CN108117655A - Method for producing polyimide film, and polyimide film - Google Patents
Method for producing polyimide film, and polyimide film Download PDFInfo
- Publication number
- CN108117655A CN108117655A CN201710535303.7A CN201710535303A CN108117655A CN 108117655 A CN108117655 A CN 108117655A CN 201710535303 A CN201710535303 A CN 201710535303A CN 108117655 A CN108117655 A CN 108117655A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- manufacturing
- film according
- monomer
- inorganic particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000010954 inorganic particle Substances 0.000 claims abstract description 38
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 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 abstract description 25
- 150000004985 diamines Chemical class 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 19
- 239000004952 Polyamide Substances 0.000 claims description 40
- 229920002647 polyamide Polymers 0.000 claims description 40
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 34
- 229940113088 dimethylacetamide Drugs 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 27
- -1 dimethyl formyl Amine Chemical class 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000011938 amidation process Methods 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- 230000009435 amidation Effects 0.000 description 14
- 238000007112 amidation reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 12
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000017525 heat dissipation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 244000137827 Rumex acetosa Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 2
- 235000005291 Rumex acetosa Nutrition 0.000 description 2
- 235000015807 Rumex acetosa ssp. acetosa Nutrition 0.000 description 2
- 235000015447 Rumex acetosa ssp. alpestris Nutrition 0.000 description 2
- 235000015448 Rumex acetosa ssp. ambiguus Nutrition 0.000 description 2
- 235000015437 Rumex acetosa ssp. arifolius Nutrition 0.000 description 2
- 235000015436 Rumex acetosa ssp. lapponicus Nutrition 0.000 description 2
- 235000015441 Rumex acetosa ssp. pseudoxyria Nutrition 0.000 description 2
- 235000015439 Rumex acetosa ssp. thyrsiflorus Nutrition 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 235000003513 sheep sorrel Nutrition 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 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 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HNHQPIBXQALMMN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HNHQPIBXQALMMN-UHFFFAOYSA-N 0.000 description 1
- RTZYKEGJECYEPD-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline 1,1'-biphenyl Chemical group c1ccc(cc1)-c1ccccc1.Nc1ccc(Oc2ccc(cc2)-c2ccc(Oc3ccc(N)cc3)cc2)cc1 RTZYKEGJECYEPD-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 241001123248 Arma Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OTZFCCQPIUGYIF-UHFFFAOYSA-N C1=CC=CC=C1.NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1 Chemical compound C1=CC=CC=C1.NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1 OTZFCCQPIUGYIF-UHFFFAOYSA-N 0.000 description 1
- CXZSNJPUJRPEEB-UHFFFAOYSA-N C=1C=CC=CC=1[Si](C)(O[SiH2]C)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1[Si](C)(O[SiH2]C)C1=CC=CC=C1 CXZSNJPUJRPEEB-UHFFFAOYSA-N 0.000 description 1
- DXYLECNPBQRBQL-UHFFFAOYSA-N CCC.NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 Chemical compound CCC.NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1 DXYLECNPBQRBQL-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
- HGKYUNQUBLLAJU-UHFFFAOYSA-N NC1=CC=C(OC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.C1=CC=CC=C1 Chemical compound NC1=CC=C(OC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.C1=CC=CC=C1 HGKYUNQUBLLAJU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a method for manufacturing a polyimide film and the polyimide film. Then, the polyamic acid mixture is heated at a drying temperature to form a polyamic acid film. Subsequently, the polyamic acid film is imidized to form a polyimide film. The weight percentage of the inorganic particles is 10 wt% to 50 wt% relative to the total weight of the inorganic particles, the diamine monomer and the tetracarboxylic dianhydride monomer, and the thermal conductivity of the polyimide film is greater than or equal to 0.4W/mK.
Description
Technical field
Manufacturing method and polyimide film of the present invention on a kind of polyimide film have good especially with regard to one kind
The manufacturing method and polyimide film of the polyimide film of thermal conductivity.
