KR102531268B1 - Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same - Google Patents
Polyimideprecursor, method for producing thereof and method for producing polyimide film using the sameDownload PDFInfo
- Publication number
- KR102531268B1 KR102531268B1KR1020150190977AKR20150190977AKR102531268B1KR 102531268 B1KR102531268 B1KR 102531268B1KR 1020150190977 AKR1020150190977 AKR 1020150190977AKR 20150190977 AKR20150190977 AKR 20150190977AKR 102531268 B1KR102531268 B1KR 102531268B1
- Authority
- KR
- South Korea
- Prior art keywords
- bis
- crosslinking agent
- polyimide precursor
- anhydride
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- 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
- C08G73/1003—Preparatory processes
- 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
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
- 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
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Translated fromKoreanDescription
Translated fromKorean본 발명은 폴리이미드 전구체를 포함하는 폴리이미드 필름 제조용 조성물, 이의 제조 방법 및 이를 이용한 폴리이미드 필름의 제조 방법에 관한 것이다.The present invention relates to a composition for preparing a polyimide film containing a polyimide precursor, a method for preparing the same, and a method for manufacturing a polyimide film using the same.
폴리이미드 소재는 내열특성 및 내화학성이 우수하여 유연한 디스플레이의 기판 용도로 적용 가능성이 높은 소재이다.Polyimide material has excellent heat resistance and chemical resistance, so it is highly applicable as a substrate for flexible displays.
폴리이미드 기판 소재는 일반적으로 캐리어 글라스(carrier glass)에 폴리아믹산(polyamic acid; PAA)을 어플리케이터(applicator) 또는 슬릿코터를 이용하여 코팅한 후에 고온의 열적 이미드 반응을 통해 시트 타입으로 제작한다. 그러나, 연속 공정이 아닌 배치 타입(batch type)의 공정으로 컨벤션 오븐에서 큐어링 공정(즉, 열적 이미드화 공정)을 진행할 수 있는 생산량은 한정되어 있고, 400℃ 이상의 고온 공정으로 인해 오랜 공정 시간이 요구된다.A polyimide substrate material is generally manufactured in a sheet type through a high-temperature thermal imide reaction after coating polyamic acid (PAA) on a carrier glass using an applicator or a slit coater. However, as a batch type process rather than a continuous process, the amount of production that can be used for the curing process (i.e., thermal imidization process) in a convention oven is limited, and a long process time is required due to the high temperature process of 400°C or higher. It is required.
컨벤션 오븐에서의 큐어링 공정에 의해 좌우되는 생산 CAPA(capacity)는, 빠른 공정 속도를 위해서 오븐이 완전히 냉각되지 않은 120℃ 이상의 고온에서 코팅된 기판을 넣어 열적 이미드화를 진행시킨다. 이 때, 용매의 급속한 휘발로 인해 필름 표면의 레벨링(leveling) 특성이 감소된다. 이에 따라, 가교제를 사용하여 이러한 문제점을 개선하고자 하는 많은 연구가 이루어지고 있다(대한민국 등록 특허 제 10-0889910호).Production CAPA (capacity), which is influenced by the curing process in a convention oven, proceeds with thermal imidization by putting a coated substrate at a high temperature of 120 ° C. or higher in an oven that is not completely cooled for a fast process speed. At this time, the leveling property of the film surface is reduced due to the rapid volatilization of the solvent. Accordingly, many studies have been conducted to improve these problems by using a crosslinking agent (Korean Registered Patent No. 10-0889910).
본 발명은 상기 종래기술에 따른 문제점들을 해결하기 위해, 특정 함량의 가교제를 포함하는 폴리이미드 전구체를 사용하여 고온에서의 이미드화에도 폴리이미드 필름 표면의 특성을 개선시킴으로써, 본 발명을 완성하였다.In order to solve the problems of the prior art, the present invention was completed by using a polyimide precursor containing a specific content of a crosslinking agent to improve the surface properties of a polyimide film even after imidization at a high temperature.
본 발명의 일 측면은, 디아민 단량체를 함유하는 중합 용매에 안하이드라이드(anhydride) 단량체를 첨가하여 반응시키는 단계; 상기 반응 용액에 말단-캡핑 제제를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계; 및 상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계를 포함하는, 폴리이미드 전구체의 제조 방법을 제공한다.One aspect of the present invention, the reaction by adding an anhydride (anhydride) monomer to a polymerization solvent containing a diamine monomer; adding an end-capping agent to the reaction solution and reacting to synthesize polyamic acid; And it provides a method for preparing a polyimide precursor, including adding and mixing a crosslinking agent to the polyamic acid.
본 발명의 또 다른 측면은, 디아민 단량체를 함유하는 중합 용매에 안하이드라이드 단량체를 첨가하여 반응시키는 단계; 상기 반응 용액에 말단-캡핑 제제를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계; 상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계; 상기 가교제가 첨가된 폴리아믹산을 포함하는 조성물을 지지체 상에 코팅하는 단계; 및 100℃ 이상의 온도에서 상기 지지체 상에 코팅된 폴리이미드 전구체를 열적 이미드화하는 단계를 포함하는, 폴리이미드 필름의 제조 방법을 제공한다.Another aspect of the present invention is the reaction by adding an anhydride monomer to a polymerization solvent containing a diamine monomer; adding an end-capping agent to the reaction solution and reacting to synthesize polyamic acid; Adding and mixing a crosslinking agent to the polyamic acid; coating a composition containing the polyamic acid to which the crosslinking agent is added on a support; and thermally imidizing the polyimide precursor coated on the support at a temperature of 100° C. or higher.
본 발명에 따른 폴리이미드 전구체는 특정 함량의 가교제를 폴리아믹산에 추가하여 형성된 것으로, 고온의 이미드화에도 폴리이미드 필름의 표면 특성을 개선시킬 수 있다. 특히, 폴리이미드 필름의 표면의 레벨링 특성을 개선시키고 투과도 손실을 감소시킬 수 있다.The polyimide precursor according to the present invention is formed by adding a specific content of a crosslinking agent to polyamic acid, and can improve the surface properties of the polyimide film even during high-temperature imidation. In particular, it is possible to improve the leveling property of the surface of the polyimide film and reduce the transmittance loss.
