KR101481729B1 - The reactive monomers for a polyimide precursor and a polyimide precursor using the same - Google Patents
The reactive monomers for a polyimide precursor and a polyimide precursor using the same Download PDFInfo
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- KR101481729B1 KR101481729B1 KR20070140472A KR20070140472A KR101481729B1 KR 101481729 B1 KR101481729 B1 KR 101481729B1 KR 20070140472 A KR20070140472 A KR 20070140472A KR 20070140472 A KR20070140472 A KR 20070140472A KR 101481729 B1 KR101481729 B1 KR 101481729B1
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- polyimide precursor
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 60
- 239000004642 Polyimide Substances 0.000 title claims abstract description 59
- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 239000000178 monomer Substances 0.000 title claims abstract description 36
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000000962 organic group Chemical group 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- -1 2- (2-bromo-ethyl) 2- (2-chloro-ethyl) -oxirane Chemical compound 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- HWKPTBHJWBSOOP-UHFFFAOYSA-N (4-bromophenoxy)-trimethylsilane Chemical compound C[Si](C)(C)OC1=CC=C(Br)C=C1 HWKPTBHJWBSOOP-UHFFFAOYSA-N 0.000 claims description 2
- GLQNPYLKSCFVPO-UHFFFAOYSA-N 2-o-(2-hydroxypropyl) 1-o-[2-(2-methylprop-2-enoyloxy)ethyl] benzene-1,2-dicarboxylate Chemical compound CC(O)COC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C(C)=C GLQNPYLKSCFVPO-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- TXEGFNIHBZYLTQ-UHFFFAOYSA-N bromo-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Br)CC=C TXEGFNIHBZYLTQ-UHFFFAOYSA-N 0.000 claims description 2
- ACAUYCZBWABOLI-UHFFFAOYSA-N bromomethyl(trimethyl)silane Chemical compound C[Si](C)(C)CBr ACAUYCZBWABOLI-UHFFFAOYSA-N 0.000 claims description 2
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical compound CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 claims description 2
- YCXVDEMHEKQQCI-UHFFFAOYSA-N chloro-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)Cl YCXVDEMHEKQQCI-UHFFFAOYSA-N 0.000 claims description 2
- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 claims description 2
- UHHLOVCFFWGSMO-UHFFFAOYSA-N chloromethyl-dimethyl-prop-2-enylsilane Chemical compound ClC[Si](C)(C)CC=C UHHLOVCFFWGSMO-UHFFFAOYSA-N 0.000 claims description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- BSCJIBOZTKGXQP-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCO BSCJIBOZTKGXQP-UHFFFAOYSA-N 0.000 claims description 2
- IPGRTXQKFZCLJS-UHFFFAOYSA-N n-(2-hydroxypropyl)prop-2-enamide Chemical compound CC(O)CNC(=O)C=C IPGRTXQKFZCLJS-UHFFFAOYSA-N 0.000 claims description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- YKUYKENINQNULY-UHFFFAOYSA-N 2-[(4-bromophenoxy)methyl]oxirane Chemical compound C1=CC(Br)=CC=C1OCC1OC1 YKUYKENINQNULY-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 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 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 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 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 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 description 4
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 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 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RVOODBPUUNSGDF-UHFFFAOYSA-N ClC=1C=C(C=C(C1)O)O.ClC=1C=C(C=C(C1)O)O Chemical compound ClC=1C=C(C=C(C1)O)O.ClC=1C=C(C=C(C1)O)O RVOODBPUUNSGDF-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 229940117913 acrylamide Drugs 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- BKDVBBSUAGJUBA-UHFFFAOYSA-N bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O BKDVBBSUAGJUBA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
본 발명은 폴리이미드 전구체용 반응성 단량체 및 이를 이용한 폴리이미드 전구체에 관한 것으로서, 보다 상세하게는 벤젠고리에 에폭시기, 실란기, 및 아크릴기로 이루어진 군에서 선택된 2종 또는 3종의 치환기를 포함하는 폴리이미드 전구체용 반응성 단량체 및 이를 이용한 폴리이미드 전구체를 제공한다. 본 발명에 따른 상기 반응성 단량체를 이용하여 얻어진 신규 폴리이미드 전구체는 모든 기재와의 접착력이 향상될 뿐만 아니라 소량 사용으로도 물성저하가 없으며 충분한 접착력을 나타낼 수 있다.The present invention relates to a reactive monomer for a polyimide precursor and a polyimide precursor using the reactive monomer. More particularly, the present invention relates to a polyimide precursor comprising a polyimide precursor having two or three substituents selected from the group consisting of an epoxy group, a silane group, A reactive monomer for a precursor and a polyimide precursor using the same are provided. The novel polyimide precursor obtained by using the reactive monomer according to the present invention not only improves the adhesion to all the substrates but also exhibits sufficient adhesion without lowering the physical properties even when used in small amounts.