Background technology
Polyimides has the high molecular material of excellent mechanical performance, heat resistance and chemical resistance.Therefore,
Polyimides is widely used in flexible printed wiring board, such as mobile phone, camera model, touch panel module, liquid crystal display
All there is use in panel and tablet computer.However, electronic component can generate heat at work, excessive accumulation of heat can be led
It is excessively high to send a telegraph sub- product internal temperature, causes component wear, therefore the technology for improving electronic element radiating characteristic is taken seriously.
Due to polyimide film in itself have good heat resistance but thermal conductivity it is more bad, how to promote polyimides
The problem of thermal conductivity of film is to improve the accumulation of heat of flexible printed wiring board will be the current industry problem to be overcome.
The content of the invention
In view of the above problems, the present invention provides a kind of manufacturing method and polyimide film of polyimide film, so as to carrying
The thermal conductivity of polyimide film is risen, to solve the problems, such as to accumulate heat on flexible printed wiring board.
The present invention discloses a kind of manufacturing method of polyimide film, and it includes formation to include an inorganic particle, a diamines
One polyamic acid mixture of monomer and tetracarboxylic dianhydride's monomer.Then, polyamic acid mixture is heated with a drying temperature
Form a polyamide acid film.Then, polyamide acid film is subjected to a sub- amidation process and forms a polyimide film.Wherein, phase
For the total weight of inorganic particle, diamine monomer and tetracarboxylic dianhydride's monomer, the weight percent of inorganic particle for 10wt% extremely
50wt%, the thermal conductivity coefficient of polyimide film are more than or equal to 0.4W/mK.
The present invention also discloses a kind of PA membrane as obtained by the above method.
The manufacturing method and PA membrane of polyimide film according to the invention described above, due to compared with inorganic particulate
The total weight of grain, diamine monomer and tetracarboxylic dianhydride's monomer, the weight percent of inorganic particle is 10wt% to 50wt%, thus
The problem of heat is accumulated on flexible printed wiring board can be improved.Thus, as poly- obtained by sub- amidation polyamide acid film
Acid imide film can have high-termal conductivity, the problem that solving in the prior art.
The explanation of explanation and implementation below above with respect to present invention to demonstrate and explain the present invention original
Reason, and the claims for providing the present invention are further explained.
Description of the drawings
Fig. 1 is the flow chart of the polyimides film manufacturing method of one embodiment of the invention.
Specific embodiment
The detailed features and advantage of the narration present invention, content are enough to make any ability in detail in embodiments below
The technical staff in domain understands the technology contents of the present invention and implements according to this, and is wanted according to content disclosed in this specification, right
Protection domain and attached drawing are asked, any those skilled in the art can be readily understood upon the relevant purpose of the present invention and advantage.Below
Embodiment the viewpoint of the present invention is further described, it is but non-anyways to limit scope of the invention.
The production method for first introducing the polyimide film of the present invention below, refer to Fig. 1.Fig. 1 is one embodiment of the invention
Polyimide film production method flow chart.
One inorganic particle is added in a solvent and is uniformly mixed and forms a suspension (S101).
Specifically, solvent may be selected from dimethylformamide (N, N-Dimethyl formamide；DMF), dimethyl second
Amide (Dimethylacetamide；DMAc), dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide；DMSO), N- methyl -2- pyrroles
Pyrrolidone (N-methyl-2-pyrrolidone；) and its group that is formed NMP.The grain size of inorganic particle can be 0.1 micro-
Rice is to 5 microns.Inorganic particle is selected from aluminium oxide, boron nitride, zinc oxide, aluminium nitride, barium titanate and its group formed.It can borrow
By stirring inorganic particle is made to uniformly disperse in a solvent, to form suspension.Any mode or means that can reach stirring
Applied in the present invention.
Then, a diamine monomer and tetracarboxylic dianhydride's monomer are added in suspension and be uniformly mixed and form a polyamic acid
Mixture.