도 1은, 본 발명의 일 실시예에 따른 폴리이미드 필름의 이미지이다.
도 2는, 본 발명의 일 실시예에 따른 폴리이미드 필름의 이미지이다.
도 3은, 본 발명의 일 실시예에 따른 폴리이미드 필름의 이미지이다.
도 4는, 본 발명에 비교예에 따른 폴리이미드 필름의 이미지이다.
도 5는, 본 발명에 비교예에 따른 폴리이미드 필름의 이미지이다.
도 6은, 본 발명에 비교예에 따른 폴리이미드 필름의 이미지이다.
도 7은, 본 발명에 비교예에 따른 폴리이미드 필름의 이미지이다.1 is an image of a polyimide film according to an embodiment of the present invention.
2 is an image of a polyimide film according to an embodiment of the present invention.
3 is an image of a polyimide film according to an embodiment of the present invention.
4 is an image of a polyimide film according to a comparative example of the present invention.
5 is an image of a polyimide film according to a comparative example of the present invention.
6 is an image of a polyimide film according to a comparative example of the present invention.
7 is an image of a polyimide film according to a comparative example of the present invention.
이하, 첨부한 도면을 참조하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 구현예 및 실시예를 상세히 설명한다.Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily practice the present invention.
그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 구현예 및 실시예에 한정되지 않는다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.However, the present invention may be embodied in many different forms and is not limited to the embodiments and examples set forth herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.
본 발명의 일 측면은, 디아민 단량체를 함유하는 중합 용매에 안하이드라이드 단량체를 첨가하여 반응시키는 단계; 상기 반응 용액에 말단-캡핑 제제(end capping agent)를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계; 및 상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계를 포함하는, 폴리이미드 전구체의 제조 방법을 제공한다.One aspect of the present invention, the reaction by adding an anhydride monomer to a polymerization solvent containing a diamine monomer; synthesizing a polyamic acid by adding an end capping agent to the reaction solution and then reacting; And it provides a method for preparing a polyimide precursor, including adding and mixing a crosslinking agent to the polyamic acid.
본 발명의 일 구현예에 있어서, 상기 디아민 단량체는PPDA(p-phenylenediamine), ODA(4,4'-oxydianiline), MDA(4,4'-methylenedianiline), m-톨리딘(2,2'-dimethyl-4,4'-diaminobiphenyl), TPE-R(1,3-bis(4'-aminophenoxyl)benzene), TFMB(2,2'-bis(trifluoromethyl) benzidine), HFBAPP(2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), Bis-AP-AF(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB(1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS(3,3'-diaminodiphenyl sulfone), ASD(4,4'-diaminodiphenyl sulfide), BAPS(bis[4-(4-aminophenoxy)phenyl]sulfone), m-BAPS(2,2-bis[4-(3-aminophenoxy)benzene] sulfone) 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 포함할 수 있으며, 바람직하게는 PPDA일 수 있다. 상기 PPDA는 방향족 구조의 단량체로서 높은 내열 특성을 제공할 수 있다.In one embodiment of the present invention, the diamine monomer is PPDA (p-phenylenediamine), ODA (4,4'-oxydianiline), MDA (4,4'-methylenedianiline), m-tolidine (2,2'- dimethyl-4,4'-diaminobiphenyl), TPE-R (1,3-bis (4'-aminophenoxyl) benzene), TFMB (2,2'-bis (trifluoromethyl) benzidine), HFBAPP (2,2-bis[ 4-(4-aminophenoxy)phenyl]hexafluoropropane), Bis-AP-AF(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB(1,3-diamino-2,4,5,6 -tetrafluorobenzene), DDS (3,3'-diaminodiphenyl sulfone), ASD (4,4'-diaminodiphenyl sulfide), BAPS (bis[4-(4-aminophenoxy)phenyl]sulfone), m-BAPS(2,2- It may include one selected from the group consisting of bis[4-(3-aminophenoxy)benzene] sulfone) and combinations thereof, and may preferably be PPDA. The PPDA is an aromatic monomer and can provide high heat resistance.
본 발명의 일 구현예에 있어서, 상기 안하이드라이드 단량체는 방향족 디안하이드라이드 단량체일 수 있으며, 예를 들어, BTDA(3,3',4,4'-benzophenonetetracarboxylicdianhydride), PMDA(pyromellitic dianhydride), BPDA(3,3',4,4'-biphenyl tetracarboxylicacid dianhydride), 6FDA(2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride), a-BPDA(2,3,3',4-biphenyl tetracarboxylicacid dianhydride), ODPA(4,4'-oxydiphthalic anhydride), DSDA(3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA(2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride), HQDA(hydroquinone diphthalic anhydride) 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 포함할 수 있다.상기 방향족 디안하이드라이드 단량체는 하나 이상, 예를 들어 적어도 두 개의 단량체를 사용할 수 있다.In one embodiment of the present invention, the anhydride monomer may be an aromatic dianhydride monomer, for example, BTDA (3,3', 4,4'-benzophenonetetracarboxylic dianhydride), PMDA (pyromellitic dianhydride), BPDA (3,3',4,4'-biphenyl tetracarboxylicacid dianhydride), 6FDA(2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride), a-BPDA(2,3,3',4-biphenyl tetracarboxylicacid dianhydride), ODPA (4,4'-oxydiphthalic anhydride), DSDA (3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl ] propane dianhydride), hydroquinone diphthalic anhydride (HQDA), and combinations thereof. One or more aromatic dianhydride monomers, for example, at least two monomers, may be used.
