KR20230000952A - Anthraquinone derivative tetramine monomer, black intrinsic polyimide derived from anthraquinone derivative tetramine monomer and preparation methods thereof - Google Patents
Anthraquinone derivative tetramine monomer, black intrinsic polyimide derived from anthraquinone derivative tetramine monomer and preparation methods thereof Download PDFInfo
- Publication number
- KR20230000952A KR20230000952A KR1020220053136A KR20220053136A KR20230000952A KR 20230000952 A KR20230000952 A KR 20230000952A KR 1020220053136 A KR1020220053136 A KR 1020220053136A KR 20220053136 A KR20220053136 A KR 20220053136A KR 20230000952 A KR20230000952 A KR 20230000952A
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- South Korea
- Prior art keywords
- monomer
- anthraquinone
- anthraquinone derivative
- tetraamine
- black
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 118
- 229920001721 polyimide Polymers 0.000 title claims abstract description 78
- 239000004642 Polyimide Substances 0.000 title claims abstract description 60
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 title 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 23
- 125000003277 amino group Chemical group 0.000 claims description 22
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 16
- GUAACGKXPUGLAQ-UHFFFAOYSA-N 2,4,5,7-tetraamino-1,8-dihydroxyanthracene-9,10-dione Chemical compound NC1=C(C=2C(C3=C(C(=CC(=C3C(C=2C(=C1)N)=O)N)N)O)=O)O GUAACGKXPUGLAQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 8
- QBPFLULOKWLNNW-UHFFFAOYSA-N chrysazin Chemical compound O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O QBPFLULOKWLNNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- YYOOOMNEONKALI-UHFFFAOYSA-N 1,8-dihydroxy-2,4,5,7-tetranitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=C([N+]([O-])=O)C(O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC([N+]([O-])=O)=C2O YYOOOMNEONKALI-UHFFFAOYSA-N 0.000 claims description 5
- 229940076442 9,10-anthraquinone Drugs 0.000 claims description 5
- GJCHQJDEYFYWER-UHFFFAOYSA-N 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=CC(O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O GJCHQJDEYFYWER-UHFFFAOYSA-N 0.000 claims description 4
- 238000006396 nitration reaction Methods 0.000 claims description 4
- IAWQUHCVFXQBMC-UHFFFAOYSA-N 1,3-benzoxazol-5-amine Chemical compound NC1=CC=C2OC=NC2=C1 IAWQUHCVFXQBMC-UHFFFAOYSA-N 0.000 claims description 2
- ZJYIRVSPPOOPCL-UHFFFAOYSA-N 1,3-benzoxazol-6-amine Chemical compound NC1=CC=C2N=COC2=C1 ZJYIRVSPPOOPCL-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 claims description 2
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 2
- MESFSCWCECYZNL-UHFFFAOYSA-N 2-amino-5-[3-(4-amino-3-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=C(O)C(N)=CC=C1OC1=CC=CC(OC=2C=C(O)C(N)=CC=2)=C1 MESFSCWCECYZNL-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006358 imidation reaction Methods 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims 1
- IBKFNGCWUPNUHY-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-6-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2O1 IBKFNGCWUPNUHY-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 230000000802 nitrating effect Effects 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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Abstract
Description
본 출원은 유기 합성 기술분야에 관한 것으로, 더 구체적으로는, 안트라퀴논 유도체 테트라아민 단량체, 안트라퀴논 유도체 테트라아민 단량체의 제조 방법, 이 안트라퀴논 유도체 테트라아민 단량체로부터 유래된 진성 흑색 폴리이미드 및 이 진성 흑색 폴리이미드의 제조 방법에 관한 것이다.This application relates to the field of organic synthesis technology, and more specifically, to an anthraquinone derivative tetraamine monomer, a method for preparing an anthraquinone derivative tetraamine monomer, an intrinsic black polyimide derived from the anthraquinone derivative tetraamine monomer, and a binary intrinsic black polyimide derived from the anthraquinone derivative tetraamine monomer. It relates to a method for producing black polyimide.
흑색 폴리이미드(PI) 필름은 불투명하고 낮은 광 흡수성, 낮은 광 투과율 및 낮은 광 반사 계수 등의 특성이 있어서, 다음과 같은 분야에 유용하게 적용될 수 있다. (1) 연성 회로판(FPC) 기판 필름: 흑색은 빛을 효과적으로 차단하여 회로 설계가 경쟁 업체에 의해 깨지는 것을 방지할 수 있으며, 그리고 흑색은 단순한 색상임으로 간결 미학의 요구 사항에 더 부합하고; (2) 리튬 배터리: 리튬 배터리 팩의 연결 시트의 절연 보호용으로 흑색 폴리이미드는 빛을 차단하여 구리의 산화를 방지할 수 있고; (3) 무선 충전: 무선 충전에는 코일의 절연 보호용으로 초박형 흑색 폴리이미드필름 겔을 이용해야 하지만 아직까지 요구 사항을 충족할 만한 흑색 폴리이미드가 없은 현실로 인해 그 대신 일반 폴리이미드에 카본 블랙이 코팅된 것을 사용하고 있고; (4) 항공 우주: 인공 위성의 안테나용으로 촬영 시스템 및 센서에 대한 여러 가지 미광의 간섭을 제거하거나 피할 수 있으며, 고정 광학 감쇠기 및 광학 터미네이터의 제조를 위한 광흡수 필름으로 적용될 수 있다.A black polyimide (PI) film is opaque and has properties such as low light absorption, low light transmittance, and low light reflection coefficient, so it can be usefully applied to the following fields. (1) Flexible circuit board (FPC) substrate film: black can effectively block light to prevent circuit design from being broken by competitors, and black is a simple color, which more meets the requirements of concise aesthetics; (2) lithium battery: for insulation protection of the connecting sheet of the lithium battery pack, black polyimide can block light to prevent oxidation of copper; (3) Wireless charging: For wireless charging, ultra-thin black polyimide film gel must be used to protect the insulation of the coil. you are using the old one; (4) Aerospace: It can eliminate or avoid the interference of various stray light to imaging systems and sensors for antennas of artificial satellites, and can be applied as light-absorbing films for the manufacture of fixed optical attenuators and optical terminators.
현재, 흑색 PI필름의 제조 방법은 대략적으로 (1) 그래핀, 페릴렌계 블랙 및 기타 유무기 충전제를 첨가하는 방식; (2) 특수 단량체를 사용하여 폴리이미드 분자 사슬의 전하 이동 착물의 형성을 증가시키는 방식 등이 있다. 그 예로는 유(劉) 등(J Polym Res (2019) 26:171)은 전자가 풍부한 방향족 디아민 단량체, 4,4´-디아미노디페닐아민(NDA)과 PMDA를 사용하여 공중합하였는데 그러나 NDA 중합체를 100%로 사용해도 폴리머의 색상은 여전히 흑색으로 변하지 않았다. 따라서, 컨쥬게이션에 의해 폴리이미드의 완전한 흑색 구현이 불가능하고, 특수 단량체가 대량으로 사용되어서 흑색 폴리이미드 필름의 원가가 상승하게 된다. 또한 공개 번호 CN109180936A의 중국 발명은 상용화 디아민과 공중합한 방식을 사용하고 둘의 조성비를 조절하여 제조된 일련의 진성 흑색 폴리이미드를 출원했다. 공개 번호 CN111574426A의 중국 발명은 이소인디고 구조를 포함한 디아민 단량체를 설계 합성하고 이를 상용화 이무수물과 단독 중합하여 제조된 일련의 진성 흑색 폴리이미드를 출원했다.Currently, the production method of black PI film is approximately (1) a method of adding graphene, perylene-based black and other organic/inorganic fillers; (2) a method of increasing the formation of charge transfer complexes of polyimide molecular chains by using special monomers; and the like. For example, Yu et al. (J Polym Res (2019) 26:171) copolymerized an electron-rich aromatic diamine monomer, 4,4'-diaminodiphenylamine (NDA), with PMDA, but the NDA polymer Even when 100% was used, the color of the polymer still did not change to black. Therefore, it is impossible to realize a complete black color of polyimide by conjugation, and a large amount of special monomers are used, which increases the cost of the black polyimide film. In addition, the Chinese invention publication number CN109180936A has filed a series of intrinsic black polyimides prepared by copolymerizing with commercially available diamines and adjusting the composition ratio of the two. The Chinese invention publication number CN111574426A has filed a series of intrinsic black polyimides prepared by designing and synthesizing diamine monomers with isoindigo structures and homopolymerizing them with commercially available dianhydrides.
그러나, 상술한 흑색 폴리이미드 제조 방법은 다음과 같은 문제점이 있다.However, the black polyimide manufacturing method described above has the following problems.