Specifically, diamine monomer is selected from p-phenylenediamine (Isosorbide-5-Nitrae-diamino benzene), m-phenylene diamine (MPD) (1,3-
Diamino benzene), 4,4'- diaminodiphenyl ethers (4,4'-oxydianiline), 3,4'- diaminodiphenyl ethers (3,4'-
Oxydianiline), 4,4'- diamino hexichol alkane (4,4'-methylene dianiline), DPD di p phenylenediamine (N, N-
Diphenylethylenediamine), diamino benzophenone (diaminobenzophenone), diamines diphenyl sulfone
(diamino diphenyl sulfone), two naphthylenediamines (1,5-naphthalene diamine), diaminodiphenyl sulfide
Double (the 3- amino phenols oxygroup) benzene (1,3-Bis (3- of (4,4'-diamino diphenyl sulfide), 1,3-
Aminophenoxy) benzene), double (the 4- amino phenols oxygroup) benzene (1,4-Bis (4-aminophenoxy) benzene) of 1,4-,
Double (the 4- amino phenols oxygroup) benzene (1,3-Bis (4-aminophenoxy) benzene) of 1,3-, double [4- (the 4- amino phenols oxygen of 2,2-
Base) phenyl] propane (2,2-Bis [4- (4-amino phenoxy) phenyl] propane), 4,4'- double (4- amino phenols oxygroup)
Double (the 3- amino phenols oxygroup) biphenyl (4,4'-bis- of biphenyl (4,4'-bis- (4-aminophenoxy) biphenyl), 4,4'-
(3-aminophenoxy) biphenyl), 1,3- dipropyl amido -1,1', 3,3'- tetramethyl disiloxanes (1,3-Bis (3-
Aminopropyl) -1,1', 3,3'-tetramethyldisiloxane), 1,3- dipropyl amido -1,1', 3,3'- tetraphenyl two
Siloxanes (1,3-Bis (3-aminopropyl) -1,1', 3,3'-tetraphenyldisiloxane), 1,3- dipropyls amido -
1,1- dimethyl -3,3- diphenyl disiloxane (1,3-Bis (aminopropyl) -
) and its group that is formed dimethyldiphenyldisiloxane.
Tetracarboxylic dianhydride's monomer is selected from pyromellitic acid anhydride (1,2,4,5Benzene tetracarboxylic
Dianhydride), biphenyl tetracarboxylic dianhydride (3,3', 4,4'-Biphenyl tetracarboxylic dianhydride),
Oxydiphthalic (4,4'-Oxydiphthalic anhydride), benzophenone tetracarboxylic dianhydride
(Benzophenonetetracarboxylic dianhydride), diphenyl sulfone tetracarboxylic dianhydride (3,3', 4,4'-
Diphenyl sulfonetetracarboxylic dianhydride), naphthalene tetracarboxylic dianhydride (1,2,5,6-naphthalene
Tetracarboxylic dianhydride), naphthalene dicarboxylic anhydride (Naphthalenetetracaboxylic Dianhydride),
Double-(3,4- phthalate anhydrides) dimethylsilane (bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride), 1,3- double (3,4- dicarboxyphenyis) -1,1', 3,3'- tetramethyl disiloxanes dianhydride (1,3-bis (3,4-
Phthalic anhydride)-tetramethyldisiloxane) and its group that is formed.Wherein, diamine monomer and four
The molar ratio of carboxylic acid dianhydride monomer can be 0.98：1 to 1.05:1.
Specifically, the step of forming polyamic acid mixture further includes the following steps.
Diamine monomer is added in, a mixture (S102) containing diamine monomer is formed in suspension.
Then, tetracarboxylic dianhydride's monomer is incorporated in formation polyamic acid mixture in the mixture containing diamine monomer
(S103)。
But the order of present invention addition diamine monomer and tetracarboxylic dianhydride's monomer can also be such as following step.
Tetracarboxylic dianhydride's monomer is added in, a mixture containing tetracarboxylic dianhydride's monomer is formed in suspension.
