KR20230100338A - Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film - Google Patents
Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film Download PDFInfo
- Publication number
- KR20230100338A KR20230100338A KR1020210190113A KR20210190113A KR20230100338A KR 20230100338 A KR20230100338 A KR 20230100338A KR 1020210190113 A KR1020210190113 A KR 1020210190113A KR 20210190113 A KR20210190113 A KR 20210190113A KR 20230100338 A KR20230100338 A KR 20230100338A
- Authority
- KR
- South Korea
- Prior art keywords
- polybenzoxazole
- polyimide copolymer
- diamine compound
- formula
- polyimide
- Prior art date
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 37
- 229920001721 polyimide Polymers 0.000 title claims abstract description 37
- -1 Diamine compound Chemical class 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- 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
- C08G73/22—Polybenzoxazoles
-
- 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
- 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
Abstract
본 발명의 실시예들은 디아민 화합물 및 이를 이용한 폴리벤조옥사졸-폴리이미드 공중합체, 폴리벤조옥사졸-폴리이미드 공중합체 필름에 관한 것이다. 본 발명의 일 실시예에 따른 신규한 디아민 화합물은 하기의 화학식 1로 표시되는 구조를 가질 수 있다.
[화학식 1]
[Formula 1]
Description
본 발명의 실시예들은 디아민 화합물 및 이를 이용한 폴리벤조옥사졸-폴리이미드 공중합체, 폴리벤조옥사졸-폴리이미드 공중합체 필름에 관한 것이다.Embodiments of the present invention relate to a diamine compound, a polybenzoxazole-polyimide copolymer using the diamine compound, and a polybenzoxazole-polyimide copolymer film.
폴리벤조옥사졸은 내열성, 기계적 물성, 치수안정성, 절연특성 등이 매우 우수한 슈퍼 엔지니어링 플라스틱으로서, 프린트 배선기판, 회로기판 등의 전기전자기기 등에 폭넓게 사용되고 있다. 한편, 폴리이미드는 우수한 열적, 기계적 및 전기적 성질의 우수한 특성으로 인해 많은 첨단 제품 및 필름 등의 용도에 사용되어 왔다. 특히 최근에는 분리막이나 디스플레이용 기판 소재로 많이 사용되고 있다. Polybenzoxazole is a super engineering plastic with excellent heat resistance, mechanical properties, dimensional stability, and insulating properties, and is widely used in electric and electronic devices such as printed wiring boards and circuit boards. On the other hand, polyimide has been used in many high-tech products and applications such as films due to its excellent thermal, mechanical and electrical properties. In particular, recently, it has been widely used as a substrate material for separators or displays.
폴리벤조옥사졸은 폴리이미드보다 내열성이나 기계적 물성이 우수하지만 히드록시기를 갖는 디아민을 디카브복실산과 반응시켜 전구체를 얻고 이를 고온에서 탈수 반응을 진행시켜 제조함에 따라 제조방법이 까다로우며 다양한 구조의 모노머를 얻을 수 없다는 점이 불리하다. 반면에 폴리이미드는 디아민과 디안하이드라이드를 상온에서 반응시켜 폴리이미드 전구체를 얻고 이를 고온에서 탈수 반응을 진행하여 얻을 수 있다. 또한, 다양한 구조의 디아민과 디안하이드라이드를 이용하여 투과도, 내열성, 기계적 물성 등의 특성을 쉬게 조절할 수 있는 장점이 있다. Polybenzoxazole has better heat resistance and mechanical properties than polyimide, but the production method is difficult and monomers with various structures are produced by obtaining a precursor by reacting diamine having a hydroxyl group with dicarboxylic acid and dehydrating it at high temperature. It is disadvantageous that you cannot obtain . On the other hand, polyimide can be obtained by reacting diamine and dianhydride at room temperature to obtain a polyimide precursor and dehydrating it at high temperature. In addition, there is an advantage in that properties such as transmittance, heat resistance, and mechanical properties can be easily controlled using diamines and dianhydrides of various structures.
따라서 이와 같이 폴리베조옥사졸 및 폴리이미디의 두 가지 고분자의 장점을 동시에 구현하기 위하여 폴리벤조옥사졸-폴리이미드 공중합체를 제조하는 방법이 제공될 필요가 있다.Therefore, it is necessary to provide a method for preparing a polybenzoxazole-polyimide copolymer in order to simultaneously realize the advantages of the two polymers of polybezoxazole and polyimide.