폴리이미드 전구체, 반응성 단량체, 접착력 Polyimide precursor, reactive monomer, adhesion
Description
본 발명은 반응성 단량체 및 이를 이용한 폴리이미드 전구체에 관한 것으로, 더욱 상세하게는 기존의 폴리이미드 전구체에 기재와의 접착력을 강화하기 위하여 벤젠고리에 에폭시기, 실란기, 및 아크릴기로 이루어진 군에서 선택된 2종 또는 3종의 치환기를 포함하도록 제조된 반응성 단량체 및 이를 이용하여 기재와의 접착력이 향상된 폴리이미드 전구체에 관한 것이다.The present invention relates to a reactive monomer and a polyimide precursor using the reactive monomer. More particularly, the present invention relates to a polyimide precursor using two reactive species selected from the group consisting of an epoxy group, a silane group, and an acrylic group Or three kinds of substituents, and a polyimide precursor having improved adhesion to a substrate using the reactive monomer.
디아민 단량체와 테트라카르복실산 이무수물 단량체를 중합하여 얻어지는 폴리이미드는 내화학성, 내열성, 기계적 물성, 및 전기 절연성이 우수하여 반도체 및 디스플레이 등 전기 전자 분야에 많이 응용되어왔다.Polyimide obtained by polymerizing a diamine monomer and a tetracarboxylic acid dianhydride monomer has been widely applied to electric and electronic fields such as semiconductors and displays because of its excellent chemical resistance, heat resistance, mechanical properties, and electrical insulation.
그러나, 일반적인 폴리이미드는 아크릴 수지나 에폭시 수지에 비해 실리콘 웨이퍼, 유리, 및 기타 여러 종류의 금속 기재와의 접착력이 떨어지기 때문에, 이러한 취약한 접착력을 극복하기 위하여 종래기술은 실리콘 성분을 함유한 접착조제 를 배합하거나 실리콘 디아민을 공중합하여 사용하였다. 하지만, 접착조제를 사용하는 경우나, 실리콘 디아민을 공중합하는 경우는 접착력의 증대효과가 미미하며, 이들을 과량 사용할 경우에는 필름물성이 저하되거나 저장안정성에 문제가 있었다.However, since general polyimide has a lower adhesive force with respect to silicon wafers, glass, and various kinds of metal substrates than acrylic resin or epoxy resin, in order to overcome such weak adhesion, Or silicone diamine was copolymerized. However, in the case of using an adhesion promoter or in the case of copolymerizing silicone diamine, the effect of increasing the adhesive force is insignificant, and when they are used in excess, the film properties are deteriorated and the storage stability is problematic.
상기 종래기술의 문제점을 해결하고자, 본 발명의 목적은 폴리이미드 전구체의 접착력을 향상시킬 수 있는 반응성 단량체 화합물의 제조방법 및 이로부터 얻어진 반응성 단량체 화합물을 제공하는 것이다.It is an object of the present invention to provide a method for producing a reactive monomer compound capable of improving the adhesion of a polyimide precursor and a reactive monomer compound obtained therefrom.
본 발명의 다른 목적은 상기 반응성 단량체를 이용하여 접착력이 향상된 신규 폴리이미드 전구체를 제공하는 것이다.Another object of the present invention is to provide a novel polyimide precursor having improved adhesion by using the reactive monomer.
상기 목적을 달성하기 위하여, 본 발명은In order to achieve the above object,
(a) 하기 화학식 2로 표시되는 화합물과 하기 화학식 3의 화합물을 반응시키고, 및(a) reacting a compound represented by the following formula 2 with a compound represented by the following formula 3, and
(b) 상기 반응 결과물에 하기 화학식 4 및 화학식 5로 표시되는 화합물을 반응시키는 단계(b) reacting the reaction product with a compound represented by the following general formula (4) or (5)
를 포함하는 하기 화학식 1로 표시되는 폴리이미드 전구체용 반응성 단량체의 제조방법을 제공한다:A reactive monomer for a polyimide precursor represented by the following general formula (1)
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[화학식 3] [화학식 4] [화학식 5][Chemical Formula 3]
R1-OH R2-X2 R3-X2 R 1 -OH R 2 -X 2 R 3 -X 2
여기서, X1 및 X2는 각각 Cl 또는 Br이며, R1은 탄소수 3 내지 20의 지방족 또는 방향족 불포화 이중결합을 1개 이상 함유한 1가의 유기기이고, R2는 탄소수 2 내지 20의 실리콘 성분을 함유한 1가의 유기기이며, R3는 탄소수 2 내지 20의 에폭시기를 1개 이상 함유한 1가의 유기기이다.Herein, X 1 and X 2 are each Cl or Br, R 1 is a monovalent organic group containing at least one aliphatic or aromatic unsaturated double bond having 3 to 20 carbon atoms, R 2 is a silicon component having 2 to 20 carbon atoms And R 3 is a monovalent organic group containing at least one epoxy group having 2 to 20 carbon atoms.
본 발명은 또한, 상기 방법으로 제조되는 상기 화학식 1로 표시되는 폴리이미드 전구체용 반응성 단량체 화합물을 제공한다.The present invention also provides a reactive monomer compound for a polyimide precursor represented by the above formula (1), prepared by the above method.