Then, diamine monomer is added in and polyamic acid mixture is formed in the mixture containing tetracarboxylic dianhydride's monomer.
Furthermore polyamic acid mixture is coated on a base material (S104).
Specifically, base material can be a supporting steel band or roller etc., but be not limited thereto.As for used coating side
Method, any existing coating technique is applied both to the present invention, such as slot coated method (slit coating) or mould can be used
Has rubbing method (die coating).
Then, heat drying polyamic acid mixture forms a polyamide acid film (S105).
Specifically, be coated with polyamic acid mixture base material be positioned in 120 DEG C to 200 DEG C of hot environment into
Row heat drying.Thus, which the solvent in polyamic acid mixture is left polyamic acid mixture by thermal evaporation, and make
Not vaporized polyamic acid mixture forms polyamide acid film.After the solvent in polyamic acid mixture by after thermal evaporation,
By polyamide acid film peeling base, polyamide acid film is obtained.One drying temperature of heat drying can be matched with the boiling point of solvent.
In section Example of the present invention, drying temperature is 120 DEG C to 200 DEG C, but is not limited thereto.
Uniaxial extension polyamide acid film is carried out at the same time sub- amidation process and forms polyimide film (S106).
Specifically, 0.05MPa (N/mm are applied to polyamide acid film2) to 0.5MPa (N/mm2) a uniaxial tension
Power makes polyamide acid film uniaxially carrying out sub- amidation process along in the state of stretching to form polyimide film.Sub- amidation
(imidization) reaction can be higher than the temperature of heat drying polyamide acid film is heated, and make polyamide garden sorrel
In polyamic acid dehydration and endless loop and form polyimide film.Sub- amidation process can also be added in polyamic acid
Dehydrating agent (such as：Acid anhydrides) or catalyst (polymer icarceration type catalyst) polyamic acid in polyamide garden sorrel is made to be dehydrated and dead
It cycles (chemical imidization method) and forms polyimide film.Wherein, heating temperature is higher, and polyamide acid film carries out sub- amidation
(imidization) time needed for reaction generation polyimide film is shorter.However, if the temperature of reaction is excessively high, then may
The bond between the atom in polyimide molecule can be destroyed so that polyimides is degraded (degradation) because of high temperature.
In section Example of the present invention, heating makes the temperature of the sub- amidation process of polyamide acid film progress be 250 DEG C to 450 DEG C, but
It is not limited thereto.
Uniaxial extension refers to the tensile stress that a direction is substantially only bestowed to polyamide acid film, and in tensile stress side
To vertical direction on, tension substantially is not bestowed to polyamide acid film.In an embodiment of the present invention, the polyamides formed
Amino acid film is a strip winding shape, and heating stepses are that polyamide acid film is allowed slowly to pass through high temperature furnace.Therefore, implementation of the invention
In example, the direction of uniaxial extension is parallel to the moving direction of polyamide acid film, that is, uniaxial extension is oriented parallel to polyamides
The long side direction of amino acid film, but not limited to this.In the other embodiment of the present invention, the direction of uniaxial extension is selected from polyamide
The either side of sorrel to.
It is inorganic compared with the total weight of the inorganic particle, the diamine monomer and tetracarboxylic dianhydride's monomer in the present embodiment
The weight percent of particle is 10wt% to 50wt%, preferably 20wt% to 35wt%, is more preferably 23wt% to 31.5wt%.
If inorganic particle is more than in the total weight content compared with the inorganic particle, the diamine monomer and tetracarboxylic dianhydride's monomer
50wt%, the then easy embrittlement of polyimide film increase cut-off knife consume without easily molded or polyimide film bad cut really up to the mark.
If inorganic particle content in compared with the total weight of the inorganic particle, the diamine monomer with tetracarboxylic dianhydride's monomer is less than
10wt%, then the heat dissipation effect of polyimide film is not notable.Furthermore the thermal conductivity coefficient of polyimide film is more than or equal to 0.4W/mK,
Preferably 0.45W/mK to 0.75W/mK.