1. 기계적 특성이 불균일한 현상과 핀홀을 피하기 위해 PI 매트릭스에 균일하게 분산하도록 충전제를 미리 개질해야 하므로 제조 공정이 복잡하다.1. The manufacturing process is complicated because the filler must be modified in advance to be uniformly dispersed in the PI matrix to avoid pinholes and non-uniform mechanical properties.
2. 무기 충전제의 도입은 PI 필름의 기계적 특성과 열적 특성을 어느 정도로 높일 수 있지만 PI 필름의 절연성 및 파열 강도를 파괴하게 되여 전자 산업 분야에서의 적용에 악영향을 미칠 것이다.2. The introduction of inorganic fillers can improve the mechanical and thermal properties of the PI film to some extent, but will destroy the insulation and burst strength of the PI film, adversely affecting its application in the electronic industry.
3. 유기 안료의 도입은 PI 필름의 전기적 특성에 미칠 영향을 피할 수 있지만 낮은 열분해 온도로 인해 고온 분야에서 PI 필름의 적용을 방해하며 환경 요인에 의해 쉽게 분해되어 내후성이 약해지게 된다. 3. The introduction of organic pigments can avoid the influence on the electrical properties of the PI film, but its low thermal decomposition temperature hinders the application of the PI film in high-temperature fields, and it is easily decomposed by environmental factors, resulting in poor weatherability.
4. 기존의 진성 흑색 폴리이미드는 광 투과율이 여전히 부족하고 가시광선 전대역에 걸쳐 모두 1% 미만이 된 것이 확보될 수 없다.4. Existing intrinsic black polyimides are still insufficient in light transmittance and cannot be secured to be less than 1% in all visible light bands.
이에, 진성 흑색 폴리이미드 및 그의 제조 방법에 대한 개발이 당업계에서 계속적으로 요구되고 있다.Accordingly, there is a continuous demand in the art for development of intrinsic black polyimide and a method for preparing the same.
본 출원의 목적은 상기와 같은 문제점을 해결하기 위한 것으로 안트라퀴논 구조에 다수의 조색단을 도입함으로써 그 흡수 파장을 넓은 범위로 확장시킬 수 있는 몰 흡수 계수가 높고 신규한 안트라퀴논 유도체 단량체를 제공하는 데 있다.An object of the present application is to solve the above problems, and to provide a novel anthraquinone derivative monomer having a high molar absorption coefficient and capable of extending its absorption wavelength to a wide range by introducing a plurality of auxochromes into the anthraquinone structure. there is
본 출원의 다른 목적은 안트라퀴논 유도체 테트라아민 단량체의 제조 방법을 제공하는 데 있다. Another object of the present application is to provide a method for preparing an anthraquinone derivative tetraamine monomer.
본 출원의 또 다른 목적은 이 안트라퀴논 유도체 테트라아민 단량체를 이용하여 합성된 진성 흑색 폴리이미드를 제공하는 데 있다.Another object of the present application is to provide an intrinsic black polyimide synthesized using the anthraquinone derivative tetraamine monomer.
본 출원의 또 다른 목적은 진성 흑색 폴리이미드의 제조 방법을 제공하는 데 있다. Another object of the present application is to provide a method for producing intrinsic black polyimide.
상술한 기술 과제를 해결하기 위한 본 출원의 기술적 해결 수단은, 제1 측면에 따르면, 하기 식 I로 표시된 구조를 갖는 것을 특징으로 하는 안트라퀴논 유도체 테트라아민 단량체를 제공한다:According to the first aspect, the technical solution of the present application for solving the above technical problems provides an anthraquinone derivative tetraamine monomer characterized by having a structure represented by the following formula I:
식 I Formula I
일 구체적인 실시예에 있어서, 이 안트라퀴논 유도체 테트라아민 단량체 중 2개의 아민기만은 중축합 반응이 가능하므로 선형 중합체를 얻을 수 있다.In one specific embodiment, a linear polymer can be obtained because only two amine groups in the anthraquinone derivative tetraamine monomer can undergo a polycondensation reaction.
제2 측면에 따르면, 본 출원은 제1 측면에 따른 안트라퀴논 유도체 테트라아민 단량체의 제조 방법에 있어서, 진한 황산 및 진한 질산의 존재하에, 1,8-디히드록시-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함하는 것을 특징으로 하는 안트라퀴논 유도체 테트라아민 단량체의 제조 방법을 제공한다.According to the second aspect, the present application provides a method for producing an anthraquinone derivative tetraamine monomer according to the first aspect, in the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8-dihydroxy-9,10-anthraquinone Nitration with 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and reduction of the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5, Obtaining 7-tetraamino-9,10-anthraquinone; It provides a method for producing an anthraquinone derivative tetraamine monomer comprising the.
다른 실시예에 있어서, 본 출원은 제1 측면에 따른 안트라퀴논 유도체 테트라아민 단량체의 제조 방법에 있어서, 진한 황산 및 진한 질산의 존재하에, 1,8-디히드록시-4,5-디니트로-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함하는 것을 특징으로 하는 안트라퀴논 유도체 테트라아민 단량체의 제조 방법을 제공한다.In another embodiment, the present application provides a method for preparing an anthraquinone derivative tetraamine monomer according to the first aspect, in the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8-dihydroxy-4,5-dinitro- 9,10-anthraquinone is nitrated with 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and the nitro group is reduced to an amino group to obtain 1,8-dihydroxy Obtaining -2,4,5,7-tetraamino-9,10-anthraquinone; provides a method for producing an anthraquinone derivative tetraamine monomer comprising the steps of:
제3 측면에 따르면, 본 출원은 제1 측면에 따른 안트라퀴논 유도체 테트라아민 단량체, 디아민 단량체 및 무수물 단량체를 반응시켜 형성되고, 상기 안트라퀴논 유도체 테트라아민 단량체는 중량% 기준으로 안트라퀴논 유도체 테트라아민 단량체와 디아민 단량체의 총 몰수에 대하여 4% 내지 100%로 포함되는 것을 특징으로 하는 진성 흑색 폴리이미드를 제공한다. 바람직한 일 실시예에 있어서, 상기 안트라퀴논 유도체 테트라아민 단량체는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 총 몰수에 대하여 4% 내지 80%로 포함되는 것이다. 바람직한 일 실시예에 있어서, 상기 안트라퀴논 유도체 테트라아민 단량체는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체 총 몰수에 대하여 4% 내지 10%로 포함되는 것이다. According to the third aspect, the present application is formed by reacting the anthraquinone derivative tetraamine monomer, the diamine monomer and the anhydride monomer according to the first aspect, wherein the anthraquinone derivative tetraamine monomer is based on weight%. and 4% to 100% based on the total number of moles of diamine monomers. In a preferred embodiment, the anthraquinone derivative tetraamine monomer is included in an amount of 4% to 80% based on the total number of moles of the anthraquinone derivative tetraamine monomer and the diamine monomer. In a preferred embodiment, the anthraquinone derivative tetraamine monomer is included in an amount of 4% to 10% based on the total number of moles of the anthraquinone derivative tetraamine monomer and the diamine monomer.
제1 측면에 따른 일 실시예에 있어서, 반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1 :1이다. 이 실시예에 있어서, 안트라퀴논 유도체 테트라아민 단량체는 분자내에 수소결합이 존재하므로 오르토 아민기와 파라 아민기의 활성이 상이하며, 오르토 위치의 2개 아민기만이 공중합 반응에 참여할 수 있는 것이다.In one embodiment according to the first aspect, the ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction This is 1:1. In this embodiment, since the anthraquinone derivative tetraamine monomer has a hydrogen bond in the molecule, the activities of the ortho amine group and the para amine group are different, and only two amines at the ortho position can participate in the copolymerization reaction.
제1 측면에 따른 일 실시예에 있어서, 상기 무수물 단량체는 4,4’-(아세틸렌-1,2,-디일)디프탈릭 언하이드라이드, 피로멜리틱디안하이드라이드, 3,3’,4,4’-비페닐테트라카르복실릭디안하이드라이드, 3,3',4,4'-벤조페논테트라카복실릭디안하이드라이드, 2,2’-비스(3,4-디카르복실산)헥사플루오로프로판 디안하이드라이드, 4,4'-옥시디프탈릭안하이드라이드, 2,3,3',4'-비페닐테트라카르복실릭 디언하이드라이드, 3,3′,4,4′-디페닐술폰 테트라카복실릭 디언하이드라이드, 나프탈렌-1,4,5,8-테트라카르복실릭 디언하이드라이드 및 디페닐 설파이드 디안하이드라이드에서 선택된 하나 또는 그 이상인 것이다.In one embodiment according to the first aspect, the anhydride monomer is 4,4'-(acetylene-1,2,-diyl) diphthalic anhydride, pyromellitic dianhydride, 3,3',4, 4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid) hexafluoro Lopropane dianhydride, 4,4'-oxydiphthalic anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl It is one or more selected from sulfone tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride and diphenyl sulfide dianhydride.
