianhydride (BHTA) in a molar ratio of 70:30, a polyamic acid composition was prepared at 30:70.
상기 실시예 및 비교예의 조성비를 하기 표 1에 나타내었다.
The composition ratios of the Examples and Comparative Examples are shown in Table 1 below.
시험예.Test example.
1. 중량변화 측정: 상기 실시예 및 비교예에서 제조된 폴리이미드 필름에 대하여 전체 중량의 1%가 감소하기 시작하는 온도를 열중량측정분석장치(Thermogravimetric analysis, TGA)를 이용하여 측정하였다.1. Measurement of weight change: The temperature at which 1% of the total weight starts to decrease with respect to the polyimide films prepared in Examples and Comparative Examples was measured using a thermogravimetric analysis (TGA).
2. 용액점도 측정: 상기 실시예 및 비교예에서 제조된 폴리아믹산 조성물에 대하여 점도측정장치(Brookfield viscometer)를 이용하여 측정하였다. 2. Solution Viscosity Measurement: The polyamic acid composition prepared in Examples and Comparative Examples was measured by using a viscometer (Brookfield viscometer).
위 표 2에 나타낸 바와 같이, 본 발명에 따라 제조된 실시예 1 내지 6의 폴리아믹산 조성물은 비교예 1 및 3과 유사한 분자량을 유지하면서 점도는 낮은 것으로 확인되었다.As shown in Table 2, the polyamic acid composition of Examples 1 to 6 prepared according to the present invention was confirmed to have a low viscosity while maintaining a molecular weight similar to Comparative Examples 1 and 3.
반면, 비교예 2 및 4는 점도가 낮지만 분자량 및 TGA 온도 역시 낮은 것으로 확인되었다.On the other hand, Comparative Examples 2 and 4 were found to have low viscosity but also low molecular weight and TGA temperature.
특히, 디/트리 아민 혼합물과 디/트리언하이드라이드 혼합물을 사용한 실시예 5가 높은 분자량을 유지하면서 다른 실시예 보다 더 낮은 점도를 갖는 것으로 확인되었다. In particular, it was found that Example 5, using di / tri amine mixtures and di / trianhydride mixtures, has a lower viscosity than other examples while maintaining high molecular weight.
실시예 1 내지 6은 높은 분자량을 유지하므로 열적 안정성도 우수한 것으로 확인되었다.
Examples 1 to 6 were found to be excellent thermal stability because of maintaining a high molecular weight.
Claims (13)
A polyamic acid composition characterized by polycondensation of an aromatic diamine and an aromatic anhydride in which an aromatic diamine and an aromatic triamine having three amine groups are mixed in a molar ratio of 70:30 to 99: 1.
The polyamic acid composition according to claim 1, wherein the aromatic anhydride is mixed with two aromatic dianhydrides having two unhydride groups in a molar ratio of 10:90 to 50:50.
The method of claim 1, wherein the aromatic unhydride has at least one aromatic dianhydride having two unhydride groups and an aromatic trianhydride having three unhydride groups in a molar ratio of 70:30 to 99: 1. A polyamic acid composition, characterized in that mixed.
The method of claim 1, wherein the aromatic triamine is 1,3,5-triazine-2,4,6-triamine (1,3,5-triazine-2,4,6-triamine), 1,2, 4-phenylenetriamine (1,2,4-phenylenetriamine), 1,3,5-phenylenetriamine (1,3,5-phenylenetriamine), 4,5,6-triamino-2-methylpyrimidine (4,5,6-triamino-2-methylpyrimidine), 2,4,6-trimethylbenzene-1,3,5-triamine (2,4,6-trimethylbenzen-1,3,5-triamine), 4H Polya, characterized in that at least one selected from the group consisting of -1,2,4-triazole-3,4,5-triamine (4H-1,2,4-triazole-3,4,5-triamine) Mixed acid composition.
Aromatic di / trianhydride compound and aromatic diamine in which at least one aromatic dianhydride and an aromatic trianhydride having three unhydride groups are mixed in a molar ratio of 70:30 to 99: 1 are characterized in that they are polycondensed. Polyamic acid composition to be.