Illustrate the manufacturing method of PA membrane disclosed in the present application below by way of several embodiments and comparative example, and into
Row experiment test is to compare its nature difference.
Comparative example 1
The 4,4'- diamino two of 96.23g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Phenylate (ODA), and stirred to dissolve.
Secondly, add in the pyromellitic acid anhydride (PDMA) of 103.77g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.
Then, polyamic acid mixture is coated on base material.Then, it is dried 10 minutes at 150 DEG C of temperature, it will
Polyamic acid mixture obtains the polyamide acid film that thickness is 12.5 microns to 75 microns by being removed on base material.
Furthermore in the state of uniaxial extension polyamide acid film, heat polyamide acid film 10 minutes with 300 DEG C, carry out sub-
Amidation process, and obtain polyimide film.The long side direction for being oriented parallel to polyamide acid film of uniaxial extension, is applied to poly-
The uniaxially pulling force of amide sorrel is 0.1MPa (0.1N/mm2)。
Embodiment 1-1
The aluminium oxide of 49.63g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g, it then, will
Dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 72.35g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 78.02g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 1-2
The step of embodiment 1-2, is similar to embodiment 1-1, and embodiment 1-2 is in embodiment 1-1 differences in poly- sub- acyl
Aminating process fixed form is different, and the corner of polyimide film in the stationary state, polyamides is heated with 300 DEG C by embodiment 1-2
Amino acid film 10 minutes carries out sub- amidation process, and obtains polyimide film.
Embodiment 2-1
The aluminium oxide and 4.41g of 48.53g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Boron nitride, then, dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 70.76g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 76.3g, and stir 6 it is small when to carry out polymerisation, and obtain
Polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, single shaft
Extension is identical with comparative example one, just repeats no more herein.
Embodiment 2-2
The step of embodiment 2-2, is similar to embodiment 2-1, and embodiment 2-2 is in embodiment 2-1 differences in poly- sub- acyl
Aminating process fixed form is different, and the corner of polyimide film in the stationary state, polyamides is heated with 300 DEG C by embodiment 2-2
Amino acid film 10 minutes carries out sub- amidation process, and obtains polyimide film.
Embodiment 3-1
The aluminium oxide and 8.63g of 47.48g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Boron nitride, then, dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 69.23g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 74.66g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 3-2
The step of embodiment 3-2, is similar to embodiment 3-1, and embodiment 3-2 is in embodiment 3-1 differences in poly- sub- acyl
Aminating process fixed form is different, and the corner of polyimide film in the stationary state, polyamides is heated with 300 DEG C by embodiment 3-2
Amino acid film 10 minutes carries out sub- amidation process, and obtains polyimide film.
Embodiment 4-1
The aluminium oxide and 12.68g of 46.47g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Boron nitride, then, dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 67.77g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 73.08g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 4-2
The step of embodiment 4-2, is similar to embodiment 4-1, and embodiment 4-2 is in embodiment 4-1 differences in poly- sub- acyl
Aminating process fixed form is different, and the corner of polyimide film in the stationary state, polyamides is heated with 300 DEG C by embodiment 4-2
Amino acid film 10 minutes carries out sub- amidation process, and obtains polyimide film.
Embodiment 5-1
The aluminium oxide and 16.55g of 45.52g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Boron nitride, then, dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 66.36g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 71.57g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 5-2
The step of embodiment 5-2, is similar to embodiment 5-1, and embodiment 5-2 is in embodiment 5-1 differences in poly- sub- acyl
Aminating process fixed form is different, and the corner of polyimide film in the stationary state, polyamides is heated with 300 DEG C by embodiment 5-2
Amino acid film 10 minutes carries out sub- amidation process, and obtains polyimide film.