제1 측면에 따른 일 실시예에 있어서, 상기 디아민 단량체는 m-페닐렌디아민, p-페닐렌디아민, 4,4’-디아미노비페닐, 4,4’-디아미노디페닐에테르, 3,4’-디아미노디페닐에테르, 4,4’-디아미노벤조페논, 4,4'-디아미노디페닐메탄, 1,3-비스(4-아미노페녹시)벤젠, 1,4-비스(4-아미노페녹시)벤젠, 4,4’-디아미노-2,2’-디메틸비페닐, 2-(4-아미노페닐)-5-아미노벤족사졸, 2-(4-아미노페닐)-5-아미노벤즈이미다졸, 1,4-비스(3-아미노페녹시)벤젠, 1,3-비스(3-하이드록시-4-아미노페녹시)벤젠, 2-(4-아미노페닐)-6-아미노벤족사졸, 2,2-p-페닐-비스(5-아미노벤족사졸) 및 2,2’-p-페닐-비스(6-아미노벤족사졸)에서 선택된 하나 또는 그 이상인 것이다.In one embodiment according to the first aspect, the diamine monomer is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis( 4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5 -Aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6- It is one or more selected from aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoxazole), and 2,2'-p-phenyl-bis(6-aminobenzoxazole).
제4 측면에 따르면, 본 출원은 제3 측면에 따른 진성 흑색 폴리이미드의 제조 방법에 있어서,According to a fourth aspect, the present application provides a method for producing an intrinsic black polyimide according to the third aspect,
(1) 무수 및 무산소 조건에서 제1 측면에 따른 안트라퀴논 유도체 테트라아민 단량체와 디아민 단량체를 기 설정된 중량비로 혼합하고 용해될 때까지 교반하여 균질화된 용액을 형성한 후에, 산무수물 단량체를 첨가하고 냉수욕조에서 기 설정된 시간 동안 교반하면서 반응시켜 흑색 폴리아믹산 용액을 수득하는 단계;(1) Under anhydrous and oxygen-free conditions, the anthraquinone derivative tetraamine monomer and diamine monomer according to the first aspect are mixed in a predetermined weight ratio and stirred until dissolved to form a homogenized solution, then acid anhydride monomer is added and cold water Obtaining a black polyamic acid solution by reacting while stirring for a predetermined time in a bath;
(2) 흑색 폴리아믹산 용액을 이미드화시켜 진성 흑색 폴리이미드를 수득하는 단계;를 포함하는 것을 특징으로 하는 진성 흑색 폴리이미드의 제조 방법을 제공한다. (2) imidizing the black polyamic acid solution to obtain intrinsic black polyimide;
제4 측면에 따른 일 실시예에 있어서, 상기 흑색 폴리아믹산 용액을 이미드화시키는 단계는 흑색 폴리아믹산 용액을 소포하고, 깨끗하고 건조한 유리판에 자동 코팅기로 균일하게 코팅하여, 열 이미드화 방식에 의해 이미드화 반응시키는 단계;를 포함하며, 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행된 것이다.In one embodiment according to the fourth aspect, in the step of imidizing the black polyamic acid solution, the black polyamic acid solution is defoamed, uniformly coated on a clean and dry glass plate with an automatic coater, and already obtained by thermal imidization. Including, the temperature raising and curing process is performed in the order of 80 ℃ / 3h, 100 ℃ / 1h, 200 ℃ / 2h, 300 ℃ / 4h.
종래기술과 비해, 본 출원에 따른 흑색 폴리이미드는 차광 특성이 우월하고, 우수한 기계적 특성, 열적 안정성 및 유전 특성을 가지며 전대역에 걸쳐 광 투과율이 1% 미만인 효과가 있다.Compared to the prior art, the black polyimide according to the present application has superior light blocking properties, excellent mechanical properties, thermal stability and dielectric properties, and has an effect of having a light transmittance of less than 1% over all bands.
도 1은 실시예 1에 따른 안트라퀴논 유도체 테트라아민 단량체의 자외선 흡수 스펙트럼을 나타낸 것이다.
도 2는 실시예 1에 따른 안트라퀴논 유도체 테트라아민 단량체의 적외선 스펙트럼을 나타낸 것이다.
도 3은 실시예 1에 따른 안트라퀴논 유도체 테트라아민 단량체의 수소 NMR 스펙트럼을 나타낸 것이다.
도 4는 실시예 3에 따른 폴리이미드의 백색 A4 용지에서의 광학 사진을 나타낸 것이다.Figure 1 shows the ultraviolet absorption spectrum of the anthraquinone derivative tetraamine monomer according to Example 1.
Figure 2 shows the infrared spectrum of the anthraquinone derivative tetraamine monomer according to Example 1.
Figure 3 shows the hydrogen NMR spectrum of the anthraquinone derivative tetraamine monomer according to Example 1.
4 shows an optical photograph of the polyimide according to Example 3 on a white A4 paper.
흑색 폴리이미드는 광범위한 적용 잠재력을 가지고 있어 국내외 많은 연구팀의 관심을 불러일으키고 있다. Black polyimide has a wide range of application potential and is attracting the attention of many research teams at home and abroad.
예를 들어, 특허 공개 번호 CN105860112B의 중국 발명에는 PI의 전구체인 폴리아믹산(PAA) 용액과 폴리아크릴로니트릴 용액을 블렌딩함으로써 PI로서의 우수한 기계적 특성과 예비 산화된 PAN으로서의 불투명도를 동시 갖는 흑색 필름을 획득하는 방법이 개시되었다. For example, in the Chinese invention of Patent Publication No. CN105860112B, a polyamic acid (PAA) solution, which is a precursor of PI, and a polyacrylonitrile solution are blended to obtain a black film having both excellent mechanical properties as PI and opacity as pre-oxidized PAN. A method has been disclosed.
공개 번호 CN105482115B의 중국 발명에는 폴리아믹산 용액에 카본 블랙 또는 탄소 섬유 분말과 같은 흑색 충전제 및 커플링제를 첨가하고, 소포하여 필름으로 캐스팅하는 방법이 개시되었다. Chinese Invention Publication No. CN105482115B discloses a method of adding a black filler such as carbon black or carbon fiber powder and a coupling agent to a polyamic acid solution, followed by defoaming and casting into a film.
공개 번호 CN108017910A의 중국 출원 발명에는 카본 블랙 안료를 폴리아믹산 용액에 첨가하고, 여과하여 응집제를 첨가하고 소포하여 필름으로 캐스팅하는 방법이 개시되었다.The Chinese application for invention of Publication No. CN108017910A discloses a method of adding a carbon black pigment to a polyamic acid solution, filtering, adding a coagulant, defoaming, and casting into a film.
공개 번호 CN110387040A의 중국 출원 발명에는 전이 금속 질화물, 전이 금속 탄화물, 전이 금속 붕화물과 귀금속 및 그래핀, 탄소계 나노물질, 흑색 안료, 흑색 염료 등과 같은 전도성 나노 입자를 폴리아믹산 용액에 첨가하고 소포하여 필름으로 캐스팅함으로써 차폐 특성을 ⒣ 높인 방법이 개시되었다. In the invention of the Chinese application of Publication No. CN110387040A, transition metal nitride, transition metal carbide, transition metal boride and noble metal, and conductive nanoparticles such as graphene, carbon-based nanomaterials, black pigments, black dyes, etc. are added to a polyamic acid solution and defoamed, A method of increasing the shielding property (⒣) by casting into a film has been disclosed.
공개 번호 CN108976447A의 중국 출원 발명에는 입자 크기가 다른 카본 블랙 을 폴리아믹산 용액에 첨가하고, 소포하여 코팅하고 초박형 블랙 폴리이미드 필름을 제조하는 방법이 개시되었다.The Chinese application for invention publication number CN108976447A discloses a method for producing an ultra-thin black polyimide film by adding carbon black having different particle sizes to a polyamic acid solution, followed by defoaming and coating.
진성 흑색 폴리이미드는 차광성이 우수할 뿐만 아니라 단량체의 종류와 양에 대한 조절에 의해 기계적, 열적, 전기적 특성을 더욱 향상시킬 수 있다. 따라서 신규한 진성 흑색 폴리이미드의 제조 방법을 지속적으로 개발하는 것은 큰 의미가 있다.Intrinsic black polyimide not only has excellent light blocking properties, but also can further improve mechanical, thermal, and electrical properties by adjusting the type and amount of monomers. Therefore, it is of great significance to continuously develop a novel intrinsic black polyimide production method.