본 발명의 실시예들은 상기 문제점들을 해결하기 위한 것으로서, 내열성이 우수한 디아민 화합물 및 이를 이용한 폴리벤조옥사졸-폴리이미드 공중합체, 폴리벤조옥사졸-폴리이미드 공중합체 필름을 제공하기 위한 것이다.Embodiments of the present invention are to solve the above problems, and to provide a diamine compound with excellent heat resistance, a polybenzoxazole-polyimide copolymer using the diamine compound, and a polybenzoxazole-polyimide copolymer film.
또한, 본 발명의 실시예들은 내열성이 우수한 디아민 화합물 및 이를 이용한 폴리벤조옥사졸-폴리이미드 공중합체, 폴리벤조옥사졸-폴리이미드 공중합체 필름을 제조하는 방법을 제공하기 위한 것이다.In addition, embodiments of the present invention are to provide a diamine compound with excellent heat resistance and a method for preparing a polybenzoxazole-polyimide copolymer and a polybenzoxazole-polyimide copolymer film using the diamine compound.
본 발명은 하기 화학식 1로 표시되는 구조를 가지는 디아민 화합물을 제공한다.The present invention provides a diamine compound having a structure represented by Formula 1 below.
[화학식 1][Formula 1]
또한, 본 발명은 상기 디아민 화합물을 이용하여 제조되는 하기 화학식 2로 표시되는 반복단위를 갖는 폴리벤조옥사졸-폴리이미드 공중합체를 제공한다.In addition, the present invention provides a polybenzoxazole-polyimide copolymer having a repeating unit represented by Formula 2 prepared using the diamine compound.
[화학식 2] [Formula 2]
(상기 화학식 2에서, n은 반복단위의 수로서 10≤n≤100의 정수이고, Ar은 4가의 반응기를 가지는 디안하이드라이드이다)(In Chemical Formula 2, n is the number of repeating units and is an integer of 10≤n≤100, and Ar is a dianhydride having a tetravalent reactive group)
또한, 상기 Ar은 하기 식으로 표시되는 것 중에서 선택될 수 있다. In addition, the Ar may be selected from those represented by the following formula.
또한, 본 발명은 상기 디아민 화합물을 이용하여 제조되는 폴리벤조옥사졸-폴리이미드 공중합체 필름을 제공한다.In addition, the present invention provides a polybenzoxazole-polyimide copolymer film prepared using the diamine compound.
본 발명의 실시예들에 따르면, 기존 폴리이미드에 비하여 우수한 내열성을 가지는 폴리벤조옥사졸-폴리이미드 공중합체를 제공한다. According to embodiments of the present invention, a polybenzoxazole-polyimide copolymer having excellent heat resistance compared to conventional polyimide is provided.
또한, 본 발명의 실시예들에 따르면, 기계적 물성, 특히 탄성율(Young's Modulus)이 우수한 폴리벤조옥사졸-폴리이미드 공중합체를 제공한다.In addition, according to embodiments of the present invention, a polybenzoxazole-polyimide copolymer having excellent mechanical properties, particularly Young's Modulus, is provided.
또한, 본 발명의 실시예들에 따르면 폴리벤조옥사졸보다 낮은 온도에서 경화반응이 가능한 폴리벤조옥사졸-폴리이미드 공중합체를 제공한다.In addition, according to embodiments of the present invention, a polybenzoxazole-polyimide copolymer capable of curing at a lower temperature than polybenzoxazole is provided.
도 1은 본 발명의 일 실시예에 따른 디아민 화합물의 1H NMR 그래프
도 2는 본 발명의 폴리벤조옥사졸-폴리이미드 공중합체와 비교예인 폴리이미드 중합체의 TGA 그래프1 is a 1H NMR graph of a diamine compound according to an embodiment of the present invention
Figure 2 is a TGA graph of the polybenzoxazole-polyimide copolymer of the present invention and the polyimide polymer as a comparative example
이하, 도면을 참조하여 구체적인 실시형태를 설명하기로 한다. 이하의 상세한 설명은 본 명세서에서 기술된 방법, 장치 및/또는 시스템에 대한 포괄적인 이해를 돕기 위해 제공된다. 그러나 이는 예시에 불과하며 개시되는 실시예들은 이에 제한되지 않는다.Hereinafter, specific embodiments will be described with reference to the drawings. The detailed descriptions that follow are provided to provide a comprehensive understanding of the methods, devices and/or systems described herein. However, this is only an example and disclosed embodiments are not limited thereto.