또한, 본 발명은 하기 화학식 1로 표시되는 반응성 단량체 및 하기 화학식 6으로 표시되는 화합물을 반응시키는 단계를 포함하는 하기 화학식 7로 표시되는 폴리이미드 전구체의 제조방법 및 이로부터 제조된 신규한 화학식 7의 폴리이미드 전구체를 제공한다: The present invention also provides a process for preparing a polyimide precursor represented by the following general formula (7), comprising reacting a reactive monomer represented by the following general formula (1) and a compound represented by the following general formula (6) A polyimide precursor is provided:
[화학식 1][Chemical Formula 1]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
여기서, R1, R2 및 R3는 상기에서 정의된 바와 같으며, R3'은 R3에 포함되어 있는 에폭시기의 반응에 의해 생성된 탄소수 2 내지 20의 알코올기를 함유한 1가의 유기기이고, R4는 수소 또는 탄소수 1 내지 20의 알킬기이고, X는 탄소수 4 내지 30 의 방향족환 또는 지방족환을 포함하는 4가의 유기기이고, Y는 탄소수 6 내지 30의 방향족 2가의 유기기를 나타낸다.Wherein R 1 , R 2 and R 3 are as defined above, and R 3 'is a monovalent organic group containing an alcohol group having 2 to 20 carbon atoms and produced by the reaction of an epoxy group contained in R 3 , R 4 is hydrogen or an alkyl group having 1 to 20 carbon atoms, X is a tetravalent organic group containing an aromatic ring or an aliphatic ring having 4 to 30 carbon atoms, and Y is an aromatic divalent organic group having 6 to 30 carbon atoms.
이하에서 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 접착력 향상을 위하여 벤젠고리에 에폭시기, 실란기 및 아크릴기로 이루어진 군에서 선택된 2종 또는 3종의 치환기를 포함하는 반응성 단량체와, 이를 이용하여 제조된 접착력이 향상된 신규 폴리이미드 전구체에 관한 것이다. 바람직하게, 본 발명의 화학식 1의 반응성 단량체는 에폭시기, 실란기 및 아크릴기 의 3종의 치환기를 포함하거나, 에폭시기 및 아크릴기의 2종의 치환기를 포함할 수 있다.In order to improve the adhesive strength, the present invention relates to a composition containing two or three kinds of substituents selected from the group consisting of an epoxy group, a silane group and an acrylic group in a benzene ring And a novel polyimide precursor having improved adhesion prepared by using the reactive monomer. Preferably, the reactive monomer of formula (1) of the present invention contains three substituents such as an epoxy group, a silane group and an acrylic group, or may include two kinds of substituent groups, that is, an epoxy group and an acrylic group.
본 발명은 상기 반응성 단량체 화합물을 이용하여 폴리이미드 전구체 화합물의 접착력을 향상시킬 수 있으며, 이에 따라 폴리이미드 전구체 화합물은 적은양으로도 원하는 접착력을 나타낼 수 있게 한다.The present invention can improve the adhesive force of the polyimide precursor compound using the reactive monomer compound, and thus the polyimide precursor compound can exhibit a desired adhesive force even in a small amount.
이러한 본 발명의 신규 반응성 단량체는 (a) 하기 화학식 2로 표시되는 화합물과 하기 화학식 3의 화합물을 반응시키고, 및 (b) 상기 반응 결과물에 하기 화학식 4 및 화학식 5로 표시되는 화합물을 반응시키는 단계를 포함하여 제조할 수 있다.(A) reacting a compound represented by the following formula (2) with a compound represented by the following formula (3), and (b) reacting a compound represented by the following formula (4) or . ≪ / RTI >
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[화학식 3] [화학식 4] [화학식 5][Chemical Formula 3]
R1-OH R2-X2 R3-X2 R 1 -OH R 2 -X 2 R 3 -X 2
여기서, X1 및 X2는 각각 Cl 또는 Br이며, R1은 탄소수 3 내지 20의 지방족 또는 방향족 불포화 이중결합을 1개 이상 함유한 1가의 유기기이고, R2는 탄소수 2 내지 20의 실리콘 성분을 함유한 1가의 유기기이며, R3는 탄소수 2 내지 20의 에폭시기를 1개 이상 함유한 1가의 유기기이다.Herein, X 1 and X 2 are each Cl or Br, R 1 is a monovalent organic group containing at least one aliphatic or aromatic unsaturated double bond having 3 to 20 carbon atoms, R 2 is a silicon component having 2 to 20 carbon atoms And R 3 is a monovalent organic group containing at least one epoxy group having 2 to 20 carbon atoms.