일 실시예에 있어서, 본 출원은 하기 식 I로 표시된 구조를 갖는 신규한 안트라퀴논 유도체 테트라아민 단량체를 제공한다:In one embodiment, the present application provides a novel anthraquinone derivative tetraamine monomer having the structure represented by Formula I:
식 I Formula I
일 실시예에 있어서, 본 출원은 상술한 안트라퀴논 유도체 테트라아민 단량체의 제조 방법에 있어서, 진한 황산 및 진한 질산의 존재하에, 1,8-디히드록시-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함하는 안트라퀴논 유도체 테트라아민 단량체의 제조 방법을 제공한다.In one embodiment, the present application relates to the preparation method of the above-described anthraquinone derivative tetraamine monomer, in the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8-dihydroxy-9,10-anthraquinone is mixed with 1,8 Nitration with -dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and reduction of the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetra Obtaining amino-9,10-anthraquinone; provides a method for preparing an anthraquinone derivative tetraamine monomer, including.
다른 실시예에 있어서, 안트라퀴논 유도체 테트라아민 단량체의 제조 방법은 진한 황산 및 진한 질산의 존재하에, 1,8-디히드록시-4,5-디니트로-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함할 수 있다.In another embodiment, a method for preparing an anthraquinone derivative tetraamine monomer is prepared by converting 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone to 1,8-dihydroxy-4,5-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid. Nitration with -dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and reduction of the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetra Obtaining amino-9,10-anthraquinone; may include.
일 실시예에 있어서, 본 출원은 상술한 안트라퀴논 유도체 테트라아민 단량체, 디아민 단량체 및 무수물 단량체를 반응시켜 형성된 진성 흑색 폴리이미드를 제공한다. 본 실시예에서는 안트라퀴논 유도체 테트라아민 단량체의 함량은 전체 아민계 단량체 총 몰수의 4% 내지 100%인 것이 바람직하다. 만약, 안트라퀴논 유도체 테트라아민 단량체의 함량은 전체 아민계 단량체 총 몰수의 4% 미만인 경우, 제조된 폴리이미드는 순수한 흑색이 아닌 황색 내지 짙은 녹색을 띤다. 또한 안트라퀴논 유도체 테트라아민 단량체의 함량은 전체 아민계 단량체 총 몰수의 10%를 초과하는 경우, 수득한 흑색 진성 폴리이미드 필름의 LAB 값은 크게 변하지 않는다. 따라서, 바람직한 일 구현예에 있어서, 안트라퀴논 유도체 테트라아민 단량체의 함량은 전체 아민 단량체의 총 몰수의 4% 내지 10%인 것이 바람직하다.In one embodiment, the present application provides an intrinsic black polyimide formed by reacting the above-described anthraquinone derivative tetraamine monomer, diamine monomer, and anhydride monomer. In this embodiment, the content of the anthraquinone derivative tetraamine monomer is preferably 4% to 100% of the total number of moles of the total amine monomers. If the content of the anthraquinone derivative tetraamine monomer is less than 4% of the total number of moles of the amine monomers, the prepared polyimide is not pure black but yellow to dark green. Also, when the content of the anthraquinone derivative tetraamine monomer exceeds 10% of the total number of moles of the total amine monomers, the LAB value of the obtained black intrinsic polyimide film does not change significantly. Therefore, in a preferred embodiment, the content of the anthraquinone derivative tetraamine monomer is preferably 4% to 10% of the total number of moles of the total amine monomers.
본 출원은 상술한 진성 흑색 폴리이미드의 제조 방법에 있어서, 먼저 안트라퀴논 유도체 테트라아민 단량체, 디아민 단량체 및 무수물 단량체를 반응시킴으로써 폴리아믹산 용액을 수득하는 단계; 폴리아믹산 용액을 이미드화시켜 진성 흑색 폴리이미드를 수득하는 단계;를 포함하는 진성 흑색 폴리이미드의 제조 방법에 더 관한 것이다.The present application relates to the above-described intrinsic black polyimide production method, comprising: first reacting an anthraquinone derivative tetraamine monomer, a diamine monomer, and an anhydride monomer to obtain a polyamic acid solution; It further relates to a method for producing an intrinsic black polyimide comprising the step of imidizing the polyamic acid solution to obtain an intrinsic black polyimide.
실시예 Example
이하, 실시예를 참조하여 본 출원을 더욱 상세하게 설명하기로 한다. 특별히 설명되지 않는 한 사용된 모든 화학 원료는 시장에서 구입할 수 있는 것이다. 하기 실시예가 단지 예시적인 것이며, 이는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 기술자라면 잘 이해할 수 있는 것이다. 후술할 실시예에 사용된 특성 평가 방법은 다음과 같다.Hereinafter, the present application will be described in more detail with reference to examples. All chemical raw materials used were commercially available unless otherwise specified. The following examples are merely illustrative, which can be well understood by those skilled in the art to which the present invention belongs. The characteristic evaluation method used in Examples to be described later is as follows.
수소 NMR 스펙트럼(1H NMR):Hydrogen NMR spectrum ( 1 H NMR):
반응 생성물 및 중간체에 대한 NMR (1H NMR) 스펙트럼은 Bruker AVANCE III HD 400/500(독일)로 얻었다. 시료는 약 10 mg의 샘플을 깨끗하고 건조한 유리 NMR 튜브에 중수소로 치환된 시약 0.5 mL에 완전히 용해시킨 방법에 의해 제조되었다. 잘 용해되는 생성물은 중수소로 치환된 클로로포름(CDCl3)을 용매로 사용하여 실온에서 용해시키고, 덜 용해되는 생성물은 중수소로 치환된 디메틸 설폭사이드(DMSO-d6)를 용매로 사용하고, DMSO-d6은 낮은 실온에서 응고되기 쉬워서 투입 전에 헤어 드라이어로 불어 융화해야 한다. 상온에서 측정 시 테트라메틸실란(TMS)을 내부 표준 물질로 사용하여 화학적 이동은 0ppm이다.NMR ( 1 H NMR) spectra for reaction products and intermediates were obtained on a Bruker
푸리에 변환 적외분광법(FT-IR):Fourier Transform Infrared Spectroscopy (FT-IR):
건조한 환경에서 Nicolet iS5(ThermoFisher Scientific, Inc., USA) 푸리에 변환 적외선 분광기(FTIR)의 ATR 모드로 측정하였는데, 측정 전에, 먼저 단량체(4NADA)를 80℃의 진공 오븐에 넣어 2시간 동안 수분을 제거하였다. 스캔 범위는 4000-650cm-1, 해상도는 2cm-1, 스캔 횟수는 32회로 설정하여 평균값을 자동으로 구하였다.The ATR mode of a Nicolet iS5 (ThermoFisher Scientific, Inc., USA) Fourier Transform Infrared Spectrometer (FTIR) was measured in a dry environment. Prior to measurement, the monomer (4NADA) was first placed in a vacuum oven at 80 ° C to remove moisture for 2 hours. did The scan range was set to 4000-650 cm −1 , the resolution was 2 cm −1 , and the number of scans was set to 32, and the average value was automatically obtained.
자외선-가시광선 스펙트럼(UV - Vis):Ultraviolet-Visible Spectrum (UV - Vis):
진성 흑색 폴리이미드 필름의 광 투과율은Shimadzu UV-2600 분광광도계(Shimadzu사, 일본)로 분석하였는데, 스캐닝 범위는 360-800cm-1로 설정하였다. 단량체의 UV 흡광도는 Shimadzu UV-2600 분광광도계(Shimadzu사, 일본)로 분석하였는데, 희석 용액에서의 흡광도를 측정하였다. 단량체의 농도는 30μM이고 선택된 용매는 N,N-디메틸포름아미드이다.The light transmittance of the intrinsic black polyimide film was analyzed with a Shimadzu UV-2600 spectrophotometer (Shimadzu, Japan), and the scanning range was set to 360-800 cm -1 . The UV absorbance of the monomer was analyzed with a Shimadzu UV-2600 spectrophotometer (Shimadzu, Japan), and the absorbance in the diluted solution was measured. The concentration of monomer is 30 μM and the chosen solvent is N,N-dimethylformamide.