실시예들을 설명함에 있어서, 관련된 공지기술에 대한 구체적인 설명이 개시되는 실시예들의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략하기로 한다. 그리고, 후술되는 용어들은 개시되는 실시예들에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. 상세한 설명에서 사용되는 용어는 단지 실시예들을 기술하기 위한 것이며, 결코 제한적이어서는 안 된다. 명확하게 달리 사용되지 않는 한, 단수 형태의 표현은 복수 형태의 의미를 포함한다. 본 설명에서, "포함" 또는 "구비"와 같은 표현은 어떤 특성들, 숫자들, 단계들, 동작들, 요소들, 이들의 일부 또는 조합을 가리키기 위한 것이며, 기술된 것 이외에 하나 또는 그 이상의 다른 특성, 숫자, 단계, 동작, 요소, 이들의 일부 또는 조합의 존재 또는 가능성을 배제하도록 해석되어서는 안 된다.In describing the embodiments, if it is determined that a detailed description of related known technologies may unnecessarily obscure the gist of the disclosed embodiments, the detailed description will be omitted. In addition, terms to be described later are terms defined in consideration of functions in the disclosed embodiments, which may vary according to intentions or customs of users or operators. Therefore, the definition should be made based on the contents throughout this specification. Terminology used in the detailed description is only for describing the embodiments and should in no way be limiting. Unless expressly used otherwise, singular forms of expression include plural forms. In this description, expressions such as "comprising" or "comprising" are intended to indicate any characteristic, number, step, operation, element, portion or combination thereof, one or more other than those described. It should not be construed to exclude the existence or possibility of any other feature, number, step, operation, element, part or combination thereof.
본 발명의 일 실시예에 따른 신규한 디아민 화합물은 하기의 화학식 1로 표시되는 구조를 가질 수 있다.A novel diamine compound according to an embodiment of the present invention may have a structure represented by Formula 1 below.
[화학식 1][Formula 1]
신규한 디아민 화합물은 다음과 같은 방법으로 합성할 수 있다.A novel diamine compound can be synthesized by the following method.
2,2-Bis(3-amino-4-hydroxyphenyl)propane(10g)과 Amidol(11.05g,)을 100 g의 반응 용매인 PPA에 넣고 순차적으로 180 oC까지 온도를 올린 후 180 oC에서 12시간을 반응을 진행시킬 수 있다. 반응이 완료된 반응 혼합물은 상온으로 식힌 후, 반응 혼합물의 pH를 변화시키기 위하여 과포화된 sodiumbicarbonate(NaHCO3) 용액을 반응 혼합물에 첨가하여 pH를 8의 상태로 맞추어 줄 수 있다. 이때 형성된 고체인 원(crude) 생성물을 여과 과정을 통하여 얻었으며, 이를 재결정 방법을 이용하여 메탄올(methanol)에서 정제하여 16.8 g(36.39 mmol) 얻을 수 있다. 2,2-Bis (3-amino-4-hydroxyphenyl) propane (10 g) and Amidol (11.05 g,) were added to 100 g of PPA, a reaction solvent, and the temperature was raised to 180 o C sequentially, followed by 12 at 180 o C. Time can allow the reaction to proceed. After the reaction is completed, the reaction mixture is cooled to room temperature, and then a supersaturated sodium bicarbonate (NaHCO 3 ) solution is added to the reaction mixture to change the pH of the reaction mixture to adjust the pH to 8. At this time, the crude product, which is a solid, was obtained through a filtration process, and 16.8 g (36.39 mmol) can be obtained by purifying it in methanol using a recrystallization method.
상기 방법에 따라 합성된 본 발명의 일 실시예에 따른 디아민 화합물의 1H NMR 그래프는 도 1에 나타낸 바와 같다.A 1H NMR graph of the diamine compound according to an embodiment of the present invention synthesized according to the above method is shown in FIG. 1.
도 1의 8.26 ppm의 화학적 이동은 d 수소, 7.60 ppm의 화학적 이동은 e 수소, 7.45ppm의 화학적 이동은 c 수소, 6.89 ppm의 화학적 이동은 c 수소, 6.72 ppm의 화학적 이동은 b 수소, 6.70 ppm의 화학적 이동은 a 수소, 그리고 5.75 ppm의 화학적 이동은 f 수소에 해당한다.1, the chemical shift of 8.26 ppm is d hydrogen, the chemical shift of 7.60 ppm is e hydrogen, the chemical shift of 7.45 ppm is c hydrogen, the chemical shift of 6.89 ppm is c hydrogen, the chemical shift of 6.72 ppm is b hydrogen, 6.70 ppm has a chemical shift of a hydrogen, and a chemical shift of 5.75 ppm corresponds to f hydrogen.