본 발명의 일 구현예에 있어서, 상기 중합 용매는 본 분야에서 사용되는 용매라면 제한 없이 사용될 수 있으며, 예를 들어, 아미드계 용매, 케톤계 용매, 에테르계 용매, 에스테르계 용매, 대칭 글리콜디에테르류 용매, 에테르류 용매 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 포함할 수 있다. 상기 아미드계 용매는 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAC), n-메틸피롤리돈(NMP) 등을 포함할 수 있으며, 상기 케톤계 용매는 아세톤, 메틸에틸케톤(MEK), 메틸이소부틸케톤(MIBK), 시클로펜탄온, 시클로헥산온 등을 포함할 수 있다. 상기 에테르계 용매는 테트라히드로퓨란(THF), 1,3-디옥솔란및 1,4-디옥산등을 포함할 수 있으며, 상기 에스테르계 용매는 아세트산메틸, 아세트산에틸, 아세트산부틸, γ-부티로락톤, α-아세트락톤, β-프로피오락톤, δ-발레로락톤등을 포함할 수 있다. 상기 대칭 글리콜디에테르류 용매는 메틸모노글라임(1,2-디메톡시에탄), 메틸디글라임(비스(2-메톡시에틸)에테르), 메틸트리글라임(1,2-비스(2-메톡시에톡시)에탄), 메틸테트라글라임(비스[2-(2-메톡시에톡시에틸)]에테르), 에틸모노글라임(1,2-디에톡시에탄),에틸디글라임(비스(2-에톡시에틸)에테르), 부틸디글라임(비스(2-부톡시에틸)에테르) 등을 포함할 수 있으며, 상기 에테르류 용매는 글리콜디에테르류, 디프로필렌글리콜메틸에테르, 트리프로필렌글리콜메틸에테르, 프로필렌글리콜n-프로필에테르, 디프로필렌글리콜n-프로필에테르, 프로필렌글리콜n-부틸에테르, 디프로필렌글리콜n-부틸에테르, 트리피렌글리콜n-프로필에테르, 프로필렌글리콜페닐에테르, 디프로필렌글리콜디메틸에테르, 1,3-디옥솔란, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노에틸에테르등을 포함할 수 있다. 상기 중합 용매는 적어도 1 개 이상의 용매가 사용되는 것이 바람직하며, 예를 들어, NMP를 사용할 수 있다.In one embodiment of the present invention, the polymerization solvent may be used without limitation as long as it is a solvent used in the field, for example, amide solvent, ketone solvent, ether solvent, ester solvent, symmetrical glycol diether solvents, ether solvents, and combinations thereof. The amide-based solvent may include dimethylformamide (DMF), dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), and the like, and the ketone-based solvent may include acetone, methyl ethyl ketone (MEK), methyl It may include isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, and the like. The ether-based solvent may include tetrahydrofuran (THF), 1,3-dioxolane and 1,4-dioxane, and the ester-based solvent may include methyl acetate, ethyl acetate, butyl acetate, γ-butyro Lactone, α-acetlactone, β-propiolactone, δ-valerolactone and the like may be included. The symmetric glycol diether solvents are methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2- methoxyethoxy) ethane), methyl tetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis ( 2-ethoxyethyl) ether), butyl diglyme (bis (2-butoxyethyl) ether), and the like, and the ether solvents are glycol diethers, dipropylene glycol methyl ether, tripropylene glycol methyl Ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tryrene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether , 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and the like. Preferably, at least one solvent is used as the polymerization solvent, and for example, NMP may be used.
본 발명의 일 구현예에 있어서, 상기 말단-캡핑 제제는 중합 반응을 조절하기 위해 사용되는 것으로서, 안하이드라이드 형태의 단량체를 사용할 수 있다. 상기 안하이드라이드 형태의 단량체는 예를 들어, PA(phthallic anhydride), TSA(tetradecyl succinic anhydride),HAS(hexadecyl succinic anhydride), OSA(octadecyl succinic anhydride) 및 이들의 조합들로 이루어진 군으로부터 선택된 것일 수 있으며, 바람직하게는 PA일 수 있다. 상기 말단-캡핑 제제는 모노-안하이드라이드 형태로 고분자의 분자량을 조절하고, 미반응물의 함량을 감소시키며, 보관 안정성을 향상시킬 수 있다.In one embodiment of the present invention, the end-capping agent is used to control the polymerization reaction, and an anhydride type monomer may be used. The anhydride-type monomer may be, for example, selected from the group consisting of phthalic anhydride (PA), tetradecyl succinic anhydride (TSA), hexadecyl succinic anhydride (HAS), octadecyl succinic anhydride (OSA), and combinations thereof. And, preferably, it may be PA. The end-capping agent may control the molecular weight of the polymer in the form of a mono-anhydride, reduce the content of unreacted substances, and improve storage stability.
본 발명의 일 구현예에 있어서, 상기 폴리아믹산을 합성한 후 제조하고자 하는 제품 기준에 맞는 고형분과 점도 조절을 위해 용매를 첨가하는 단계를 추가 포함할 수 있다. 상기 용매는 상기 합성 용매와 동일한 용매를 사용할 수 있으며, 물성 개선을 위해 다른 종류의 용매를 사용할 수도 있다.In one embodiment of the present invention, after synthesizing the polyamic acid, a step of adding a solvent may be further included to adjust the solid content and viscosity that meet the standards for a product to be manufactured. The same solvent as the synthetic solvent may be used, and other types of solvents may be used to improve physical properties.