CIELAB 색 공간:CIELAB color space:
제조된 진성 흑색 폴리이미드 필름의 반사율은 LAMBDA 950 UV/Vis/NIR 분광광도계(PerkinElmer사, 미국)로 측정되었는데, 사용된 CIE 표준 조명체 D65의 상대 스펙트럼 기능 분포와 CIE1976 표준 색도 관찰기를 결합하여, 내장된 변환 공식에 의해 색역 변환을 걸쳐 L*, a*, b* 매개 변수 값을 산출했다. 사용된 광원은 표준 광원 D65이고 관찰 각도는 10°이다.The reflectance of the prepared intrinsic black polyimide film was measured with a LAMBDA 950 UV/Vis/NIR spectrophotometer (PerkinElmer, USA), combining the relative spectral function distribution of the used CIE standard illuminator D65 with the CIE1976 standard chromaticity observer, The L * , a * , and b * parameter values were calculated across the color gamut conversion by the built-in conversion formula. The light source used is standard light source D65 and the viewing angle is 10°.
열적 특성 분석(TGA&DMA&TMA):Thermal Characterization (TGA&DMA&TMA):
진성 흑색 폴리이미드 필름의 열중량은 질소 분위기에서 TA Discovery 550 열중량 분석기(TGA)로 측정되었는데, 가스 흐름은 50mL/min이고 온도는 20℃/min 속도로 실온에서 120℃까지 승온하고 15분 동안 체류한 후, 다시 10℃/min 속도로 50℃에서 800℃까지 승온하였다.The thermogravimetry of the intrinsic black polyimide film was measured with a TA Discovery 550 thermogravimetric analyzer (TGA) in a nitrogen atmosphere, with a gas flow of 50 mL/min and a temperature of 20 °C/min from room temperature to 120 °C for 15 minutes. After staying, the temperature was raised again from 50°C to 800°C at a rate of 10°C/min.
유리전이온도(Tg)는 TA Q800 Dynamic Thermomechanical Analyzer(DMA)로 측정되었는데, 진성 흑색 폴리이미드 필름을 동일한 폭 0.5cm의 직사각형 스트립으로 절단하고, 질소 분위기에서 인가 주파수는 1Hz로 설정하고 온도는 5℃/min 속도로 30℃에서 500℃까지 승온하였다.The glass transition temperature (T g ) was measured with a TA Q800 Dynamic Thermomechanical Analyzer (DMA), in which the intrinsic black polyimide film was cut into rectangular strips with the same width of 0.5 cm, and the applied frequency was set to 1 Hz and the temperature was 5 The temperature was raised from 30°C to 500°C at a rate of °C/min.
진성 흑색 폴리이미드 필름의 열적 치수 안정성은 TA Q400 thermal mechanical analyzer(TMA)의 인장 모드로 온도 증가에 따른 샘플 스트립 크기의 변화를 측정하여 분석하였다. 진성 흑색 폴리이미드 필름은 폭(0.5cm)이 균일하고 가느다란 스트립 형상으로 준비하고, 정하중이 0.05N이고 승온 속도가 10℃/min이고 승온 범위가 실온 400℃까지이고 질소 유속이 50mL/min이다. 승온 절차는 2 단계로 나누어 수행되었는데, 제1 단계에서 동일한 속도로 승온한 후 냉각하여 이미드화 공정에서 필름에 잔존된 내부 응력을 제거하고, 제2 단계에서 400℃까지 승온함에 따른 곡선 데이터를 기록했다.The thermal dimensional stability of the intrinsic black polyimide film was analyzed by measuring the change in sample strip size with increasing temperature in the tensile mode of a TA Q400 thermal mechanical analyzer (TMA). The intrinsic black polyimide film is prepared in a thin strip shape with a uniform width (0.5 cm), a static load of 0.05 N, a heating rate of 10 ° C/min, a temperature raising range up to room temperature of 400 ° C, and a nitrogen flow rate of 50 mL/min. . The temperature raising procedure was performed in two steps. In the first step, the temperature was raised at the same rate and then cooled to remove the internal stress remaining in the film in the imidation process, and in the second step, the curve data was recorded as the temperature was raised to 400 ° C. did.
기계적 특성 분석:Mechanical Characterization:
진성 흑색 폴리이미드 필름의 기계적 특성은 SUST CMT1104 전자 만능 시험기(Sansi Taijie사)로 측정되었는데, 시편을 폭 1cm의 직사각형 스트립으로 절단하고 인장 속도는 5mm/min이고, ASTM D882-02 테스트 기준에 따라 여러 번 측정하여 유효한 결과치의 평균을 취했다.The mechanical properties of the intrinsic black polyimide film were measured with a SUST CMT1104 electronic universal testing machine (Sansi Taijie). The specimen was cut into rectangular strips with a width of 1 cm, the tensile speed was 5 mm/min, and several tests were performed according to the ASTM D882-02 test standard. Measurements were made and the average of valid results was taken.
유전 특성 분석:Dielectric characterization:
진성 흑색 폴리이미드 필름의 유전 특성은 N5227B 네트워크 분석기(Keysight사, 캐나다)로 측정되었는데, 시편은 측면 길이가 3*4mm보다 큰 직사각형 시편을 준비하고 유전 상수 및 유전 손실을 측정했다. 80℃에서 2시간 동안 건조한 후 센서에 넣고 테스트 주파수를 선택하여 측정되었다. 테스트 주파수는 24GHz, 40GHz 및 60GHz이고 샘플 두께는 25μm이고 매체는 공기이다. The dielectric properties of the intrinsic black polyimide film were measured with an N5227B network analyzer (Keysight, Canada). Rectangular specimens with side lengths greater than 3*4 mm were prepared and dielectric constant and dielectric loss were measured. After drying at 80° C. for 2 hours, it was put into a sensor and measured by selecting a test frequency. The test frequencies are 24 GHz, 40 GHz and 60 GHz, the sample thickness is 25 μm and the medium is air.
단량체 합성 실시예 Monomer Synthesis Example
실시예 1Example 1
1,8-디히드록시-9,10-안트라퀴논 (1.0mmol)을 3-neck 플라스크에 넣고, 0℃에서 진한 황산 5ml 및 진한 질산 4ml를 첨가하고 4 시간 동안 강하게 기계적으로 교반한 후, 분쇄된 얼음을 첨가하고, 용매를 흡인 여과로 제거하고, 고형분을 포화 탄산수소나트륨 수용액으로 세척하여 진공에서 건조시키고, 밤새 방치하여 황색 조 생성물 1을 수득했다.1,8-dihydroxy-9,10-anthraquinone (1.0 mmol) was put in a 3-neck flask, 5 ml of concentrated sulfuric acid and 4 ml of concentrated nitric acid were added at 0 ° C, and after vigorous mechanical stirring for 4 hours, pulverization Ice was added, the solvent was removed by suction filtration, and the solids were washed with saturated aqueous sodium hydrogen carbonate solution, dried in vacuo and left overnight to give yellow crude product 1.
실리카겔 크로마토그래피(?은 컬럼)에 의해 조 생성물 1을 정제하고, 용리액(메탄올)으로 용리하여 황색 생성물인 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논을 수득했다.Crude product 1 was purified by silica gel chromatography (silver column) and eluted with eluent (methanol) to obtain a yellow product, 1,8-dihydroxy-2,4,5,7-tetranitro-9,10- Anthraquinone was obtained.
상기 황색 생성물 1mmol을 칭량하여 플라스크에 넣어 에탄올에 용해시키고, Na2S·9H2O 8mmol을 칭량하여 증류수로 포화 상태까지 용해시켜 플라스크에 넣었다. 혼합물을 12 시간 동안 환류 반응시키고, 실온까지 냉각시킨 후, 준비된 얼음-물 혼합물에 첨가하면서 지속적으로 교반하였다. 여과한 후 물로 세척하고 밤새 방치하고 진공 건조하여 흑색 목적 생성물인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득했다.1 mmol of the above yellow product was weighed and put into a flask to dissolve in ethanol, and 8 mmol of Na 2 S·9H 2 O was weighed and dissolved in distilled water to saturation, and then placed in a flask. The mixture was refluxed for 12 hours, cooled to room temperature and added to the prepared ice-water mixture while stirring continuously. After filtration, it was washed with water, left overnight, and vacuum dried to obtain the desired black product, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.