상기의 신규한 디아민 화합물을 이용하여 하기 화학식 2로 표시되는 반복단위를 갖는 폴리벤조옥사졸-폴리이미드 공중합체가 제조될 수 있다..A polybenzoxazole-polyimide copolymer having a repeating unit represented by Formula 2 below can be prepared using the novel diamine compound.
[화학식 2] [Formula 2]
상기 화학식 2에서, n은 반복단위의 수로서 10≤n≤100의 정수이고, Ar은 4가의 반응기를 가지는 디안하이드라이드일 수 있다. 디안하이드라이드는 특별히 제한되지 않으나 주로 하기 식으로 표시되는 것 중에서 선택될 수 있다.In Chemical Formula 2, n is the number of repeating units and is an integer of 10≤n≤100, and Ar may be a dianhydride having a tetravalent reactive group. The dianhydride is not particularly limited, but may be selected from those mainly represented by the following formula.
이러한 폴리벤조옥사졸-폴리이미드 공중합체는 하기의 반응식 1과 같이 신규한 디아민 화합물을 디안하이드라이드와 반응시켜서 제조될 수 있다.Such a polybenzoxazole-polyimide copolymer can be prepared by reacting a novel diamine compound with a dianhydride as shown in Scheme 1 below.
[반응식 1] [Scheme 1]
신규한 디아민 화합물을 이용하여 제조되는 폴리벤조옥사졸-폴리이미드 공중합체를 이용하여 폴리벤조옥사졸-폴리이미드 공중합체 필름이 제조될 수 있다.A polybenzoxazole-polyimide copolymer film may be prepared using the polybenzoxazole-polyimide copolymer prepared using a novel diamine compound.
[실시예][Example]
이하, 본발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited by the examples.
(실시예 1)(Example 1)
질소 분위기하에서 3구 플라스크에 화학식 1의 디아민 화합물 10.0g(17.59mmol)을 50g의 N-메틸피롤리돈에 녹인 다음 비페닐디안하이드라이드 5.175g(BPDA, 17.59mmol)을 서서히 첨가하며 상온에서 24시간 동안 저어 주었다. 얻어진 중합체를 겔투과 크로마토그래피(GPC)를 이용하여 분자량 측정시 중량 평균 분자량이 35,000 g/mol로 확인되었다. 10.0 g (17.59 mmol) of the diamine compound of Formula 1 was dissolved in 50 g of N-methylpyrrolidone in a three-necked flask under a nitrogen atmosphere, and then 5.175 g (BPDA, 17.59 mmol) of biphenyldianhydride was slowly added and stirred at room temperature for 24 hours. Stir for an hour. When the molecular weight of the obtained polymer was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 35,000 g/mol.
얻어진 폴리머 용액을 스핀코터를 이용하여 유리판 위에 10μm 두께로 코팅한후 질소분위기가 유지되는 고온용 오븐을 이용하여 300
(실시예 2)(Example 2)
실시예 1과 같은 방법으로 화학식 1의 디아민 화합물 10.0g(17.59mmol)과 옥시디프탈릭안하이드라이드 5.456g (ODPA, 17.59mmol)을 반응시켜 폴리벤조옥사졸-폴리이미드 공중합체를 얻었다. GPC를 이용하여 측정한 분자량은 37,000 g/mol 이었다. 열분해온도 및 기계적 물성치를 비교실시예의 경우와 함께 표 1과 도 2에 나타내었다.In the same manner as in Example 1, 10.0 g (17.59 mmol) of the diamine compound of Formula 1 and 5.456 g (ODPA, 17.59 mmol) of oxydiphthalic anhydride were reacted to obtain a polybenzoxazole-polyimide copolymer. The molecular weight measured using GPC was 37,000 g/mol. The thermal decomposition temperature and mechanical properties are shown in Table 1 and FIG. 2 together with the comparative examples.