상기 화학식 3으로 표시되는 화합물은 N-(하이드록시메틸)메타크릴아미드, 2-하이드록시프로필-2-(메타크릴로일옥시)에틸 프탈레이트, 4-하이드록시부틸 아크릴레이트, N-(하이드록시메틸)메타크릴아미드, 2-하이드록시에틸메타크릴레이트, 2-하이드록시에틸아크릴레이트, N-(2-하이드록시에틸)메타크릴아미드 및 2-하이드록시프로필 아크릴아미드로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다.The compound represented by the general formula (3) is preferably selected from the group consisting of N- (hydroxymethyl) methacrylamide, 2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate, 4-hydroxybutyl acrylate, N- (Meth) acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, N- (2-hydroxyethyl) methacrylamide and 2-hydroxypropylacrylamide You can use what is selected.
또한, 상기 화학식 4로 표시되는 화합물은 브로모메틸 트리메틸실란, 알릴브로모 다이메틸실란, 클로로다이메틸 페닐실란, 클로로메틸 트리메틸실란, 부틸 다이메틸클로로실란, 클로로다이메틸 아이소프로필실란, 클로로다이메틸 에틸실란, 알릴클로로메틸 다이메틸실란, 4-브로모페녹시 트리메틸실란, 3-클로로프로필 트리에톡시실란 및 3-클로로프로필 트리메톡시실란으로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다.In addition, the compound represented by the above-mentioned general formula (4) may be used in combination with bromomethyltrimethylsilane, allyl bromodimethylsilane, chlorodimethylphenylsilane, chloromethyltrimethylsilane, butyldimethylchlorosilane, chlorodimethylisopropylsilane, Ethyl silane, allyl chloromethyl dimethyl silane, 4-bromophenoxy trimethyl silane, 3-chloropropyl triethoxy silane and 3-chloropropyl trimethoxy silane.
또한, 상기 화학식 5로 표시되는 화합물은 에피브로모 히드린, 2-(4-브로모-페녹시메틸)-옥시란, 2-(2-브로모-에틸)-옥시란, 2-(4-클로로-3-메틸-페녹시메틸)-옥시란, 에피클로로히드린, 2-(4-클로로-페녹시메틸)-옥시란 및 2-(2-클로로-에틸)-옥시란으로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다. 하지만, 본원 발명의 화학식 3 내지 5의 화합물이, 상기한 예로 한정되는 것은 아니다. In addition, the compound represented by the above-mentioned general formula (5) may be used in combination with epibromohydrin, 2- (4-bromo-phenoxymethyl) Chloro-3-methyl-phenoxymethyl) -oxirane, epichlorohydrin, 2- (4-chloro-phenoxymethyl) May be used. However, the compounds of the formulas (3) to (5) of the present invention are not limited to the above examples.
상기 (a)단계에서 화학식 3으로 표시되는 화합물은 화학식 2로 표시되는 화합물에 대하여 100 내지 120 의 몰비로 사용하는 것이 바람직하다.In the step (a), the compound represented by the general formula (3) is preferably used in a molar ratio of 100 to 120 with respect to the compound represented by the general formula (2).
상기 (a)단계의 반응온도는 0 ℃ 내지 70 ℃이고, 반응시간은 1 시간 내지 48 시간 일 수 있지만, 본 발명이 이에 한정되는 것은 아니다.The reaction temperature in step (a) may be 0 ° C to 70 ° C, and the reaction time may be 1 hour to 48 hours, but the present invention is not limited thereto.
상기 (b)단계에서 화학식 4로 표시되는 화합물은 화학식 2로 표시되는 화합물에 대하여 0 내지 120의 몰비로 사용하는 것이 바람직하다.In the step (b), the compound represented by the formula (4) is preferably used in a molar ratio of 0 to 120 with respect to the compound represented by the formula (2).
상기 (b)단계에서 화학식 5로 표시되는 화합물은 화학식 2로 표시되는 화합물에 대하여 100 내지 220의 몰비로 사용하는 것이 바람직하다.In the step (b), the compound represented by the formula (5) is preferably used in a molar ratio of 100 to 220 with respect to the compound represented by the formula (2).
상기 (b)단계의 반응온도는 0 ℃ 내지 70 ℃ 이고, 반응시간은 1 시간 내지 48 시간 일 수 있지만, 본 발명이 이에 한정되는 것은 아니다.The reaction temperature in the step (b) may be 0 ° C to 70 ° C, and the reaction time may be 1 hour to 48 hours, but the present invention is not limited thereto.
또한, 본 발명은 상기 화학식 1로 표시되는 반응성 단량체를 이용하고, 이것을 하기 화학식 6으로 표시되는 화합물과 반응시켜 접착력이 향상된 화학식 7로 표시되는 폴리이미드 전구체를 제공하는 특징이 있다.The present invention also provides a polyimide precursor represented by the general formula (7) having improved adhesion by reacting the reactive monomer represented by the general formula (1) with a compound represented by the following general formula (6).