상기 단량체의 자외선 흡수 스펙트럼 및 적외선 스펙트럼을 측정하였고, 그 결과를 각각 도 1 및 도 2에 나타내었다. 도 1에 도시된 바와 같이, 단량체는 400-700 nm의 가시광선 대역에서 강한 흡수도를 가지면서 반치폭이 거의 150nm에 이르며, 자체의 평면 공액 구조와 분자내 수소 결합의 영향에 의해 단량체는 흑색을 띠게 된 것이다. 도 2에 도시된 바와 같이, 3500-3200 cm-1 구간에 나타난 적외선 흡수 피크는 오르토 아미노기와 파라 아미노기에 차례로 해당하고, 피크의 이동과 피크의 확장은 후자가 분자내 수소 결합을 가지고 있고, 즉 두 아미노기 사이의 반응성에 차이가 있음을 모두 나타낼 수 있다. 1567cm-1 에 나타난 카르보닐 피크는 역시 분자 내에 다양한 수소 결합이 있고, 즉 카르보닐기는 히드록실기 및 파라 아미노기와 모두 분자내 수소 결합을 형성함을 나타낼 수 있다. 이러한 특이한 수소 결합으로 인해 일반적으로 1700cm-1 부근에서 흔히 나타냈던 카르보닐 피크가 1567cm-1로 떨어지게 했다.An ultraviolet absorption spectrum and an infrared spectrum of the monomer were measured, and the results are shown in FIGS. 1 and 2, respectively. As shown in FIG. 1, the monomer has a strong absorption in the visible light range of 400-700 nm and a full width at half maximum of nearly 150 nm. it has become As shown in Figure 2, the infrared absorption peak appearing in the 3500-3200 cm -1 section corresponds to the ortho amino group and the para amino group in turn, and the shift of the peak and the broadening of the peak indicate that the latter has an intramolecular hydrogen bond, that is Both can indicate that there is a difference in reactivity between the two amino groups. The carbonyl peak appearing at 1567cm -1 can also indicate that there are various hydrogen bonds in the molecule, that is, the carbonyl group forms intramolecular hydrogen bonds with both the hydroxyl group and the para-amino group. Due to this specific hydrogen bond, the carbonyl peak, which was generally shown around 1700 cm -1 , fell to 1567 cm -1 .
도 3에서도 이러한 아미노기 사이의 활성 차이, 즉 오르토 아미노기 수소의 NMR 피크가 더 높은 필드에 나타난 것은 확인되었다.In FIG. 3, it was also confirmed that the activity difference between these amino groups, that is, the NMR peak of the hydrogen of the ortho amino group appeared in a higher field.
실시예 1에 따른 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논의 몰 흡광 계수도 측정되었다.The molar extinction coefficient of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone according to Example 1 was also measured.
몰 흡광 계수의 측정 방법은 다음과 같다.The method for measuring the molar extinction coefficient is as follows.
몰 흡광 계수는 농도가 1mol/L일 때의 흡광 계수를 의미하며, ε으로 나타난다. 하기 식에 의해 산출한다. The molar extinction coefficient means the extinction coefficient when the concentration is 1 mol/L, and is represented by ε. It is calculated by the following formula.
여기서 A는 UV 분광 광도계로 측정된 UV 흡광도이고, ε는 몰 흡광 계수이고, b는 흡수 셀의 두께이고, c는 측정 대상 액체의 몰 농도이다.where A is the UV absorbance measured with a UV spectrophotometer, ε is the molar extinction coefficient, b is the thickness of the absorption cell, and c is the molar concentration of the liquid to be measured.
따라서, 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논의 UV 흡수 스펙트럼을 참조하면, 최대 흡수 파장 λmax에서의 몰 흡광 계수는 약 105 L/(mol·cm)이며, 이때 측정 대상 액체의 몰 농도가 30μM이고 흡수 셀의 두께가 1cm이고, 최대 흡수 파장에서의 흡광도가 0.296이며, 이때 희석액은 여전히 진한 파란색을 띠고 몰 흡광 계수가 충분히 강한 것을 나타낼 수 있다.Therefore, referring to the UV absorption spectrum of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, the molar extinction coefficient at the maximum absorption wavelength λmax is about 10 5 L/ (mol cm), where the molar concentration of the liquid to be measured is 30 μM, the thickness of the absorption cell is 1 cm, and the absorbance at the maximum absorption wavelength is 0.296. can indicate
실시예 2 Example 2
1,8-디히드록시-4,5-디니트로-9,10-안트라퀴논 1.0 mmol을 3-neck 플라스크에 넣고, 0℃에서 진한 황산 3ml 및 진한 질산 2ml를 첨가하고 4 시간 동안 강하게 기계적으로 교반한 후, 분쇄된 얼음을 첨가하고, 용매를 흡인 여과로 제거하고, 고형분을 포화 탄산수소나트륨 수용액으로 세척하여 진공에서 건조시키고, 밤새 방치하여 황색 조 생성물 1을 수득했다.1.0 mmol of 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone was placed in a 3-neck flask, 3 ml of concentrated sulfuric acid and 2 ml of concentrated nitric acid were added at 0 ° C, and the mixture was mechanically stirred for 4 hours. After stirring, crushed ice was added, the solvent was removed by suction filtration, and the solids were washed with saturated aqueous sodium hydrogen carbonate solution, dried in vacuo and left overnight to obtain a yellow crude product 1.
조 생성물 1을 메탄올에 용해시킨 후 사이클로헥산을 첨가하고 재결정하여 황색 생성물인 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논을 수득했다.After dissolving crude product 1 in methanol, cyclohexane was added and recrystallized to obtain 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone as a yellow product.
상기 황색 생성물 1mmol을 칭량하여 플라스크에 넣어 N,N-디메틸포름아마이드에 용해시키고, 팔라듐 카본 0.01g을 칭량하여 플라스크에 넣었다. 혼합물을 표준 대기압 및 수소 분위기에서 12시간 동안 환류시키고, 실온까지 냉각한 후 준비된 물에 첨가하면서 지속적으로 교반하였다. 여과한 후 물로 세척하고 진공에서 건조시키고 밤새 방치하여 흑색 목적 생성물인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득했다.1 mmol of the above yellow product was weighed and put into a flask, dissolved in N,N-dimethylformamide, and 0.01 g of palladium carbon was weighed and put into a flask. The mixture was refluxed under standard atmospheric pressure and hydrogen atmosphere for 12 hours, cooled to room temperature, and then added to prepared water while stirring continuously. After filtration, washed with water, dried in vacuo and left overnight to give the desired black product, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.
상기 단량체의 자외선 흡수 스펙트럼 및 적외선 스펙트럼을 측정하였는데, 그 결과를 각각 도 1 및 도 2에 나타내었다.An ultraviolet absorption spectrum and an infrared spectrum of the monomer were measured, and the results are shown in FIGS. 1 and 2, respectively.
상기 정제 및 환원 수단은 실시예 1의 정제 및 환원 수단과 서로 바꿔서 사용될 수 있다.The purification and reduction means may be used interchangeably with the purification and reduction means of Example 1.
진성 흑색 폴리이미드 제조 실시예 Intrinsic Black Polyimide Preparation Examples
실시예 3Example 3
본 실시예는 진성 흑색 폴리이미드 PI-1의 합성에 관한 것이다.This example relates to the synthesis of intrinsic black polyimide PI-1.
몰비가 4:96인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논과 4,4'-디아미노디페닐에테르(ODA) 및 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.3%인 흑색 폴리이미드 필름을 제조하였다. 반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1:1이다.1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and 4,4'-diaminodiphenyl ether (ODA) in a molar ratio of 4:96 and pyromelliticdiane A black polyimide film having a solid content of 15.3% was prepared using hydride (PMDA). The ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100mL 3-neck 둥근 바닥 플라스크에 목표 단량체 0.36mmol, ODA 5.64mmol 및 DMAc 10ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 흑색 폴리아믹산 용액을 수득했다. Water and oxygen were sufficiently removed, and 0.36 mmol of the target monomer, 5.64 mmol of ODA, and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a cold water bath in a nitrogen atmosphere, and dissolved into a homogenized solution. After stirring until formed, a total of 6 mmol of PMDA was added to the solution three times, stirred in a cold water bath for 14 hours to react, and a black polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행되었다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process was performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
실시예 4Example 4
본 실시예는 진성 흑색 폴리이미드 PI-2의 합성에 관한 것이다.This example relates to the synthesis of intrinsic black polyimide PI-2.
몰비가 6:94인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논과 4,4'-디아미노디페닐에테르(ODA) 및 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.3%인 흑색 폴리이미드 필름을 제조하였다. 반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1:1이다.1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and 4,4'-diaminodiphenyl ether (ODA) in a molar ratio of 6:94 and pyromelliticdiane A black polyimide film having a solid content of 15.3% was prepared using hydride (PMDA). The ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100mL 3-neck 둥근 바닥 플라스크에 목표 단량체 0.36mmol, ODA 5.64mmol 및 DMAc 10ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 흑색 폴리아믹산 용액을 수득했다. Water and oxygen were sufficiently removed, and 0.36 mmol of the target monomer, 5.64 mmol of ODA, and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a cold water bath in a nitrogen atmosphere, and dissolved into a homogenized solution. After stirring until formed, a total of 6 mmol of PMDA was added to the solution three times, stirred in a cold water bath for 14 hours to react, and a black polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행되었다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process was performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
실시예 5Example 5
본 실시예는 진성 흑색 폴리이미드 PI-3의 합성에 관한 것이다.This example relates to the synthesis of intrinsic black polyimide PI-3.