본 발명의 일 구현예에 있어서, 상기 가교제는4,4’-메틸렌비스(N,N-디글리시딜아닐린)을 포함할 수 있다. 상기 가교제는 바람직하게는 하기 화학식을 갖는 4,4’-메틸렌비스(N,N-디글리시딜아닐린)일 수 있다:In one embodiment of the present invention, the crosslinking agent may include 4,4'-methylenebis(N,N-diglycidylaniline). The crosslinking agent may preferably be 4,4'-methylenebis(N,N-diglycidylaniline) having the formula:
본 발명의 일 구현예에 있어서, 상기 가교제는 단량체 대비 약 2000 내지 약 4000 ppm의 양으로 첨가될 수 있다. 상기 가교제가 2000 ppm 미만의 함량으로 첨가될 경우, 폴리이미드 필름의 표면이 불량해질 수 있으며, 4000 ppm 초과의 함량으로 첨가될 경우, 폴리이미드 필름의 투과도가 낮아질 수 있다.In one embodiment of the present invention, the crosslinking agent may be added in an amount of about 2000 to about 4000 ppm compared to the monomers. When the crosslinking agent is added in an amount of less than 2000 ppm, the surface of the polyimide film may deteriorate, and if it is added in an amount greater than 4000 ppm, the transmittance of the polyimide film may decrease.
본 발명의 다른 측면은 본원에 따른 폴리이미드 전구체의 제조 방법에 의해 제조된 폴리이미드 전구체를 포함하는 폴리이미드 필름 제조용 조성물을 제공한다.Another aspect of the present invention provides a composition for producing a polyimide film comprising a polyimide precursor prepared by the method for producing a polyimide precursor according to the present application.
본 발명의 일 구현예에 있어서, 상기 폴리이미드 전구체는 폴리아믹산 중합체 형태를 포함할 수 있다.In one embodiment of the present invention, the polyimide precursor may include a polyamic acid polymer form.
본 발명의 일 구현예에 있어서, 상기 폴리이미드 전구체는 특정 함량의 가교제를 폴리아믹산에 추가하여 형성된 것으로, 고온의 이미드화에도 폴리이미드 필름의 표면 특성을 개선시킬 수 있다. 특히, 폴리이미드 필름의 표면의 레벨링 특성을 개선시키고 투과도 손실을 감소시킬 수 있다.In one embodiment of the present invention, the polyimide precursor is formed by adding a crosslinking agent of a specific content to polyamic acid, and can improve the surface properties of the polyimide film even during high-temperature imidation. In particular, it is possible to improve the leveling property of the surface of the polyimide film and reduce the transmittance loss.
본 발명의 또 다른 측면은, 디아민 단량체를 함유하는 중합 용매에 안하이드라이드 단량체를 첨가하여 반응시키는 단계; 상기 반응 용액에 말단-캡핑 제제를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계; 상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계; 상기 가교제가 첨가된 폴리아믹산을 포함하는 조성물을 지지체 상에 코팅하는 단계; 및 100℃ 이상의 온도에서 상기 지지체 상에 코팅된 폴리이미드 전구체를 열적 이미드화하는 단계를 포함하는, 폴리이미드 필름의 제조 방법을 제공한다.Another aspect of the present invention is the reaction by adding an anhydride monomer to a polymerization solvent containing a diamine monomer; adding an end-capping agent to the reaction solution and reacting to synthesize polyamic acid; Adding and mixing a crosslinking agent to the polyamic acid; coating a composition containing the polyamic acid to which the crosslinking agent is added on a support; and thermally imidizing the polyimide precursor coated on the support at a temperature of 100° C. or higher.
본원의 일 구현예에 있어서, 상기 열적 이미드화는, 예를 들어, 약 100℃ 내지 약 500℃, 약 100℃ 내지 약 400℃, 약 100℃ 내지 약 300℃, 약 100℃ 내지 약 200℃, 약 200℃ 내지 약 500℃, 약 300℃ 내지 약 500℃, 약 400℃ 내지 약 500℃에서 실행될 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the thermal imidization is, for example, about 100 ℃ to about 500 ℃, about 100 ℃ to about 400 ℃, about 100 ℃ to about 300 ℃, about 100 ℃ to about 200 ℃, It may be performed at about 200 ° C to about 500 ° C, about 300 ° C to about 500 ° C, and about 400 ° C to about 500 ° C, but may not be limited thereto.
이하, 본 발명의 실시예를 통하여 보다 구체적으로 설명하며, 본 실시예에 의하여 본 발명의 범위가 제한되는 것은 아니다.Hereinafter, it will be described in more detail through examples of the present invention, and the scope of the present invention is not limited by the examples.
[실시예][Example]
실시예 1Example 1
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol) 및 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA 0.43 g(0.0029 mol)을 투입하고 16 시간 동안 반응시켜 PAA 중합을 완료하였다. 그런 다음, 단량체(PPDA, BPDA 및 PMDA) 함량의2000 ppm의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.15874 g)을 동일 반응 용매인 NMP에 용해시킨 후 상기 PAA에 첨가하여 혼합하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were added sequentially. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete PAA polymerization. Then, 2000 ppm of 4,4'-methylenebis(N,N-diglycidylaniline) (0.15874 g) of monomers (PPDA, BPDA and PMDA) was dissolved in NMP, the same reaction solvent, and the PAA was added and mixed.
실시예 2Example 2
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)를 첨가하여 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol)과 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA 0.43 g(0.0029 mol)을 투입하였다. 16 시간의 반응 후, 단량체(PPDA, BPDA 및 PMDA) 함량의 3000 ppm의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.23811 g)을 동일 반응 용매인 NMP에 용해시킨 후 상기 PAA에 넣어 추가 혼합을 진행하였다.21.62 g (0.2 mol) of PPDA was added to 529.2 g of NMP maintained at room temperature to completely dissolve it, and then 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added. After 16 hours of reaction, 3000 ppm of 4,4'-methylenebis (N, N-diglycidylaniline) (0.23811 g) of monomers (PPDA, BPDA and PMDA) was dissolved in NMP, the same reaction solvent. After that, it was added to the PAA and further mixing was performed.
실시예 3Example 3
상온으로 유지된 NMP 529.2g에 PPDA 21.62g(0.2mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol)과 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후에 PA 0.43 g(0.0029 mol)을 투입하였다. 16시간의 반응 후, 단량체(PPDA, BPDA 및 PMDA) 함량의 4000 ppm의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.31748 g)을 용매에 녹여 반응이 끝난 PAA에 넣어 추가 혼합을 진행하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added. After 16 hours of reaction, 4,4'-methylenebis(N,N-diglycidylaniline) (0.31748 g) of 4000 ppm of monomers (PPDA, BPDA and PMDA) was dissolved in a solvent to added to proceed with further mixing.