The method of claim 1, wherein the aromatic diamine is p-phenylenediamine (p-PDA), oxydianiline (ODA), p-methylenediamine (p-MDA), 4,4'-diaminodi Phenylsulfone (DDS), bis trifluoromethylbenzidine (TFDB), m-phenylenediamine (mPDA), cyclohexanediamine (13CHD, 14CHD), bisaminophenoxyphenylpropane (6HMDA), bisaminohydroxyphenylhexa At least one selected from the group consisting of fluoropropane (DBOH), bisaminophenoxydiphenylsulfone (DBSDA), diacetylethylenediamine (DAED), tetraacetylethylenediamine (TAED) and toluylenediamine (TDA) Polyamic acid composition.
6. The dianhydride of claim 2, wherein the dianhydride is pyromellitic acid dianhydride (PMDA) and 2,2-bis (3,4-dicarboxyphenyl) hexafluoro. 7. Lorophandian hydride (6FDA), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dihydride (TDA), benzophenonetetracarboxylic dianhydride (BTDA), biphenyltetracarboxylic dianhydride (s-BPDA), oxydiphthalic dianhydride (ODPA), biscarboxyphenyldimethylsilanedihydride A polyamic acid composition, characterized in that it is at least one selected from the group consisting of a hydride (SiDA), bisdicarboxyphenoxy diphenylsulfidedian hydride (BDSDA) and cyclobutane tetracarboxylic dianhydride (CBDA).
The polyamic acid composition according to claim 3 or 5, wherein the trianhydride is benzenehexacarboxylic trianhydride.
The solvent according to claim 1 or 5, wherein the solvent for dissolving the aromatic amine and the aromatic anhydride is N-methyl-2-pyrrolidone, N, N`-dimethylformamide. (N, N`-dimethylformamide), N, N`-dimethylacetamide (N, N`-dimethylacetamide), dimethylformamide (DMF), dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO) Polyamic acid composition, characterized in that at least one selected.
The polyamic acid composition according to claim 1 or 5, wherein the aromatic amine and the aromatic anhydride are polycondensed in a molar ratio of 1: 1.
The polyamic acid composition according to claim 1 or 5, wherein the polyamic acid composition has a molecular weight of 90,000 to 120,000 Mw and a viscosity of 10,000 to 20,000 Cp.
A polyimide film prepared using the polyamic acid composition of claim 1.
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WO2018074738A1 (en) * | 2016-10-21 | 2018-04-26 | 한국전기연구원 | Imide-based polymer colloidal dispersion for electrodeposition coating and method for producing same |
KR101988809B1 (en) * | 2018-11-19 | 2019-06-12 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid Composition for Packaging Electronic Component and Method for Packaging Electronic Component by Using the Same |
WO2020106002A1 (en) * | 2018-11-19 | 2020-05-28 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid composition for packaging electronic components, and method for packaging electronic components by using same |
KR20230089991A (en) | 2021-12-14 | 2023-06-21 | 단국대학교 산학협력단 | Manufacturing method for making flexible polyimide film, the film and display substrate comprising the film |
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KR20210116067A (en) * | 2020-03-17 | 2021-09-27 | 주식회사 두산 | Polyimide film having excellent moisture resistance and low water absorption |
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US4058505A (en) * | 1973-05-25 | 1977-11-15 | University Of Notre Dame Du Lac | Chain-extending amine end-capped polyimides |
US5270438A (en) * | 1990-04-03 | 1993-12-14 | Hitachi Chemical Company, Ltd. | Fluorine-containing polyimides and precursors thereof |
KR100568569B1 (en) * | 2004-10-26 | 2006-04-07 | 주식회사 이녹스 | Composition for polyimide adhesive and adhesive tape using the same |
EP2128193B1 (en) * | 2007-03-19 | 2013-06-19 | Ibiden Co., Ltd. | Porous polyimide |
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WO2018074738A1 (en) * | 2016-10-21 | 2018-04-26 | 한국전기연구원 | Imide-based polymer colloidal dispersion for electrodeposition coating and method for producing same |
KR101988809B1 (en) * | 2018-11-19 | 2019-06-12 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid Composition for Packaging Electronic Component and Method for Packaging Electronic Component by Using the Same |
WO2020105893A1 (en) * | 2018-11-19 | 2020-05-28 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid composition for packaging electronic components, and method for packaging electronic components using same |
WO2020106002A1 (en) * | 2018-11-19 | 2020-05-28 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid composition for packaging electronic components, and method for packaging electronic components by using same |
KR20230089991A (en) | 2021-12-14 | 2023-06-21 | 단국대학교 산학협력단 | Manufacturing method for making flexible polyimide film, the film and display substrate comprising the film |
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