몰비가 8:92인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논과 4,4'-디아미노디페닐에테르(ODA) 및 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.3%인 흑색 폴리이미드 필름을 제조하였다. 반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1:1이다.1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and 4,4'-diaminodiphenyl ether (ODA) in a molar ratio of 8:92 and pyromelliticdiane A black polyimide film having a solid content of 15.3% was prepared using hydride (PMDA). The ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100mL 3-neck 둥근 바닥 플라스크에 목표 단량체 0.36mmol, ODA 5.64mmol 및 DMAc 10ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 흑색 폴리아믹산 용액을 수득했다. Water and oxygen were sufficiently removed, and 0.36 mmol of the target monomer, 5.64 mmol of ODA, and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a cold water bath in a nitrogen atmosphere, and dissolved into a homogenized solution. After stirring until formed, a total of 6 mmol of PMDA was added to the solution three times, stirred in a cold water bath for 14 hours to react, and a black polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행되었다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process was performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
실시예 6Example 6
본 실시예는 진성 흑색 폴리이미드 PI-4의 합성에 관한 것이다.This example relates to the synthesis of intrinsic black polyimide PI-4.
몰비가 10:90인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논과 4,4'-디아미노디페닐에테르(ODA) 및 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.3%인 흑색 폴리이미드 필름을 제조하였다. 반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1:1이다.1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and 4,4'-diaminodiphenyl ether (ODA) in a molar ratio of 10:90 and pyromelliticdiane A black polyimide film having a solid content of 15.3% was prepared using hydride (PMDA). The ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100mL 3-neck 둥근 바닥 플라스크에 목표 단량체 0.36mmol, ODA 5.64mmol 및 DMAc 10ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 흑색 폴리아믹산 용액을 수득했다. Water and oxygen were sufficiently removed, and 0.36 mmol of the target monomer, 5.64 mmol of ODA, and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a cold water bath in a nitrogen atmosphere, and dissolved into a homogenized solution. After stirring until formed, a total of 6 mmol of PMDA was added to the solution three times, stirred in a cold water bath for 14 hours to react, and a black polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행되었다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process was performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
실시예 7Example 7
몰비가 80:20인 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논과 4,4'-디아미노디페닐에테르(ODA) 및 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.3%인 흑색 폴리이미드 필름을 제조하였다. 반응에 관여하는 상기 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1 : 1이다.1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and 4,4'-diaminodiphenyl ether (ODA) in a molar ratio of 80:20 and pyromelliticdiane A black polyimide film having a solid content of 15.3% was prepared using hydride (PMDA). The ratio of the total number of moles of amine groups of the tetraamine monomer and the diamine monomer involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer involved in the reaction is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100 mL 3-neck 둥근 바닥 플라스크에 목표 단량체 0.36 mmol, ODA 5.64 mmol 및 DMAc 10 ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6 mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 흑색 폴리아믹산 용액을 수득했다. Water and oxygen were sufficiently removed, and 0.36 mmol of the target monomer, 5.64 mmol of ODA, and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, a mechanical stirrer, and a cold water bath in a nitrogen atmosphere to form a homogenized solution. After stirring until dissolved and formed, a total of 6 mmol of PMDA was added to the solution three times, stirred for 14 hours in a cold water bath to react, and a black polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행되었다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process was performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
실시예 6에 따른 진성 흑색 폴리이미드에 비해, 실시예 7에 따른 진성 흑색 폴리이미드는 광학 특성이 낮고, 모듈러스가 높아지고, 파단 신율 및 인장 강도가 떨어지고, 유전 특성이 거의 변하지 않는다.Compared to the intrinsic black polyimide according to Example 6, the intrinsic black polyimide according to Example 7 has lower optical properties, higher modulus, lower elongation at break and tensile strength, and little change in dielectric properties.
비교예 1Comparative Example 1
본 실시예는 PMDA-ODA형 PI 필름의 합성에 관한 것이다.This example relates to the synthesis of a PMDA-ODA type PI film.
몰비가 1 : 1인 4,4'-디아미노디페닐에테르(ODA)와 피로멜리틱디안하이드라이드(PMDA)를 사용하여 고형분 함량이 15.1%인 Kapton형 폴리이미드 필름을 제조하였다. 상기 디아민 단량체의 아민기 총 몰수와 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1 : 1이다.A Kapton-type polyimide film having a solid content of 15.1% was prepared using 4,4'-diaminodiphenyl ether (ODA) and pyromellitic dianhydride (PMDA) in a molar ratio of 1:1. The ratio of the total number of moles of amine groups of the diamine monomer to the total number of moles of carboxylic acid anhydride groups of the anhydride monomer is 1:1.
물과 산소를 충분히 제거하고, 질소 분위기에서 질소 주입구, 기계적 교반기 및 냉수욕조가 구비된 100 mL 3-neck 둥근 바닥 플라스크에 ODA 6 mmol 및 DMAc 10 ml를 첨가하여 균질화된 용액으로 용해하여 형성될 때까지 교반하고, 상기 용액에 PMDA 총 6 mmol을 3회에 걸쳐 첨가하고, 냉수욕조에서 14시간 동안 교반하여 반응시킨 후, 일정한 점도의 옅은 황색 폴리아믹산 용액을 수득했다.After sufficient removal of water and oxygen, 6 mmol of ODA and 10 ml of DMAc were added to a 100 mL 3-neck round bottom flask equipped with a nitrogen inlet, mechanical stirrer and cold water bath in a nitrogen atmosphere to form a homogenized solution. After stirring, a total of 6 mmol of PMDA was added to the solution three times, stirred in a cold water bath for 14 hours to react, and a pale yellow polyamic acid solution having a constant viscosity was obtained.
상기 폴리아믹산 용액은 탈포하고, 깨끗하고 건조한 유리판에 자동 코팅기에 의해 균일하게 코팅되며, 열 이미드화 방식으로 이미드화 반응을 시켰다. 승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행된다.The polyamic acid solution was degassed, uniformly coated on a clean and dry glass plate by an automatic coating machine, and subjected to an imidization reaction by a thermal imidization method. The temperature raising and curing process is performed in the order of 80°C/3h, 100°C/1h, 200°C/2h, and 300°C/4h.
비교예 2Comparative Example 2
비교예 2는 Ningbo Jinshan로부터 구입된 등급 BY112인 고광택 도핑 흑색 필름이다.Comparative Example 2 is a high gloss doped black film, grade BY112, purchased from Ningbo Jinshan.
비교예 3Comparative Example 3
비교예 3은 Ningbo Jinshan로부터 구입된 등급 BY122인 매트 도핑 블랙 필름이다.Comparative Example 3 is a matte doped black film, grade BY122, purchased from Ningbo Jinshan.
특성 평가characteristic evaluation
실시예 3 내지 6 및 비교예 1 내지 3에 따른 폴리이미드는 UV 흡수 스펙트럼 및 LAB 값, 유전 특성, 열적 특성 및 기계적 특성을 측정하고, 그 측정 결과를 하기 표 1 내지 4에 나타내었다.UV absorption spectra, LAB values, dielectric properties, thermal properties, and mechanical properties of the polyimides according to Examples 3 to 6 and Comparative Examples 1 to 3 were measured, and the measurement results are shown in Tables 1 to 4 below.
표 1. 실시예 3 내지6 및 비교예 1 내지 3의 폴리이미드의 600nm 투과율 T600(%) 및 LAB 값Table 1. 600 nm transmittance T 600 (%) and LAB values of the polyimides of Examples 3 to 6 and Comparative Examples 1 to 3
표 2. 실시예 3 내지 6 및 비교예 1 내지 3의 폴리이미드의 열적 특성 데이터 및 기계적 특성 데이터Table 2. Thermal property data and mechanical property data of the polyimides of Examples 3 to 6 and Comparative Examples 1 to 3
표 3. 실시예 3 내지 6 및 비교예 1 내지 3의 폴리이미드의 기계적 특성 데이터Table 3. Mechanical property data of the polyimides of Examples 3 to 6 and Comparative Examples 1 to 3
표 4. 실시예 3 내지 6 및 비교예 1 내지 3의 폴리이미드의 유전 특성 데이터Table 4. Dielectric property data of the polyimides of Examples 3 to 6 and Comparative Examples 1 to 3
상기 표에 나타난 바와 같이, 전체 아민계 단량체의 몰수 중에 본 출원에 따른 안트라퀴논 유도체 테트라아민 단량체의 몰수가 4% 이상인 경우, 제조된 흑색 폴리이미드는 차광 특성이 우월하고, 우수한 기계적 특성, 열적 안정성 및 유전 특성을 가지며 전대역에 걸쳐 광 투과율이 1% 미만이다.As shown in the table above, when the number of moles of the anthraquinone derivative tetraamine monomer according to the present application is 4% or more among the total number of moles of amine monomers, the prepared black polyimide has superior light-shielding properties, excellent mechanical properties, and thermal stability and dielectric properties, and a light transmittance of less than 1% over the entire band.