Embodiment 6
The boron nitride of 49.63g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g, it then, will
Dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, 4, the 4'- diaminodiphenyl ethers (ODA) of 47.62g and the p-phenylenediamine of 17.14g are added in suspension
(PPDA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 85.61g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 7
The boron nitride of 57.14g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g, the person of connecing will
Dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 67.73g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 74.12g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 8
The aluminium oxide and 16.55g of 45.52g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g
Zinc oxide, dimethylacetamide solution is uniformly mixed to form suspension by the person of connecing.
Secondly, in suspension add in 66.36g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 71.57g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 9
The aluminium nitride of 49.63g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g, it then, will
Dimethylacetamide solution is uniformly mixed to form suspension.
Secondly, in suspension add in 72.35g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 78.02g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Embodiment 10
The barium titanate of 49.63g is added in the dimethyl acetamide (DMAc) (purity 99.95wt%) of 800g, then, is mixed
Conjunction is formed uniformly suspension.
Secondly, in suspension add in 72.35g 4,4'- diaminodiphenyl ethers (ODA), and be uniformly mixed make its dissolving.
Then, add in the pyromellitic acid anhydride (PDMA) of 78.02g, and stir 6 it is small when to carry out polymerisation, and obtain
To polyamic acid mixture.The temperature of polymerisation is controlled at 20 DEG C to 30 DEG C.Next drying and forming-film, sub- amidation, list
Axis extension is identical with comparative example one, just repeats no more herein.
Table one is referred to, table one forms for the polyimide component of 15 embodiments of the invention and a comparative example, is solid
Determine mode and its Correlated Case with ARMA Measurement result.
Table one
Comparative example 1 measures the thermal conductivity coefficient of the polyimide film come under conditions of no added any inorganic particle
Less than 0.4W/mK, the problem of by causing heat dissipation effect bad.Embodiment 1-1 to embodiment 10 addition inorganic particle polyamides
In imines film, the thermal conductivity coefficient measured is all more than 0.4W/mK, there is preferable heat dissipation effect.
Embodiment 1-1, embodiment 2-1, embodiment 3-1, the inorganic matter adding proportion point of embodiment 4-1 and embodiment 5-1
It is not identical with embodiment 1-2, embodiment 2-2, embodiment 3-2, embodiment 4-2 and embodiment 5-2, poly- sub- acyl is only that at difference
Aminating process fixed form.Embodiment 1-1, embodiment 2-1, embodiment 3-1, the polyimide of embodiment 4-1 and embodiment 5-1
Change process fixed form is uniaxial extension, embodiment 1-2, embodiment 2-2, embodiment 3-2, embodiment 4-2 and embodiment 5-2
Polyimide process fixed form is by the Corner Strapped of polyimide film.Polyimide is understood by the measurement of table one
When process fixed form is uniaxial extension, polyimide film can obtain higher thermal conductivity coefficient, it is possible to provide preferable heat dissipation effect.
Embodiment 1-1 to the 4,4'- diaminodiphenyl ethers of embodiment 10, pyromellitic acid anhydride and inorganic particle gross weight
Measure as 200 g, the computational methods of adding proportion (wt%) for inorganic particle weight (g) divided by 200 g multiplied by with
100% and obtain.
The inorganic particle added in embodiment 1-1 be aluminium oxide, embodiment 2-1, embodiment 3-1, embodiment 4-1 and reality
It is respectively aluminium oxide and boron nitride to apply the inorganic particle added in a 5-1, wherein, embodiment 1-1, embodiment 2-1, embodiment
The aluminium oxide additive amount of 3-1, embodiment 4-1 and embodiment 5-1 be respectively 49.63g, 48.53g, 47.48g, 46.47g and
45.52g, embodiment 2-1, embodiment 3-1, embodiment 4-1, the nitridation Boron addition of embodiment 5-1 be respectively 4.41g,
8.63g, 12.68g and 16.55g.Understand that boron nitride adding proportion gets over high available in polyimide film by the measurement of table one
Higher thermal conductivity coefficient provides preferable heat dissipation effect.