[화학식 6][Chemical Formula 6]
[화학식 7](7)
(여기서, R1, R2 및 R3는 상기에서 정의된 바와 같으며, R3'은 R3에 포함되어 있는 에폭시기의 반응에 의해 생성된 탄소수 2 내지 20의 알코올기를 함유한 1가의 유기기이고, R4는 수소 또는 탄소수 1 내지 20의 알킬기이고, X는 탄소수 4 내지 30 의 방향족환 또는 지방족환을 포함하는 4가의 유기기이고, Y는 탄소수 6 내지 30의 방향족 2가의 유기기를 나타낸다.)(Wherein, R 1 , R 2 And R 3 is as defined above, R 3 'is a monovalent organic group containing an alcohol group having 2 to 20 carbon atoms and formed by the reaction of an epoxy group contained in R 3 , R 4 is hydrogen or a X is an aromatic ring having 4 to 30 carbon atoms or a tetravalent organic group containing an aliphatic ring and Y is an aromatic divalent organic group having 6 to 30 carbon atoms.
즉, 상기 화학식 7의 접착력이 향상된 신규 폴리이미드 전구체는 화학식 6의 폴리이미드 전구체와 화학식 1의 R3의 반응으로 제조된다. 본 발명의 폴리이미드 수지는 폴리아믹산을 열적으로 탈수, 폐환하여 얻을 수 있는 것이다. 상기 화학식 7의 폴리이미드 전구체의 제조시 화학식 1로 표시되는 화합물은 화학식 6으로 표시되는 화합물의 X 에 대하여 5 내지 100의 몰비로 사용하는 것이 바람직하며, 반응조건은 30 ℃ 내지 100 ℃의 온도에서 3시간 내지 72시간 동안 반응을 수행하는 것이 바람직하다. That is, the novel polyimide precursor having improved adhesion of Formula 7 is prepared by the reaction of the polyimide precursor of Formula 6 with R 3 of Formula 1. The polyimide resin of the present invention can be obtained by thermally dehydrating and ring closure of polyamic acid. In the preparation of the polyimide precursor of formula (7), the compound represented by formula (1) is preferably used in a molar ratio of 5 to 100 with respect to X of the compound represented by formula (6) It is preferable to carry out the reaction for 3 to 72 hours.
본 발명에서 상기 화학식 6의 화합물은 하기 화학식 8로 표시되는 방향족 또는 지방족산 이무수물과 하기 화학식 9로 표시되는 방향족 다이아민을 N-메틸-2- 피롤리돈(NMP)과 같은 유기 용제 중에서 축합반응시킴으로 얻을 수 있다.In the present invention, the compound of formula (6) may be prepared by condensing an aromatic or aliphatic acid dianhydride represented by the following formula (8) and an aromatic diamine represented by the following formula (9) in an organic solvent such as N-methyl-2-pyrrolidone .
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
여기서, 상기 화학식 8로 표시되는 이무수물의 예를 구체적으로 나타내면, 3,3',4,4'-벤조페논테트라카복실릭 디언하이드라이드(3,3',4,4'-benzophenonetetracarboxylic dianhydride), 3,3',4,4'-옥시디프탈릭 디언하이드라이드(3,3',4,4'-oxydiphthalic dianhydride), 피로멜리틱 디언하이드라이드(pyromellitic dianhydride), 4,4'-바이프탈릭 언하이드라이드(4,4'-biphthalic anhydride; Diphenyl-3,3',4,4'-tetracarboxylic Dianhydride), 4,4-설포닐디프탈릭 디언하이드라이드(4,4-sulfonyldiphthalic dianhydride), 3,3',4,4'-비페닐트테라카복실릭 디언하이드라이드(3,3',4,4'-biphenyltetracarboxylic dianhydride), 4,4-(헥사플로로이소프로필리덴)디프탈릭 언하이드라이드(4,4-(hexafluoroisopropylidene) diphthalic anhydride), 1,2,3,4-사이클로펜탄테트라카복실릭 디언하이드라이드(1,2,3,4-cyclopentanetetracarboxylic dianhydriede), 1,2,3,4-사이클로부탄테트라카복실릭 디언하이드라이드(1,2,3,4-cyclobutanetetracarboxylic dianhydriede), 비사이클로[2,2,2]옥트-7-엔-2,3,5,6- 테트라카복실릭 디언하이드라이드(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydriede) 등이 있다.Examples of dianhydrides represented by the formula (8) include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, , 3 ', 4,4'-oxydiphthalic dianhydride, pyromellitic dianhydride, 4,4'-biphthalic anhydride, 4,4'-biphthalic anhydride (Diphenyl-3,3 ', 4,4'-tetracarboxylic Dianhydride), 4,4-sulfonyldiphthalic dianhydride, 3,3 4,4'-biphenyltetracarboxylic dianhydride, 4,4- (hexafluoroisopropylidene) diphthalic anhydride (4, 4'-biphenyltetracarboxylic dianhydride) , 4- (hexafluoroisopropylidene) diphthalic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetra Carbop Bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride , 2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride).