이상에서 실시예에 대한 설명은 본 발명이 속하는 기술 분야에서 통상의 지식을 갖는 자가 본 출원을 이해하고 적용할 수 있도록 하기 위한 것이다. 이러한 실시예에 대해 다양한 수정이 용이하게 이루어질 수 있고, 여기에 설명된 일반적인 원리를 더 이상의 노력 없이 다른 실시예에 적용할 수 있음은 숙련된 당업자에게 명백할 것이다. 따라서, 본 출원은 여기의 실시예들에 한정되지 않으며, 본 발명이 속하는 기술 분야에서 통상의 지식을 갖는 자가 본 출원에 개시된 내용에 기초하여 본 출원의 청구 범위 및 사상을 벗어나지 않는 범위 내에서 개선 및 수정을 할 수 있고 그 개선 및 수정도 본 출원의 범위에 속할 것이다.The description of the embodiments above is intended to enable those skilled in the art to understand and apply the present application. It will be apparent to those skilled in the art that various modifications may readily be made to these embodiments, and that the general principles described herein may be applied to other embodiments without further effort. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art can make improvements based on the contents disclosed in the present application within the range that does not deviate from the scope and spirit of the present application. and modifications may be made, and improvements and modifications thereof shall also fall within the scope of this application.
Claims (10)
식 I
Formula I
진한 황산 및 진한 질산의 존재 하에서, 1,8-디히드록시-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함하는 것을 특징으로 하는 안트라퀴논 유도체 테트라아민 단량체의 제조 방법.In the method for preparing the anthraquinone derivative tetraamine monomer according to claim 1,
In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8-dihydroxy-9,10-anthraquinone was converted to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone. nitration and reducing the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone; an anthraquinone derivative comprising A method for producing tetraamine monomers.
진한 황산 및 진한 질산의 존재 하에서, 1,8-디히드록시-4,5-디니트로-9,10-안트라퀴논을 1,8-디히드록시-2,4,5,7-테트라니트로-9,10-안트라퀴논으로 니트로화시키고, 니트로기를 아미노기로 환원하여 1,8-디히드록시-2,4,5,7-테트라아미노-9,10-안트라퀴논을 수득하는 단계;를 포함하는 것을 특징으로 하는 안트라퀴논 유도체 테트라아민 단량체의 제조 방법.In the method for producing the anthraquinone derivative tetraamine monomer according to claim 1,
In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone was converted to 1,8-dihydroxy-2,4,5,7-tetranitro- nitrating with 9,10-anthraquinone and reducing the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone; Method for producing an anthraquinone derivative tetraamine monomer, characterized in that.
상기 안트라퀴논 유도체 테트라아민 단량체는 상기 안트라퀴논 유도체 테트라아민 단량체와 상기 디아민 단량체의 총 몰수에 대하여 4% 내지 10%로 포함되는 것을 특징으로 하는 진성 흑색 폴리이미드.According to claim 4,
The intrinsic black polyimide, characterized in that the anthraquinone derivative tetraamine monomer is included in an amount of 4% to 10% based on the total number of moles of the anthraquinone derivative tetraamine monomer and the diamine monomer.
반응에 관여하는 상기 안트라퀴논 유도체 테트라아민 단량체 및 상기 디아민 단량체의 아민기 총 몰수와 반응에 관여하는 상기 무수물 단량체의 카르복실산 무수물 그룹의 총 몰수의 비율이 1 : 1인 것을 특징으로 하는 진성 흑색 폴리이미드.According to claim 4,
The ratio of the total number of moles of amine groups of the anthraquinone derivative tetraamine monomers and the diamine monomers involved in the reaction to the total number of moles of carboxylic acid anhydride groups of the anhydride monomers involved in the reaction is 1:1. polyimide.
상기 무수물 단량체는 4,4'-(아세틸렌-1,2,-디일)디프탈릭 언하이드라이드, 피로멜리틱 디안하이드라이드, 3,3',4,4'-비페닐테트라카르복실릭 디안하이드라이드, 3,3',4,4'-벤조페논테트라카복실릭 디안하이드라이드, 2,2'-비스(3,4-디카르복실산)헥사플루오로프로판 디안하이드라이드, 4,4'-옥시디프탈릭 안하이드라이드, 2,3,3',4'-비페닐테트라카르복실릭 디언하이드라이드, 3,3′,4,4′-디페닐술폰 테트라카복실릭 디언하이드라이드, 나프탈렌-1,4,5,8-테트라카르복실릭 디언하이드라이드 및 디페닐 설파이드 디안하이드라이드에서 선택된 하나 또는 그 이상인 것을 특징으로 하는 진성 흑색 폴리이미드.According to claim 4,
The anhydride monomer is 4,4'-(acetylene-1,2,-diyl)diphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride Ride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxylic acid) hexafluoropropane dianhydride, 4,4'- Oxydiphthalic anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, naphthalene-1 An intrinsic black polyimide, characterized in that it is one or more selected from 4,5,8-tetracarboxylic dianhydride and diphenyl sulfide dianhydride.
상기 디아민 단량체는 m-페닐렌디아민, p-페닐렌디아민, 4,4'-디아미노비페닐, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 4,4'-디아미노벤조페논, 4,4'-디아미노디페닐메탄, 1,3-비스(4-아미노페녹시)벤젠, 1,4-비스(4-아미노페녹시)벤젠, 4,4'-디아미노-2,2'-디메틸비페닐, 2-(4-아미노페닐)-5-아미노벤족사졸, 2-(4-아미노페닐)-5-아미노벤즈이미다졸, 1,4-비스(3-아미노페녹시)벤젠, 1,3-비스(3-하이드록시-4-아미노페녹시)벤젠, 2-(4-아미노페닐)-6-아미노벤족사졸, 2,2-p-페닐-비스(5-아미노벤족사졸) 및 2,2'-p-페닐-비스(6-아미노벤족사졸)에서 선택된 하나 또는 그 이상인 것을 특징으로 하는 진성 흑색 폴리이미드.According to claim 4,
The diamine monomer is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4, 4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4 '-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis (3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl An intrinsic black polyimide characterized by being one or more selected from bis(5-aminobenzoxazole) and 2,2'-p-phenyl-bis(6-aminobenzoxazole).
(1) 무수 및 무산소 조건에서 제1항에 의한 안트라퀴논 유도체 테트라아민 단량체와 디아민 단량체를 기 설정된 중량비로 혼합하고 용해될 때까지 교반하여 균질화된 용액을 형성한 후에, 산무수물 단량체를 첨가하고 냉수욕조에서 기 설정된 시간 동안 교반하면서 반응시켜 흑색 폴리아믹산 용액을 수득하는 단계;
(2) 흑색 폴리아믹산 용액을 이미드화시켜 진성 흑색 폴리이미드를 수득하는 단계;를 포함하는 것을 특징으로 하는 진성 흑색 폴리이미드의 제조 방법.In the method for producing the intrinsic black polyimide according to claim 4,
(1) Under anhydrous and oxygen-free conditions, the anthraquinone derivative tetraamine monomer and diamine monomer according to claim 1 are mixed in a predetermined weight ratio and stirred until dissolved to form a homogenized solution, then acid anhydride monomer is added and cold water Obtaining a black polyamic acid solution by reacting while stirring for a predetermined time in a bath;
(2) imidizing the black polyamic acid solution to obtain intrinsic black polyimide;
상기 흑색 폴리아믹산 용액을 이미드화시키는 단계는
흑색 폴리아믹산 용액을 소포하고, 깨끗하고 건조한 유리판에 자동 코팅기로 균일하게 코팅하여, 열 이미드화 방식에 의해 이미드화 반응시키는 단계;를 포함하며,
승온 및 경화 공정은 80℃/3h, 100℃/1h, 200℃/2h, 300℃/4h의 순서로 수행된 것을 특징으로 하는 진성 흑색 폴리이미드의 제조 방법.According to claim 9,
The step of imidizing the black polyamic acid solution is
Defoaming the black polyamic acid solution, uniformly coating it on a clean and dry glass plate with an automatic coater, and performing an imidization reaction by a thermal imidation method; including,
A method for producing intrinsic black polyimide, characterized in that the temperature raising and curing steps are performed in the order of 80 ° C / 3 h, 100 ° C / 1 h, 200 ° C / 2 h, and 300 ° C / 4 h.
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