In embodiment 1-1, embodiment 6, embodiment 9 and embodiment 10, the adding proportion of inorganic particle is all 24.81wt%
And the inorganic particle of single kind is only added, the thermal conductivity system of the polyimide film of addition boron nitride is understood by the measurement of table one
Number highest.The inorganic particle adding proportion of embodiment 5-1 and embodiment 8 is 31.03wt%, and embodiment 5-1 is added inorganic
Particle is aluminium oxide and boron nitride, and the inorganic particle that embodiment 8 is added is aluminium oxide, understands to implement by the measurement of table one
The thermal conductivity coefficient of example 5-1 compares 8 higher of embodiment.Therefore, the content for understanding inorganic particle by upper result can all be influenced with species
The thermal conductivity coefficient of polyimide film.
The manufacturing method and polyimide film of polyimide film according to the invention described above, add inorganic particle
Polyimide film can obtain some higher thermal conductivity coefficient, provide preferable heat dissipation effect.Thus, soft printing in the prior art
The problem of heat is accumulated on circuit board, causes electronic circuit component the problem of heat dissipation effect is bad occur and is just resolved.
Furthermore when the fixed form during polyamide acid film progress polyimide is uniaxial extension, polyimide film
Higher thermal conductivity coefficient can be obtained, it is possible to provide preferable heat dissipation effect.Thus, it is only necessary to which relatively low inorganic particle additive amount is taken
Polyimide processing procedure with uniaxial extension is that can obtain being equivalent to the poly- of higher inorganic particle additive amount collocation Corner Strapped
The high thermal conductivity coefficient that sub- amidation processing procedure is reached.Thereby, the additive amount of inorganic particle can be reduced, is obtained in making with high fever
While leading the polyimide film of coefficient, retain the machines such as high ductibility, high-tensile and the pliability of script polyimide film
Tool property.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
It knows those skilled in the art and makes various corresponding changes and deformation, but these corresponding changes and change in accordance with the present invention
Shape should all belong to the protection domain of appended claims of the invention.
Claims (16)
1. a kind of manufacturing method of polyimide film, which is characterized in that including：
Form the polyamic acid mixture for including an inorganic particle, a diamine monomer and tetracarboxylic dianhydride's monomer；
The polyamic acid mixture is heated with a drying temperature and forms a polyamide acid film；And
The polyamide acid film is subjected to a sub- amidation process and forms a polyimide film；
Wherein compared with the total weight of the inorganic particle, the diamine monomer and tetracarboxylic dianhydride's monomer, the weight of the inorganic particle
Amount percentage is 10wt% to 50wt%.
2. the manufacturing method of polyimide film according to claim 1, which is characterized in that form the polyamic acid mixture
The step of further include：
The inorganic particle is dissolved in a solvent and is uniformly mixed and forms a suspension；And
The diamine monomer is added in the suspension to be uniformly mixed to form the polyamic acid mixture with tetracarboxylic dianhydride's monomer.
3. the manufacturing method of polyimide film according to claim 2, which is characterized in that the diamine monomer and the tetrabasic carboxylic acid
The molar ratio of dianhydride monomer is 0.98：1 to 1.05:1.
4. the manufacturing method of polyimide film according to claim 1, which is characterized in that the thermal conductivity system of the polyimide film
Number is more than or equal to 0.4W/mK.
5. the manufacturing method of polyimide film according to claim 4, which is characterized in that the thermal conductivity system of the polyimide film
Number is 0.45W/mK to 0.75W/mK.
6. the manufacturing method of polyimide film according to claim 1, which is characterized in that the inorganic particle is selected from oxidation
Aluminium, boron nitride, zinc oxide, aluminium nitride, barium titanate and its group formed.
7. the manufacturing method of polyimide film according to claim 2, which is characterized in that the solvent is selected from dimethyl formyl
Amine, dimethyl acetamide, dimethyl sulfoxide (DMSO), n-methyl-2-pyrrolidone and its group formed.