또한, 상기 화학식 9로 표시되는 방향족 다이아민의 예를 구체적으로 나타내면 4,4'-메틸렌디아닐린(4,4'-methylenedianiline), 4,4'-옥시디아닐린(4,4'-oxydianiline), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), m-자일렌디아민(m-xylenediamine), 3,3'-디메틸벤지딘(3,3'-dimethylbenzidine), 1,1,1,3,3,3-헥사플로로-2,2-비스(4-아미노페닐)프로판(1,1,1,3,3,3-hexafluoro-2,2-bis(4-aminophenyl)propane), 설포닐디아닐린(sulfonyldianiline), 3,5-디아미노벤조산(3,5-dianminobenzoic acid), 2,4-디아미노벤젠설포닐산(2,4-diaminobenzenesulfonyl acid), 2,2-비스(4-(4-아미노페녹시)페닐)프로판(2,2-bis(4-(4-aminophenoxy)phenyl) propane), 4,4-벤조페논디아민(4,4-benzophenonediamine), 4,4'-디-(4-아미노페녹시)페닐설폰(4,4'-di-(4-aminophenoxy)phenylsulfone), 3,3-디메틸-4,4-디아미노디페닐메탄(3,3-dimethyl-4,4-diaminodiphenylmethane), 1,5-디아미노나프탈렌(1,5-diaminonaphthalene) 등이 있다.Examples of the aromatic diamine represented by the formula (9) include 4,4'-methylenedianiline, 4,4'-oxydianiline, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, 3,3'-dimethylbenzidine, 1 , 1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane (1,1,1,3,3,3-hexafluoro-2,2-bis aminophenyl) propane, sulfonyldianiline, 3,5-dianminobenzoic acid, 2,4-diaminobenzenesulfonyl acid, 2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 4,4-benzophenonediamine, 4, 4'-di- (4-aminophenoxy) phenylsulfone), 3,3-dimethyl-4,4-diaminodiphenylmethane (3,3- dimethyl-4,4-diaminodiphenylmethane), 1,5-diamino Talren the like (1,5-diaminonaphthalene).
또한, 본 발명에서 상기 폴리이미드 전구체 제조에 사용되는 용매의 종류는 상기한 NMP에 한정되는 것은 아니고, 본 발명이 속하는 기술분야에서 통상적으로 사용되는 용매를 사용할 수 있다.In addition, the type of the solvent used for preparing the polyimide precursor in the present invention is not limited to the above-mentioned NMP, and a solvent commonly used in the technical field of the present invention may be used.
또한, 상기 폴리이미드 전구체 제조시의 반응조건은 특별히 한정되지는 않고, 본 발명이 속하는 기술분야에서 사용되는 통상적인 방법을 이용할 수 있다.The reaction conditions for the production of the polyimide precursor are not particularly limited, and conventional methods used in the technical field of the present invention can be used.
본 발명은 접착력 향상을 위하여 벤젠고리에 에폭시기, 실란기, 및 아크릴기로 이루어진 군에서 선택되는 2종 또는 3종의 치환기를 포함하는 반응성 단량체를 제공하며, 상기 신규 단량체에 도입된 불포화 이중결합은 기재와의 접착력을 증가시킬 뿐만 아니라 가교밀도를 증가시킬 수 있다. 따라서, 일반적인 폴리이미드 전구체인 폴리아믹산이나 폴리아믹산 에스테르에 본 발명의 신규 반응성 단량체를 도입할 경우 적은 양으로도 용이하게 접착력을 향상시킬 수 있다.The present invention provides a reactive monomer containing two or three substituents selected from the group consisting of an epoxy group, a silane group and an acrylic group in a benzene ring in order to improve the adhesive strength, and the unsaturated double bond introduced into the novel monomer And the crosslinking density can be increased. Therefore, when the novel reactive monomer of the present invention is introduced into a polyamic acid or a polyamic acid ester which is a general polyimide precursor, the adhesion can be easily improved even in a small amount.
이하 본 발명을 하기 실시예를 참조로 하여 보다 상세히 설명한다. 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 하기 실시예에 의하여 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be described in more detail with reference to the following examples. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
실시예Example 1. One.
(반응성 단량체의 합성)(Synthesis of reactive monomer)
500 mL 4구 플라스크 용기에서 아세톤 300g에, 2-하이드록시에틸메타크릴레이트(2-hydroxyethylmethacrylate) 13g, 트리에틸아민 10.1g을 첨가하여 녹인 후, 5-클로로-벤젠-1,3-디올(5-Chloro-benzene-1,3-diol) 14.5g을 첨가하여 70 ℃에서 10시간 동안 환류하면서 반응시켰다. 여기에, 트리에틸아민 20.2g, 3-클로로프로필 트리메톡시실란(3-chloropropyltrimethoxysilane) 19.9g, 에피클로로히드린(epichlorohydrin) 9.3g을 첨가하여, 70 ℃에서 10시간 동안 환류하면서 신규 반응성 단량체를 합성하였다.13 g of 2-hydroxyethylmethacrylate and 10.1 g of triethylamine were added to and dissolved in 300 g of acetone in a 500 mL four-neck flask, and 5-chloro-benzene-1,3-diol (5 -Chloro-benzene-1,3-diol) was added and reacted at 70 ° C for 10 hours while refluxing. Thereafter, 20.2 g of triethylamine, 19.9 g of 3-chloropropyltrimethoxysilane and 9.3 g of epichlorohydrin were added. While refluxing at 70 ° C for 10 hours, a new reactive monomer Were synthesized.
실시예Example 2. 2.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(N-mehtyl-2-pyrrolidone; NMP) 208g에 4,4'-메틸렌디아닐린(4,4'-methylenedianiline; MDA) 19.8g과 3,3',4,4'-벤조페논테트라카복실릭 디언하이드라이드(3,3',4,4'-benzophenonetetracarboxylic dianhydride; BTDA) 32.2g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이미드 전구체를 제조하였다. 여기에, 상기 실시예 1에서 합성한 신규 단량체 2.6g을 첨가하여 70 ℃에서 24시간 반응하여 신규 폴리이미드 전구체를 제조하였다.4,4'-methylenedianiline (MDA) was added to 208 g of N-mehtyl-2-pyrrolidone (NMP) in a 500 ml four- And 32.2 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) were added, and the mixture was polymerized at room temperature for 24 hours to obtain a solid content A polyimide precursor having a content of 20% was prepared. Then, 2.6 g of the novel monomer synthesized in Example 1 was added and reacted at 70 DEG C for 24 hours to prepare a new polyimide precursor.
실시예Example 3. 3.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(NMP) 209g에 4,4'-옥시디아닐린(4,4'-oxydianiline; ODA) 20.0g과 3,3',4,4'-벤조페논테트라카복실린 디언하이드라이드(3,3',4,4'-benzophenonetetracarboxylic dianhydride; BTDA) 32.2g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이 미드 전구체를 제조하였다. 여기에, 상기 실시예 1에서 합성한 신규 단량체 2.6g을 첨가하여 70 ℃에서 24시간 반응하여 신규 폴리이미드 전구체를 제조하였다.20.0 g of 4,4'-oxydianiline (ODA) was added to 209 g of N-methyl-2-pyrrolidone (NMP) in a 500 mL four- 32.2 g of 4,4'-benzophenonetetracarboxylic dianhydride (3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride; BTDA) was added and polymerization was carried out at room temperature for 24 hours to obtain a polyimide precursor having a solid content of 20% . Then, 2.6 g of the novel monomer synthesized in Example 1 was added and reacted at 70 DEG C for 24 hours to prepare a new polyimide precursor.
실시예Example 4. 4.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(NMP) 203g에 4,4'-메틸렌디아닐린(4,4'-methylenedianiline; MDA) 19.8g과 3,3',4,4'-옥시디프탈릭 언하이드라이드(3,3',4,4'-oxydiphthalic anhydride; ODPA) 31g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이미드 전구체를 제조하였다. 여기에, 상기 실시예 1에서 합성한 신규 단량체 2.5g을 첨가하여 70 ℃에서 24시간 반응하여 신규 폴리이미드 전구체를 제조하였다.19.8 g of 4,4'-methylenedianiline (MDA) was added to 203 g of N-methyl-2-pyrrolidone (NMP) in a 500 ml four- 31 g of 4,4'-oxydiphthalic anhydride (ODPA) was added and the mixture was polymerized at room temperature for 24 hours to prepare a polyimide precursor having a solid content of 20%. Then, 2.5 g of the novel monomer synthesized in Example 1 was added and reacted at 70 DEG C for 24 hours to prepare a new polyimide precursor.
비교예Comparative Example 1. One.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(NMP) 208g에 4,4'-메틸디아닐린(4,4'-methylenedianiline; MDA) 19.8g과 3,3',4,4'-벤조페논테트라카복실릭 디언하이드라이드(3,3',4,4'-benzophenonetetracarboxylic dianhydride; BTDA) 32.2g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이미드 전구체를 제조하였다.19.8 g of 4,4'-methylenedianiline (MDA) was added to 208 g of N-methyl-2-pyrrolidone (NMP) in a 500 ml four- 32.2 g of 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) was added and the mixture was polymerized at room temperature for 24 hours to obtain a polyimide precursor having a solid content of 20% .
비교예Comparative Example 2. 2.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(NMP) 209g에 4,4'-옥시디아닐린(4,4'-oxydianiline; ODA) 20.0g과 3,3',4,4'-벤조페논테트라카복실릭 디언하이드라이드(3,3',4,4'-benzophenonetetracarboxylic dianhydride; BTDA) 32.2g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이미드 전구체를 제조하였다. 이후, 여기에 아미노프로필 트리메톡시실란(aminopropyl trimethoxy silane) 2.6g을 첨가하였다.20.0 g of 4,4'-oxydianiline (ODA) was added to 209 g of N-methyl-2-pyrrolidone (NMP) in a 500 mL four- 32.2 g of 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) was added and the mixture was polymerized at room temperature for 24 hours to obtain a polyimide precursor having a solid content of 20% . Thereafter, 2.6 g of aminopropyl trimethoxy silane was added thereto.
비교예Comparative Example 3. 3.
(폴리이미드 전구체의 제조)(Preparation of polyimide precursor)
500 mL 4구 플라스크 용기에 질소기류하에서 N-메틸-2-피롤리돈(NMP) 203g에 4,4'-메틸렌디아닐린(4,4'-methylenedianiline; MDA) 19.8g과 3,3',4,4'-옥시디프탈릭 언하이드라이드(3,3',4,4'-oxydiphthalic anhydride; ODPA) 31g을 첨가하여 상온에서 24시간 동안 중합하여 고형분 함량 20%의 폴리이미드 전구체를 제조하였다. 이후, 여기에 글리시독시프로필 트리메톡시실란(glycidoxypropyl trimethoxy silane) 2.5g을 첨가하였다.19.8 g of 4,4'-methylenedianiline (MDA) was added to 203 g of N-methyl-2-pyrrolidone (NMP) in a 500 ml four- 31 g of 4,4'-oxydiphthalic anhydride (ODPA) was added and the mixture was polymerized at room temperature for 24 hours to prepare a polyimide precursor having a solid content of 20%. Then, 2.5 g of glycidoxypropyl trimethoxy silane was added thereto.
실험예Experimental Example
(접착력 평가 시험)(Adhesive strength evaluation test)
실리콘 웨이퍼, 유리, ITO 유리, 및 Cr 기판의 4종류의 기판 위에 상기 실시예 및 비교예의 폴리이미드 전구체를 스핀 코팅하고, 110℃에서 10분, 200℃에서 30분, 300℃에서 60분 동안 가열하여 두께 약 10㎛의 폴리이미드 박막을 얻었다. 상기 폴리이미드 박막 위에 1mm 간격으로 100개의 격자를 흠집내어 80℃, 80% 상대습도하에서 48시간 동안 방치하였다. 이후, 3M사 셀로판테이프로 격자면에 부착하여 90도 각도에서 폴리이미드 박막을 박리하였다. 아래 표1에 실험결과를 나타내었다.The polyimide precursors of the above Examples and Comparative Examples were spin-coated on four kinds of substrates of silicon wafer, glass, ITO glass, and Cr substrate and heated at 110 ° C for 10 minutes, 200 ° C for 30 minutes and 300 ° C for 60 minutes Thereby obtaining a polyimide thin film having a thickness of about 10 mu m. 100 lattices were scratched at intervals of 1 mm on the polyimide thin film and left for 48 hours at 80 DEG C and 80% relative humidity. Thereafter, the polyimide thin film was peeled off at an angle of 90 degrees by attaching it to the lattice plane with 3M cellophane tape. The experimental results are shown in Table 1 below.
[표 1][Table 1]
○ : 박리가 일어나지 않음
△ : 일부 박리가 일어남
× : 전체 박리가 일어남week)
○: No peeling occurred
DELTA: Partial peeling occurred
X: full peeling occurred
상기 표 1의 결과로부터, 본 발명의 폴리이미드 박막 격자는 박리가 이루어지지 않아 폴리이미드 박막의 접착력이 우수함을 알 수 있었다. 그러나, 비교예의 경우 기판으로부터 폴리이미드 박막의 박리가 쉽게 이루어져 접착력이 불량함을 알 수 있었다.From the results shown in Table 1, it can be seen that the polyimide thin film lattice of the present invention is not peeled off, and the adhesion of the polyimide thin film is excellent. However, in the comparative example, it was found that the polyimide thin film was easily peeled off from the substrate and the adhesive strength was poor.
본 발명의 반응성 단량체 화합물은 폴리이미드 전구체에 적용되어 접착력을 향상시키고, 이러한 폴리이미드 전구체는 반도체 및 디스플레이 등의 전기 전자 분 야의 접착재료로서 적용될 수 있다.The reactive monomer compound of the present invention is applied to a polyimide precursor to improve the adhesive strength, and such polyimide precursor can be applied as an adhesive material for electrical and electronic fields such as semiconductors and displays.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990057019A (en) * | 1997-12-29 | 1999-07-15 | 유현식 | Reactive Monomer for Photosensitive Polyimide Composition |
| KR100278969B1 (en) | 1998-02-10 | 2001-11-26 | 유현식 | Reactive monomers crosslinked with polyimide precursors and compositions comprising them |
| KR20040083610A (en) * | 2003-03-24 | 2004-10-06 | 주식회사 엘지화학 | Transparent and Highly Heat-resistant Polyimide Precusor and Photosensitive Resin Composition Using the Same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990057019A (en) * | 1997-12-29 | 1999-07-15 | 유현식 | Reactive Monomer for Photosensitive Polyimide Composition |
| KR100278969B1 (en) | 1998-02-10 | 2001-11-26 | 유현식 | Reactive monomers crosslinked with polyimide precursors and compositions comprising them |
| KR20040083610A (en) * | 2003-03-24 | 2004-10-06 | 주식회사 엘지화학 | Transparent and Highly Heat-resistant Polyimide Precusor and Photosensitive Resin Composition Using the Same |
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| KR20090072379A (en) | 2009-07-02 |
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