(실시예 3)(Example 3)
실시예 1과 같은 방법으로 화학식 1의 디아민 화합물 10.0g(17.59mmol)과 헥사플로오로이소프로필레딘 다이프탈릭 안하이드라이드 7.814g (6FDA, 17.59mmol)을 반응시켜 폴리벤조옥사졸-폴리이미드 공중합체를 얻었다. GPC를 이용하여 측정한 분자량은 30,000 g/mol 이었다. 열분해온도 및 기계적 물성치를 비교실시예의 경우와 함께 표 1과 도 2에 나타내었다.In the same manner as in Example 1, 10.0 g (17.59 mmol) of the diamine compound of Formula 1 and 7.814 g (6FDA, 17.59 mmol) of hexafluoroisopropyledine diphthalic anhydride were reacted to prepare a polybenzoxazole-polyimide copolymer. got a composite. The molecular weight measured using GPC was 30,000 g/mol. The thermal decomposition temperature and mechanical properties are shown in Table 1 and FIG. 2 together with the comparative examples.
(실시예 4)(Example 4)
실시예 1과 같은 방법으로 화학식 1의 디아민 화합물 10.0g(17.59mmol)과 디페닐설폰테트라카르본산 디안하이드라이드 6.302g (DSDA, 17.59mmol)을 반응시켜 폴리벤조옥사졸-폴리이미드 공중합체를 얻었다. GPC를 이용하여 측정한 분자량은 25,000 g/mol이었다. 열분해온도 및 기계적 물성치를 비교실시예의 경우와 함께 표 1과 도 2에 나타내었다.In the same manner as in Example 1, 10.0 g (17.59 mmol) of the diamine compound of Formula 1 and 6.302 g (DSDA, 17.59 mmol) of diphenylsulfotetracarboxylic acid dianhydride were reacted to obtain a polybenzoxazole-polyimide copolymer. . The molecular weight measured using GPC was 25,000 g/mol. The thermal decomposition temperature and mechanical properties are shown in Table 1 and FIG. 2 together with the comparative examples.
(실시예 5)(Example 5)
실시예 1과 같은 방법으로 화학식 1의 디아민 화합물 10.0g(17.59mmol)과 벤조페논테트라카르본산 디안하이드라이드 5.668g (BTDA, 17.59mmol)을 반응시켜 폴리벤조옥사졸-폴리이미드 공중합체를 얻었다. GPC를 이용하여 측정한 분자량은 24,000 g/mol이었다. 열분해온도 및 기계적 물성치를 비교실시예의 경우와 함께 표 1과 도 2에 나타내었다.In the same manner as in Example 1, 10.0 g (17.59 mmol) of the diamine compound of Formula 1 and 5.668 g (BTDA, 17.59 mmol) of benzophenone tetracarboxylic acid dianhydride were reacted to obtain a polybenzoxazole-polyimide copolymer. The molecular weight measured using GPC was 24,000 g/mol. The thermal decomposition temperature and mechanical properties are shown in Table 1 and FIG. 2 together with the comparative examples.
(비교예)(Comparative example)
실시예 1과 같은 방법으로 헥사플로오로이소플필레딘 디아닐린 (Bis AAF) 화합물 5.875g(17.59mmol)과 옥시디프탈릭안하이드라이드 5.456g (ODPA, 17.59mmol)을 반응시켜 폴리이미드 중합체를 얻었다. GPC를 이용하여 측정한 분자량은 30,000 g/mol 이었다.In the same manner as in Example 1, 5.875 g (17.59 mmol) of a hexafluoroisoplefiledine dianiline (Bis AAF) compound and 5.456 g (ODPA, 17.59 mmol) of oxydiphthalic anhydride were reacted to obtain a polyimide polymer. The molecular weight measured using GPC was 30,000 g/mol.
표 1 및 도 2를 참조하면, 본 발명의 디아민 화합물(화합식 1)을 사용하여 제조한 실시예의 폴리벤조옥사졸-폴리이미드 공중합체의 내열성 및 기계적 특성이 우수한 것을 알 수 있다. 또한, 동일한 종류의 옥시프탈릭디안하이드라이드를 사용하였을 때(실시예 2와 비교예를 비교), 내열성 및 기계적 물성을 향상시키는 효과가 분명하게 나타나는 것을 확인할 수 있다. Referring to Table 1 and FIG. 2, it can be seen that the polybenzoxazole-polyimide copolymer of Example prepared using the diamine compound (Formula 1) of the present invention has excellent heat resistance and mechanical properties. In addition, when using the same type of oxyphthalic dianhydride (comparison between Example 2 and Comparative Example), it can be confirmed that the effect of improving heat resistance and mechanical properties is clearly shown.