8. the manufacturing method of polyimide film according to claim 1, which is characterized in that the diamine monomer is selected to benzene two
Amine, m-phenylene diamine (MPD), 4,4'- diaminodiphenyl ethers, 3,4'- diaminodiphenyl ethers, 4,4'- diamino hexichol alkane, DPD di p phenylenediamine,
Diamino benzophenone, diamines diphenyl sulfone, two naphthylenediamines, diaminodiphenyl sulfide, 1,3- double (3- amino phenols oxygroup) benzene, 1,4-
Double (the 4- amino phenols oxygroup) benzene of double (4- amino phenols oxygroup) benzene, 1,3-, 2,2- double [4- (4- amino phenols oxygroup) phenyl] propane, 4,
Double (the 4- amino phenols oxygroup) biphenyl of 4'-, 4,4'- double (3- amino phenols oxygroup) biphenyl, 1,3- dipropyl amido -1,1', 3,3'- tetramethyls
Base disiloxane, 1,3- dipropyl amido -1,1', 3,3'- tetraphenyls disiloxane, 1,3- dipropyl amido -1,1- dimethyl -3,3-
Diphenyl disiloxane and its group formed.
9. the manufacturing method of polyimide film according to claim 1, which is characterized in that tetracarboxylic dianhydride's monomer is selected from
Pyromellitic acid anhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic, benzophenone tetracarboxylic dianhydride, diphenyl sulfone tetrabasic carboxylic acid
Double (the 3,4- dicarboxyl benzene of dianhydride, naphthalene tetracarboxylic dianhydride, naphthalene dicarboxylic anhydride, double-(3,4- phthalate anhydrides) dimethylsilane, 1,3-
Base) -1,1', 3,3'- tetramethyl disiloxanes dianhydride and its group formed.
10. the manufacturing method of polyimide film according to claim 1, which is characterized in that the drying temperature for 120 DEG C extremely
200℃。
11. the manufacturing method of polyimide film according to claim 1, which is characterized in that the weight hundred of the inorganic particle
Divide than being 20wt% to 35wt%.
12. the manufacturing method of polyimide film according to claim 1, which is characterized in that the weight hundred of the inorganic particle
Divide than being 23wt% to 31.5wt%.
13. the manufacturing method of the polyimide film according to claim 1 to 12 any of which item, which is characterized in that by this
Polyamide acid film carries out the step of Asia amidation process forms the polyimide film and in the polyamide acid film single shaft is subject to prolong
The Asia amidation process is carried out under the situation stretched.
14. the manufacturing method of polyimide film according to claim 13, which is characterized in that carried out to the polyamide acid film
One uniaxial tension tension of the uniaxial extension is 0.05MPa to 0.5MPa.
15. the manufacturing method of polyimide film according to claim 13, which is characterized in that carried out to the polyamide acid film
One uniaxial tension tension of the uniaxial extension is 0.1MPa.
16. a kind of polyimide film, which is characterized in that it utilizes the polyamides according to claim 1 to 15 any of which item
Obtained by the manufacturing method of imines film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW105139561A TWI634141B (en) | 2016-11-30 | 2016-11-30 | Method for manufacturing polyimide film and polyimide film |
| TW105139561 | 2016-11-30 |
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| CN108117655A true CN108117655A (en) | 2018-06-05 |
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| TW (1) | TWI634141B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912878A (en) * | 2020-07-08 | 2022-01-11 | 达迈科技股份有限公司 | White polyimide film and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI715260B (en) * | 2019-10-22 | 2021-01-01 | 臺灣塑膠工業股份有限公司 | Method for synthesizing diamine compound having heterocyclic aryl groups, polyamic acid sensing film and polyimide film |
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| US20130273254A1 (en) * | 2012-04-13 | 2013-10-17 | Mortech Corporation | Polymide film and method for manufacturing the same |
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| TWI634141B (en) | 2018-09-01 |
| TW201821490A (en) | 2018-06-16 |
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