비교예1Comparative Example 1
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18mol) 및 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA 0.43 g(0.0029 mol)을 투입하고 16 시간 동안 반응시켜 PAA 중합을 완료하였다. 그런 다음, 실시예 1과 동일한 양의 용매 NMP를 반응이 끝난 상기 PAA에 넣어 추가 혼합을 진행하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete PAA polymerization. Then, the same amount of solvent NMP as in Example 1 was added to the PAA after the reaction, and further mixing was performed.
비교예 2Comparative Example 2
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol) 및 PMDA 4.36 g(0.2 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA0.43 g(0.0029 mol)을 투입하고 16 시간 동안 반응시켜 PAA 중합을 완료하였다. 그런 다음, 단량체(PPDA, BPDA 및 PMDA) 함량의 1000 ppm의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.07937 g)을 동일 반응 용매인 NMP에 용해시킨 후 상기 PAA에 첨가하여 혼합하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.2 mol) of PMDA were sequentially added. After 1 hour of complete dissolution, PA0.43 g (0.0029 mol) was added and reacted for 16 hours to complete PAA polymerization. Then, 1000 ppm of 4,4'-methylenebis(N,N-diglycidylaniline) (0.07937 g) of monomers (PPDA, BPDA and PMDA) was dissolved in NMP, the same reaction solvent, and the PAA was added and mixed.
비교예comparative example 3 3
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol) 및 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA 0.43 g(0.0029 mol)을 투입하고 16 시간 동안 반응시켜 PAA 중합을 완료하였다. 그런 다음, 단량체(PPDA, BPDA 및 PMDA) 함량의 1500 ppm의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.119055 g)을 동일 반응 용매인 NMP에 용해시킨 후 상기 PAA에 첨가하여 혼합하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were added sequentially. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete PAA polymerization. Then, 1500 ppm of 4,4'-methylenebis (N, N-diglycidylaniline) (0.119055 g) of monomers (PPDA, BPDA and PMDA) was dissolved in NMP, the same reaction solvent, and the PAA was added and mixed.
비교예comparative example 4 4
상온으로 유지된 NMP 529.2 g에 PPDA 21.62 g(0.2 mol)을 완전히 용해시킨 후 BPDA 52.96 g(0.18 mol)와 PMDA 4.36 g(0.02 mol)을 차례로 투입하였다. 완전히 용해되고 1 시간 경과 후 PA 0.43 g(0.0029 mol)를 투입하였다. 16 시간의 반응 후, 단량체(PPDA, BPDA 및 PMDA) 함량의 5000 ppm 의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)(0.39685 g)를 동일 반응 용매인 NMP에 녹인 후 반응이 끝난 PAA에 넣어 추가 혼합을 진행하였다.After completely dissolving 21.62 g (0.2 mol) of PPDA in 529.2 g of NMP maintained at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were added sequentially. After 1 hour of complete dissolution, 0.43 g (0.0029 mol) of PA was added. After 16 hours of reaction, 5000 ppm of 4,4'-methylenebis(N,N-diglycidylaniline) (0.39685 g) of monomers (PPDA, BPDA and PMDA) was dissolved in the same reaction solvent, NMP. The mixture was added to the PAA after the reaction and further mixing was performed.
실험예 1Experimental Example 1
실시예 1 내지 3 및 비교예 1 내지 4의 폴리이미드 전구체를 LCD Glass SM TECH,new glass(200*200*0.63)에 어플리케이터(Baker applicator, YBA-4)를 이용하여 wet 두께 400 ㎛으로 코팅한 후 120℃로 가열된 컨벤션 오븐에 넣어 열적 이미드 반응을 진행하였다. 그런 다음, 분당 3℃로 승온하고, 최대 450℃에서 1 시간 동안 유지시킨 후에 서냉시켰다. 냉각 후 회수하여 필름 외부 형태와 광학적 특성 등을 분석하고 그 결과를 도 1 내지 4 및 표 1 및 2에 나타냈다.The polyimide precursors of Examples 1 to 3 and Comparative Examples 1 to 4 were coated to a wet thickness of 400 μm using an applicator (Baker applicator, YBA-4) on LCD Glass SM TECH, new glass (200 * 200 * 0.63) Then, it was placed in a convention oven heated to 120° C. to perform a thermal imide reaction. Then, the temperature was raised at 3 °C per minute, maintained at a maximum of 450 °C for 1 hour, and then cooled slowly. Recovered after cooling, the external shape and optical properties of the film were analyzed, and the results are shown in FIGS. 1 to 4 and Tables 1 and 2.
(단량체 대비)content
(compared to monomers)
(단량체 대비)content
(compared to monomers)
도 1 내지 7에서 볼 수 있는 바와 같이, 2000 ppm 내지 4000 ppm 함량의 4,4’-메틸렌비스(N,N-디글리시딜아닐린)을 첨가했을 때(도 1 내지 3), 필름 표면의 레벨링 상태가 양호하나, 4,4’-메틸렌비스(N,N-디글리시딜아닐린)을 첨가하지 않았을 때(도 4) 및 1000 ppm 또는 5000 ppm의 함량으로 첨가했을 때(도 5 내지 7), 필름 표면의 레벨링 상태가 불량함을 확인할 수 있다.As can be seen in FIGS. 1 to 7, when 2000 ppm to 4000 ppm of 4,4'-methylenebis(N,N-diglycidylaniline) is added (FIGS. 1 to 3), the surface of the film The leveling state is good, but when 4,4'-methylenebis (N, N-diglycidylaniline) is not added (FIG. 4) and when added at an amount of 1000 ppm or 5000 ppm (FIGS. 5 to 7 ), it can be confirmed that the leveling state of the film surface is poor.
또한, 표 1 및 2에서 볼 수 있는 바와 같이, 2000 ppm 미만 또는 5000 ppm 이상 첨가시에 투과도가 급격히 낮아지는 것을 확인할 수 있다.In addition, as can be seen in Tables 1 and 2, it can be seen that the transmittance is rapidly lowered when less than 2000 ppm or more than 5000 ppm is added.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성요소들도 결합된 형태로 실시될 수 있다.The above description of the present invention is for illustrative purposes, and those skilled in the art can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위, 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is indicated by the claims to be described later rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof are interpreted as being included in the scope of the present invention. It should be.
Claims (10)
Translated fromKorean상기 폴리아믹산 대비 2000 내지 4000 ppm 함량인 가교제;를 포함하고,
상기 가교제는 4,4'메틸렌비스(N,N-디글리시딜아닐린)을 포함하는 것을 특징으로 하는, 폴리이미드 전구체 조성물.
polyamic acid;
A crosslinking agent having a content of 2000 to 4000 ppm compared to the polyamic acid;
The polyimide precursor composition, characterized in that the crosslinking agent comprises 4,4'methylenebis (N, N-diglycidylaniline).
디아민 단량체를 함유하는 중합 용매에 안하이드라이드 단량체를 첨가하여 반응시키는 단계;
상기 반응 용액에 말단-캡핑 제제를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계; 및
상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계를 포함하며,
상기 가교제는 4,4’-메틸렌비스(N,N-디글리시딜아닐린)을 포함하는 것이고,
상기 가교제는 사용된 단량체 전체 대비 2000 내지 4000 ppm의 양으로 첨가되는 것인, 폴리이미드 전구체의 제조 방법.
A method for producing the polyimide precursor composition according to claim 1,
reacting by adding an anhydride monomer to a polymerization solvent containing a diamine monomer;
adding an end-capping agent to the reaction solution and reacting to synthesize polyamic acid; and
Adding and mixing a crosslinking agent to the polyamic acid,
The crosslinking agent includes 4,4'-methylenebis(N,N-diglycidylaniline),
The method for producing a polyimide precursor, wherein the crosslinking agent is added in an amount of 2000 to 4000 ppm relative to the total monomers used.
상기 디아민 단량체는PPDA(p-phenylenediamine), ODA(4,4'-oxydianiline), MDA(4,4'-methylenedianiline), m-톨리딘(2,2'-dimethyl-4,4'-diaminobiphenyl), TPE-R(1,3-bis(4'-aminophenoxyl)benzene), TFMB(2,2'-bis(trifluoromethyl) benzidine), HFBAPP(2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), Bis-AP-AF(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB(1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS(3,3'-diaminodiphenyl sulfone), ASD(4,4'-diaminodiphenyl sulfide), BAPS(bis[4-(4-aminophenoxy)phenyl]sulfone), m-BAPS(2,2-bis[4-(3-aminophenoxy)benzene] sulfone) 및 이들의 조합들로 이루어진 군으로부터 선택된 것인, 폴리이미드 전구체의 제조 방법.
According to claim 2,
The diamine monomer is PPDA (p-phenylenediamine), ODA (4,4'-oxydianiline), MDA (4,4'-methylenedianiline), m-tolidine (2,2'-dimethyl-4,4'-diaminobiphenyl) , TPE-R (1,3-bis (4'-aminophenoxyl) benzene), TFMB (2,2'-bis (trifluoromethyl) benzidine), HFBAPP (2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane), Bis-AP-AF (2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane), DRFB (1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3 '-diaminodiphenyl sulfone), ASD (4,4'-diaminodiphenyl sulfide), BAPS (bis[4-(4-aminophenoxy)phenyl]sulfone), m-BAPS(2,2-bis[4-(3-aminophenoxy) A method for producing a polyimide precursor selected from the group consisting of benzene] sulfone) and combinations thereof.
상기 안하이드라이드 단량체는 방향족 디안하이드라이드 단량체인 것인, 폴리이미드 전구체의 제조 방법.
According to claim 2,
The method for producing a polyimide precursor, wherein the anhydride monomer is an aromatic dianhydride monomer.
상기 방향족 디안하이드라이드 단량체는BTDA(3,3',4,4'-benzophenonetetracarboxylicdianhydride), PMDA(pyromellitic dianhydride), BPDA(3,3',4,4'-biphenyl tetracarboxylicacid dianhydride), 6FDA(2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride), a-BPDA(2,3,3',4-biphenyl tetracarboxylicacid dianhydride), ODPA(4,4'-oxydiphthalic anhydride), DSDA(3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA(2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride), HQDA(hydroquinone diphthalic anhydride) 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 포함하는 것인, 폴리이미드 전구체의 제조 방법.
According to claim 4,
The aromatic dianhydride monomer is BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride), PMDA (pyromellitic dianhydride), BPDA (3,3',4,4'-biphenyl tetracarboxylic acid dianhydride), 6FDA (2,2 -bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride), a-BPDA(2,3,3',4-biphenyl tetracarboxylicacid dianhydride), ODPA(4,4'-oxydiphthalic anhydride), DSDA(3,3', 4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride), HQDA (hydroquinone diphthalic anhydride), and combinations thereof A method for producing a polyimide precursor, comprising:
적어도 두 개의 안하이드라이드 단량체를 첨가하는 것인, 폴리이미드 전구체의 제조 방법.
According to claim 2,
A method for preparing a polyimide precursor, wherein at least two anhydride monomers are added.
상기 중합 용매는 아미드계 용매, 케톤계 용매, 에테르계 용매, 에스테르계 용매, 대칭 글리콜디에테르류 용매, 에테르류 용매 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 포함하는 것인, 폴리이미드 전구체의 제조 방법.
According to claim 2,
The polymerization solvent includes one selected from the group consisting of amide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, symmetrical glycol diether solvents, ether solvents, and combinations thereof. manufacturing method.
상기 말단-캡핑 제제는 PA(phthallic anhydride), TSA(tetradecyl succinic anhydride), HAS(hexadecyl succinic anhydride), OSA(octadecyl succinic anhydride) 및 이들의 조합들로 이루어진 군으로부터 선택된 것인, 폴리이미드 전구체의 제조 방법.
According to claim 2,
The end-capping agent is selected from the group consisting of phthalic anhydride (PA), tetradecyl succinic anhydride (TSA), hexadecyl succinic anhydride (HAS), octadecyl succinic anhydride (OSA), and combinations thereof. Preparation of a polyimide precursor method.
상기 반응 용액에 말단-캡핑 제제를 첨가한 후 반응시켜 폴리아믹산을 합성하는 단계;
상기 폴리아믹산에 가교제를 첨가하여 혼합하는 단계;
상기 가교제가 첨가된 폴리아믹산을 포함하는 조성물을 지지체 상에 코팅하는 단계; 및
100℃ 이상의 온도에서 상기 지지체 상에 코팅된 폴리이미드 전구체를 열적 이미드화하는 단계
를 포함하며,
상기 가교제는 4,4’-메틸렌비스(N,N-디글리시딜아닐린)을 포함하는 것이고,
상기 가교제는 사용된 단량체 전체 대비 2000 내지 4000 ppm의 양으로 첨가되는 것인, 폴리이미드 필름의 제조 방법.reacting by adding an anhydride monomer to a polymerization solvent containing a diamine monomer;
adding an end-capping agent to the reaction solution and reacting to synthesize polyamic acid;
Adding and mixing a crosslinking agent to the polyamic acid;
coating a composition containing the polyamic acid to which the crosslinking agent is added on a support; and
Thermal imidization of the polyimide precursor coated on the support at a temperature of 100 ° C. or higher
Including,
The crosslinking agent includes 4,4'-methylenebis(N,N-diglycidylaniline),
The crosslinking agent is added in an amount of 2000 to 4000 ppm relative to the total monomers used, a method for producing a polyimide film.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150190977AKR102531268B1 (en) | 2015-12-31 | 2015-12-31 | Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same |
| CN201611223753.4ACN106947080B (en) | 2015-12-31 | 2016-12-27 | Composition for preparing polyimide film, preparation method thereof and preparation method of polyimide film using composition |
| JP2016255918AJP6928447B2 (en) | 2015-12-31 | 2016-12-28 | A composition for producing a polyimide film, a method for producing the same, and a method for producing a polyimide film using the same. |
| TW105144096ATWI739784B (en) | 2015-12-31 | 2016-12-30 | Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150190977AKR102531268B1 (en) | 2015-12-31 | 2015-12-31 | Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170079921A KR20170079921A (en) | 2017-07-10 |
| KR102531268B1true KR102531268B1 (en) | 2023-05-12 |
Family
ID=59271978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150190977AActiveKR102531268B1 (en) | 2015-12-31 | 2015-12-31 | Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6928447B2 (en) |
| KR (1) | KR102531268B1 (en) |
| CN (1) | CN106947080B (en) |
| TW (1) | TWI739784B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190017527A (en)* | 2017-08-11 | 2019-02-20 | 주식회사 동진쎄미켐 | Polyimide precursor composition and method for producing polyimide film using the same |
| KR20190017524A (en)* | 2017-08-11 | 2019-02-20 | 주식회사 동진쎄미켐 | Polyimide precursor composition and method for producing polyimide film using the same |
| KR101906394B1 (en)* | 2017-11-10 | 2018-10-11 | 에스케이씨코오롱피아이 주식회사 | Ultra Thin Black Polyimide Film and Method For Preparing The Same |
| KR102491338B1 (en)* | 2018-01-26 | 2023-01-27 | 주식회사 넥스플렉스 | flexible metal clad laminate and THERMOPLASTIC POLYIMIDE PRECORSOR COMPOSITION for flexible metal clad laminate |
| KR102141892B1 (en)* | 2018-04-05 | 2020-08-07 | 피아이첨단소재 주식회사 | Polyimide Film for Preparing Flexible Metal Foil Clad Laminate And Flexible Metal Foil Clad Laminate Comprising the Same |
| KR102141893B1 (en)* | 2018-04-05 | 2020-08-07 | 피아이첨단소재 주식회사 | Polyimide Film for Preparing Flexible Metal Foil Clad Laminate And Flexible Metal Foil Clad Laminate Comprising the Same |
| KR101959807B1 (en)* | 2018-08-22 | 2019-03-20 | 에스케이씨코오롱피아이 주식회사 | Polyimide Varnish for Coating Conductor Comprising Aromatic Carboxylic Acid and Method for Preparing the Same |
| WO2020166913A1 (en)* | 2019-02-14 | 2020-08-20 | 주식회사 엘지화학 | Polyimide precursor composition and polyimide film manufactured using same |
| KR102262507B1 (en) | 2019-02-14 | 2021-06-08 | 주식회사 엘지화학 | Compoistion of polyimide precursor and polyimide film prepared using same |
| KR102362385B1 (en)* | 2019-11-13 | 2022-02-15 | 피아이첨단소재 주식회사 | High Elastic and High Heat Resistant Polyimide Film and Manufacturing Method Thereof |
| KR20240053229A (en)* | 2022-10-17 | 2024-04-24 | 피아이첨단소재 주식회사 | Polyimide film and manufacturing method thereof |
| KR20250055093A (en)* | 2023-10-17 | 2025-04-24 | 피아이첨단소재 주식회사 | Polyimide with solubility and method for preparing same |
| CN117866528A (en)* | 2023-12-30 | 2024-04-12 | 连云港邃铸科技有限公司 | A polyimide composition, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123857A (en)* | 2002-10-01 | 2004-04-22 | Teijin Ltd | Polyamic acid composition and process for preparing polyamic acid |
| JP2009102494A (en)* | 2007-10-23 | 2009-05-14 | Chisso Corp | Composition for screen printing |
| JP2012184281A (en) | 2011-03-03 | 2012-09-27 | Hitachi Chemical Dupont Microsystems Ltd | Resin composition |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11305031A (en)* | 1998-02-20 | 1999-11-05 | Toray Ind Inc | Color filter and liquid crystal display device |
| US6913694B2 (en)* | 2001-11-06 | 2005-07-05 | Saehan Industries Incorporation | Selective membrane having a high fouling resistance |
| CN100427189C (en)* | 2002-07-16 | 2008-10-22 | 世韩工业株式会社 | Method for producing selective separation membrane excellent in fouling resistance |
| JP4074987B2 (en)* | 2002-10-29 | 2008-04-16 | 東レ・デュポン株式会社 | Polyimide film and stiffener for flexible circuit board using the same |
| KR100889910B1 (en)* | 2006-05-25 | 2009-03-20 | 주식회사 엘지화학 | Method for producing porous polyimide film using polymer nanoparticles and porous polyimide film produced thereby |
| KR101225842B1 (en)* | 2007-08-27 | 2013-01-23 | 코오롱인더스트리 주식회사 | Colorless polyimide film |
| JP5577591B2 (en)* | 2007-12-27 | 2014-08-27 | Ｊｎｃ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| TWI445765B (en)* | 2009-06-09 | 2014-07-21 | Asahi Kasei E Materials Corp | A resin composition, a cured product, and a circuit substrate using the same |
| KR101543478B1 (en)* | 2010-12-31 | 2015-08-10 | 코오롱인더스트리 주식회사 | Transparent Polyimide film and Method for Preparing the Same |
| WO2013055798A1 (en)* | 2011-10-10 | 2013-04-18 | Brewer Science Inc. | Spin-on carbon compositions for lithographic processing |
| JP5939066B2 (en)* | 2011-11-15 | 2016-06-22 | Jsr株式会社 | Method for producing liquid crystal aligning agent |
| JP6206071B2 (en)* | 2013-10-15 | 2017-10-04 | 東レ株式会社 | RESIN COMPOSITION, POLYIMIDE RESIN FILM USING THE SAME, COLOR FILTER CONTAINING THE SAME, TFT SUBSTRATE, DISPLAY DEVICE AND METHOD FOR PRODUCING THEM |
- 2015
- 2015-12-31KRKR1020150190977Apatent/KR102531268B1/enactiveActive
- 2016
- 2016-12-27CNCN201611223753.4Apatent/CN106947080B/enactiveActive
- 2016-12-28JPJP2016255918Apatent/JP6928447B2/enactiveActive
- 2016-12-30TWTW105144096Apatent/TWI739784B/enactive
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123857A (en)* | 2002-10-01 | 2004-04-22 | Teijin Ltd | Polyamic acid composition and process for preparing polyamic acid |
| JP2009102494A (en)* | 2007-10-23 | 2009-05-14 | Chisso Corp | Composition for screen printing |
| JP2012184281A (en) | 2011-03-03 | 2012-09-27 | Hitachi Chemical Dupont Microsystems Ltd | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI739784B (en) | 2021-09-21 |
| CN106947080B (en) | 2024-02-23 |
| JP2017119869A (en) | 2017-07-06 |
| JP6928447B2 (en) | 2021-09-01 |
| TW201736511A (en) | 2017-10-16 |
| CN106947080A (en) | 2017-07-14 |
| KR20170079921A (en) | 2017-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102531268B1 (en) | Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same | |
| JP7384546B2 (en) | Polyimide polymer composition, method for producing the same, and method for producing polyimide film using the same | |
| CN103282414B (en) | Transparent polyimide film and preparation method thereof | |
| KR102158223B1 (en) | Polyamic acid solution, polyimde film, and method for manufacturing the same | |
| JP6929355B2 (en) | Polyamic acid, polyimide, polyimide film, image display device containing this, and method for producing polyamic acid | |
| KR102251518B1 (en) | Polyamic acid, And Polyimide Resin And Polyimide Film | |
| JP7206358B2 (en) | Method for producing polyamic acid, polyamic acid produced therefrom, polyimide resin, and polyimide film | |
| CN103282416B (en) | Preparation method of polyimide film | |
| KR20160094551A (en) | Polyamic acid composition and polyimide substrate | |
| WO2022054766A1 (en) | Polymer composition, varnish, and polyimide film | |
| JP2022516281A (en) | A method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced by the method for producing the same. | |
| KR102251519B1 (en) | Polyamic acid, And Polyimide Resin And Polyimide Film | |
| US20230416464A1 (en) | Polyamic acid composition, and polyimide comprising same | |
| KR101258432B1 (en) | Polyimide film having excellent high temperature stability and substrate for display device using the same | |
| KR20160077479A (en) | Manufacturing method of polyimide precursor solution, polyimide film manufactured using the same | |
| KR102041642B1 (en) | Polyamic Acid and Polyimine-imide Film Using the Same | |
| TW201444916A (en) | Polyimide resin and polyimide film produced therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PA0109 | Patent application | Patent event code:PA01091R01D Comment text:Patent Application Patent event date:20151231 | |
| PG1501 | Laying open of application | ||
| PA0201 | Request for examination | Patent event code:PA02012R01D Patent event date:20201224 Comment text:Request for Examination of Application Patent event code:PA02011R01I Patent event date:20151231 Comment text:Patent Application | |
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection | Comment text:Notification of reason for refusal Patent event date:20220530 Patent event code:PE09021S01D | |
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration | Patent event code:PE07011S01D Comment text:Decision to Grant Registration Patent event date:20230130 | |
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment | Comment text:Registration of Establishment Patent event date:20230508 Patent event code:PR07011E01D | |
| PR1002 | Payment of registration fee | Payment date:20230509 End annual number:3 Start annual number:1 | |
| PG1601 | Publication of registration |