이상에서 본 발명의 대표적인 실시예들을 상세하게 설명하였으나, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 상술한 실시예에 대하여 본 발명의 범주에서 벗어나지 않는 한도 내에서 다양한 변형이 가능함을 이해할 것이다. 그러므로 본 발명의 권리범위는 설명된 실시예에 국한되어 정해져서는 안 되며, 후술하는 청구범위뿐만 아니라 이 청구범위와 균등한 것들에 의해 정해져야 한다.Although representative embodiments of the present invention have been described in detail above, those skilled in the art will understand that various modifications are possible to the above-described embodiments without departing from the scope of the present invention. . Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.
Claims (4)
[화학식 1]
A diamine compound having a structure represented by Formula 1 below.
[Formula 1]
[화학식 2]
(상기 화학식 2에서, n은 반복단위의 수로서 10≤n≤100의 정수이고, Ar은 4가의 반응기를 가지는 디안하이드라이드이다)
A polybenzoxazole-polyimide copolymer having a repeating unit represented by Formula 2 prepared using the diamine compound of claim 1.
[Formula 2]
(In Chemical Formula 2, n is the number of repeating units and is an integer of 10≤n≤100, and Ar is a dianhydride having a tetravalent reactive group)
상기 Ar은 하기 식으로 표시되는 것 중에서 선택되는, 폴리벤조옥사졸-폴리이미드 공중합체.
The method of claim 2,
The Ar is selected from those represented by the following formula, polybenzoxazole-polyimide copolymer.
A polybenzoxazole-polyimide copolymer film prepared using the diamine compound of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210190113A KR20230100338A (en) | 2021-12-28 | 2021-12-28 | Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210190113A KR20230100338A (en) | 2021-12-28 | 2021-12-28 | Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20230100338A true KR20230100338A (en) | 2023-07-05 |
Family
ID=87158863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210190113A KR20230100338A (en) | 2021-12-28 | 2021-12-28 | Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20230100338A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140026384A (en) | 2011-04-08 | 2014-03-05 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polybenzoxazole resin and precursor thereof |
-
2021
- 2021-12-28 KR KR1020210190113A patent/KR20230100338A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140026384A (en) | 2011-04-08 | 2014-03-05 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polybenzoxazole resin and precursor thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109486188B (en) | Polyamide acid resin and polyamide imide film | |
| CN109734908B (en) | Polyamide acid and preparation method thereof, polyimide and preparation method of polyimide film | |
| CN107531902B (en) | Polyimide resin and film using the same | |
| TW201512345A (en) | Polyimide precursor and polyimide | |
| JP2009518500A (en) | Polyimide film | |
| KR102246218B1 (en) | Polyamic acid composition, method for preparing the same and polyimide film comprising the same | |
| KR101837946B1 (en) | Polyimide Resin and Film Thereof | |
| EP1832618A1 (en) | Fluorinated diamine and polymer made from the same | |
| KR102422752B1 (en) | Novel tetracarboxylic dianhydride and polyimide and polyimide copolymer obtained from acid dianhydride | |
| KR101971155B1 (en) | Diamine monomer, transparent polyimide comprising the same, and the preparation method thereof | |
| KR20140059629A (en) | Polyimide precursor composition, polyimide prepared therefrom, and film including the polyimide | |
| KR20190003394A (en) | Polyimide-based block copolymers and polyimide-based film comprising the same | |
| KR102262746B1 (en) | Polyamic acid composition and polyimide substrate | |
| JP2021161285A (en) | Polyimide system adhesive | |
| JP2008303372A (en) | Polyimide precursor having asymmetric structure, polyimide, and their production methods | |
| JP5547874B2 (en) | Polyimide resin | |
| TW201815891A (en) | Method for preparing adamantane-containing polyimide having properties such as low dielectric constant, high glass transition temperature (Tg) and good processability | |
| KR101994976B1 (en) | Polyimide-based block copolymers and polyimide-based film comprising the same | |
| KR102439488B1 (en) | Method for producing polyimide film with excellent transparency and flexibility | |
| KR102246227B1 (en) | Polyamic acid composition, method for preparing the same and polyimide film comprising the same | |
| KR20230100338A (en) | Diamine compound and polybenzoxazole-polyimide copolymer using same, polybenzoxazole-polyimide copolymer film | |
| KR102268338B1 (en) | Precursor of polyimide and polyimide manufactured thereof and polyimide film including the same | |
| KR20150078925A (en) | Polyimidesiloxane Copolymer and Film Made Therefrom | |
| JP2003041189A (en) | Varnish and cross-linkable polyimide | |
| TWI542618B (en) | Polyamic acid blend and method for preparing the same and method for preparing polyimide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal |