CN107189066A - Polyimide, polyimide film, and flexible copper foil substrate - Google Patents
Polyimide, polyimide film, and flexible copper foil substrate Download PDFInfo
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- CN107189066A CN107189066A CN201610199667.8A CN201610199667A CN107189066A CN 107189066 A CN107189066 A CN 107189066A CN 201610199667 A CN201610199667 A CN 201610199667A CN 107189066 A CN107189066 A CN 107189066A
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- Prior art keywords
- polyimide
- copper foil
- polyimide film
- tetravalent
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 105
- 239000004642 Polyimide Substances 0.000 title claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 67
- 239000011889 copper foil Substances 0.000 title claims description 59
- 239000000758 substrate Substances 0.000 title claims description 25
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 150000003852 triazoles Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 15
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 14
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims 5
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 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 15
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 10
- -1 tetracarboxylic dianhydride compound Chemical class 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004227 thermal cracking Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- NMGBFVPQUCLJGM-UHFFFAOYSA-N 3-ethylphthalic acid Chemical compound CCC1=CC=CC(C(O)=O)=C1C(O)=O NMGBFVPQUCLJGM-UHFFFAOYSA-N 0.000 description 1
- WRFWTYGMKIUAKL-UHFFFAOYSA-N 3-methylphenol Chemical compound CC1=CC=CC(O)=C1.CC1=CC=CC(O)=C1 WRFWTYGMKIUAKL-UHFFFAOYSA-N 0.000 description 1
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 description 1
- MUBMBUGIVIAHII-UHFFFAOYSA-N 3-propylphthalic acid Chemical compound CCCC1=CC=CC(C(O)=O)=C1C(O)=O MUBMBUGIVIAHII-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- AQVOMFPTJXMAQE-UHFFFAOYSA-N 4-propylphthalic acid Chemical compound CCCC1=CC=C(C(O)=O)C(C(O)=O)=C1 AQVOMFPTJXMAQE-UHFFFAOYSA-N 0.000 description 1
- 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 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- MRSWDOKCESOYBI-UHFFFAOYSA-N anthracene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 MRSWDOKCESOYBI-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GBASTSRAHRGUAB-UHFFFAOYSA-N ethylenetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2=C1C(=O)OC2=O GBASTSRAHRGUAB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- UMSVUULWTOXCQY-UHFFFAOYSA-N phenanthrene-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1C(O)=O UMSVUULWTOXCQY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses polyimide, which comprises repeating units represented by a formula (I) and a formula (II), wherein the repeating units are arranged in a block mode or a disordered mode:(I)
Description
Technical Field
The present invention relates to polyimide, a polyimide film and a flexible copper clad laminate, and more particularly, to a polyimide polymer having a nitrogen-containing heterocycle, a polyimide film including the polyimide, and a flexible copper clad laminate including the polyimide film.
Background
With the trend of light and thin electronic products, the usage demand of the flexible printed circuit board is greatly increased. Generally, the flexible printed circuit includes a flexible substrate and a conductive trace attached to the flexible substrate, and the conductive trace has a specific layout design so as to transmit an electrical signal to a predetermined area along a predetermined path.
For the case that the flexible substrate is a polyimide substrate, the method for manufacturing the flexible circuit board may include the following steps: the polyamic acid solution is first coated on a metal foil, and then heated to cause dehydration reaction of the polyamic acid solution on the metal foil, thereby forming a polyimide film. Then, the metal foil is patterned to form a desired conductive circuit pattern. In addition, an adhesive layer may be additionally coated on the metal foil before the polyamic acid solution is coated, so as to improve the adhesion between the subsequent polyimide film and the metal foil.
However, even though the flexible printed circuit board and the method for manufacturing the same have been widely adopted in the industry, there still exist many technical defects. For example, when the metal foil is selected from rolled copper foil with low surface roughness and thin thickness, the adhesive layer still cannot provide good adhesion between the polyimide film and the copper foil, and the patterned flexible circuit board is also curled due to the presence of the adhesive layer.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a polyimide having a nitrogen-containing heterocycle, a polyimide film including the polyimide, and a flexible copper foil substrate including the polyimide film, so as to solve the above disadvantages in the prior art.
According to an embodiment of the present invention, there is provided a polyimide including repeating units represented by the following formulas (I) and (II) in a block arrangement or a random arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
According to another embodiment of the present invention, there is provided a polyimide film having a composition including repeating units represented by the following formulae (I) and (II) in a block arrangement or a disordered arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by formula (I) and formula (II), respectively, wherein e/d is 5% to 10%.
According to still another embodiment of the present invention, there is provided a flexible copper foil substrate including a copper foil and a polyimide film directly contacting the copper foil, wherein the composition of the polyimide film includes repeating units represented by the following formulae (I) and (II) in a block arrangement or a random arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
Preferably, Ar includes tetravalent biphenyl and tetravalent phenyl.
Preferably, the mole ratio of tetravalent biphenyl to tetravalent phenyl is between about 5: 1 to 4: 1.
Preferably, the molar ratio of phenylene group to phenylene ether group is between 20: 1 to 16: 1.
Preferably, the polyimide is obtained by polymerization of a monomer solution, wherein the composition of the monomer solution includes 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), p-phenylenediamine (PPD/PDA), 4,4 ' -diaminodiphenyl ether (ODA), and 3, 5-diamino-1, 2, 4-triazole (DATA).
Preferably, no adhesive layer is disposed between the copper foil and the polyimide film.
Preferably, the peel strength between the polyimide film and the copper foil is between 0.4 kgf/cm and 0.9 kgf/cm.
According to the above embodiments, since the polyimide has a certain proportion of nitrogen-containing heterocyclic ring, excellent adhesion can be generated between the corresponding polyimide film and the copper foil. In this case, even if an adhesive layer is not provided on the copper foil, excellent peel strength can be obtained between the polyimide film and the copper foil. In addition, since the step of coating the adhesive layer can be omitted, the process can be simplified, and the flexible copper foil substrate after patterning can not generate the problem of curling.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
In the following, for the purpose of describing particular numerical ranges, the term "from one numerical value to another numerical value" should be read to encompass any numerical value within the numerical range as well as smaller numerical ranges defined by any numerical value within the numerical range, as if the numerical value and the smaller numerical range were expressly recited in the specification. For the sake of brevity, the structure of each polymer or group is sometimes referred to as a bond line (skeletton formula) hereinafter, and carbon atoms, hydrogen atoms, and carbon-hydrogen bonds in the actual structure are omitted. However, when a specific atom or group of atoms is explicitly depicted in the structural formula, the depiction is the basis.
According to an embodiment of the present invention, there is provided a polyimide copolymer, wherein a structure of polyimide includes repeating units represented by the following formulae (I) and (II) in a block arrangement or a random arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
Ar in the formula (I) and the formula (II) is a tetracarboxylic dianhydride compound except for two carboxylic anhydride groups (- (CO)2O) and D, E is the other than two amino groups (-NH) in the diamine compound2) Other residues. Preferably, Ar may comprise tetravalent biphenyl and tetravalent phenyl groups, and the molar ratio therebetween is preferably about 5: 1 to 4: 1. Further, for the phenylene group and the phenylene ether group represented by D, the molar ratio of both is preferably about 20: 1 to 16: 1.
The preparation method of the above polyimide copolymer will be described in detail below. First, in a water bath (room temperature), the diamine compound in the above embodiment is added to a solvent and mixed, and completely dissolved to form a diamine monomer mixture. Wherein, when the diamine compound is 3, 5-diamino-1, 2, 4-triazole (DATA), p-phenylenediamine (PPD/PDA) and 4, 4' -diaminodiphenyl ether (ODA), the mole ratio of DATA in the diamine monomer mixture is preferably between about 5% and 10% of the total mole ratio of PPD and ODA, that is, 5% or less DATA/(PPD + ODA) or less 10%, and the mole ratio of PPD and ODA is preferably about 20: 1 to 16: 1.
The solvent may be selected from high-polarity aprotic solvents such as Hexamethylphosphoramide (HMPA), N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1, 3-Dimethylimidazolidinone (DMI), and m-cresol (m-cresol), but is not limited thereto.
It is noted that, in addition to the above-mentioned kind of diamine compound, it can be selected from the group consisting of, but not limited to: 4, 4' -diaminobenzophenone and derivatives of 3, 5-diamino-1, 2, 4-triazole. These diamine compounds may be used alone or in a mixture of plural kinds. The derivatives of the above DATA may be represented by the following structural formula:
wherein R is2And R3The carbon numbers of (A) are independent of each other and are preferably each an alkylene group having a carbon number of from 1 to 3. It should be noted that when R is2And R3When the carbon number of (2) is more than 3, the polyimide copolymer has a high thermal expansion coefficient, thereby reducing the adhesion between the polyimide copolymer and the copper foil.
After the diamine monomer mixed solution is obtained by the above process, the tetracarboxylic dianhydride monomer mixed solution which is mixed in advance can be added into the diamine monomer mixed solution in a water bath (room temperature) for condensation polymerization reaction, and after the reaction lasts for 3 to 5 hours, the needed polyamic acid solution can be formed. Among them, when the tetracarboxylic dianhydride compound is 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA), the molar ratio of BPDA to PMDA in the tetracarboxylic dianhydride monomer mixture is preferably about 5: 1 to 4: 1. At this time, the solid content of the polyamic acid solution is, for example, 15% to 20%.
In addition to the tetracarboxylic dianhydride compounds of the above-mentioned kind, it may be selected from the group consisting of, but not limited to: 2,2 '-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4, 4' -oxydiphthalic anhydride (ODPA), 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride (BTDA), ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 4- (p-phenylenedioxy) diphthalic dianhydride, 4' - (m-phenylenedioxy) diphthalic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 2,3,6, 7-anthracenetetracarboxylic dianhydride, 1,2,7, 8-phenanthrenetetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydride compounds may be used alone or in a mixture of plural kinds.
Thereafter, the polyamic acid solution was subjected to dehydration reaction under a nitrogen atmosphere to form polyimide as shown below. For the description of the symbols Ar, D, E, D, E/D, etc., reference is made to the above description of the formulae (I) and (II).
In detail, the dehydration reaction can be performed without using a catalyst, for example, the polyamic acid solution can be baked at 130 ℃ to 160 ℃ for 5 minutes to 10 minutes to remove the solvent, and then heated to 320 ℃ to 380 ℃ for 20 minutes to 40 minutes to perform the dehydration reaction. However, the present invention is not limited thereto. In another embodiment, the dehydration reaction may be carried out using a catalyst.
According to another embodiment of the present invention, there is provided a polyimide film whose main composition comprises the foregoing polyimide copolymer. Referring to the foregoing method for manufacturing a polyimide copolymer, the method for manufacturing a polyimide film includes forming a polyamic acid solution, coating the polyamic acid solution on a substrate by a coating process, and then performing a dehydration reaction. The coating process may be blade coating, spin coating or other suitable coating method, and the substrate may be copper foil or other suitable metal foil. The dehydration reaction may be performed, for example, by baking the polyamic acid solution at 130 ℃ to 160 ℃ for 5 minutes to 10 minutes to remove the solvent, and then heating to 320 ℃ to 380 ℃ for 20 minutes to 40 minutes. In addition, the polyimide film has a thickness of about 12 μm to 22 μm.
According to another embodiment of the present invention, a flexible copper foil substrate is provided, which includes a copper foil and the polyimide film. The polyimide film is used as a flexible substrate in the flexible copper foil substrate, and the copper foil can be an electrolytic copper foil, a rolled copper foil or other suitable copper foils with no specific thickness. Referring to the method for manufacturing the polyimide film, the method for manufacturing the flexible copper clad laminate may include coating a polyamic acid solution on a copper foil through a coating process, and then performing a dehydration reaction to form a polyimide film on the copper foil.
According to the embodiments, there are provided a polyimide copolymer, a polyimide film and a flexible copper clad laminate, wherein the polyimide copolymer has a divalent organic group of triazole, which can generate N — Cu bonding with copper, and the ratio between different monomers and the ratio between different repeating units are within a specific range, so that the polyimide copolymer, the corresponding polyimide film and the corresponding flexible copper clad laminate can maintain the existing physical and chemical properties, and can have excellent peel strength with a copper clad without applying an adhesive layer.
Various embodiments of the invention are described in further detail below in order to enable those skilled in the art to practice the invention. It should be noted that the following examples are merely illustrative and the present invention should not be construed as being limited thereto. That is, the materials, the amounts and the ratios of the materials, the process flows, and the like used in the respective embodiments may be appropriately changed without departing from the scope of the present invention.
Abbreviations for the respective compounds in the following examples and comparative examples and information on the sources thereof are listed below:
ODA: 4, 4' -diaminodiphenyl ether, available from JFE chemical Co., Ltd.
PDA: p-phenylenediamine, available from tokyo chemical corporation.
DATA: 3, 5-diamino-1, 2, 4-triazole, available from Dougui chemical Co.
And (3) PMDA: pyromellitic dianhydride, available from JFE chemical corporation.
BPDA: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, available from JFE chemical Co.
NMP: n-methyl-2-pyrrolidone, available from TEDIA corporation.
Copper foil: purchased from mitsui chemical company.
Example 1
In a water bath (room temperature), 1.26 g (0.006 mol%, 5mol%) of 4, 4' -diaminodiphenyl ether (ODA), 12.24 g (0.113 mol%, 90mol%) of p-Phenylenediamine (PDA), and 5 g (0.05 mol%, 5mol%) of 3, 5-diamino-1, 2, 4-triazole (DATA) were dissolved in 200 g of NMP with N-methyl-2-pyrrolidone (NMP) as a solvent, and stirred for 2 hours to form a diamine monomer mixed solution. After complete dissolution, 6.63 g (0.003 mol% of pyromellitic dianhydride (PMDA) and 40.77 g (0.138 mol% of 82mol%) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA), which had been uniformly mixed in advance, were added to the aforementioned diamine monomer mixed solution in three portions under a water bath. It is noted that in this example, the molar ratio of diamine monomer to dianhydride monomer is preferably about 1: 1, but is not limited thereto. Then, the mixed solution of the diamine monomer and the dianhydride monomer was continuously stirred, and after reacting for 3 hours, a polyamic acid solution having a solid content of 20% was obtained. Thereafter, 20 ml of the polyamic acid solution was coated on a rolled copper foil having a thickness of 1/3 ounces (oz) using a blade coating method, and then baked at 150 ℃ for 10 minutes to remove the NMP solvent. Subsequently, the copper foil coated with the polyamic acid solution was placed in an oxygen-free atmosphere at 350 ℃ for 30 minutes to perform a dehydration reaction, to obtain a polyimide film disposed on the copper foil of example 1. Finally, the copper foil was removed through an etching process to obtain the polyimide film of example 1, in which the thickness was measured with a low dynamometer, and the measured thickness was about 12 to 22 μm.
Example 2
The procedure for example 2 was substantially the same as that for example 1, except that the molar percentages of the monomers used in example 2 are shown in Table 1.
Comparative example
The procedure of the comparative example was substantially the same as that of example 1, except that the molar percentages of the monomers used in the comparative example are shown in Table 1.
Hereinafter, various methods for measuring physical properties of the foregoing polyimide film and flexible copper foil substrate will be described in detail, and the results of the measurement are shown in table 1. Each measurement item includes: thermal cracking temperature (Td), Coefficient of Thermal Expansion (CTE), tensile stress (tensile elongation), tensile elongation (elongation), tensile elastic modulus (tensile modulus), peel strength (peel elongation), solder heat resistance, and warpage after copper foil etching were measured.
Measurement of thermal cracking temperature
The thermal cracking temperature was measured according to the IPC-TM-6502.4.24.6 method. First, 0.5 g to 0.8 g of each of the polyimide films of examples 1 and 2 and comparative example was weighed out as a test film material. Then, the films were heated from 30 ℃ to 600 ℃ under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min using a thermogravimetric loss analyzer (manufactured by Seiko instruments Inc., japan, under the equipment name EXSTAR 6000), and the temperature measured when the films lost 5% by weight was taken as the thermal cracking temperature. In the industry, the thermal cracking temperature of polyimide films is generally at least 450 ℃ or higher, and the larger the value, the better the thermal stability of polyimide films.
Measurement of thermal expansion coefficient
First, the polyimide films of examples 1 and 2 and comparative example were each prepared as a film material having a length and width of 2mm × 30 mm. Next, using a thermomechanical analyzer (manufactured by Seiko Instrument Inc., japan), the equipment name is EXSTAR 6000), the temperature increase rate is set to 10 ℃/min, the films are heated from 30 ℃ to 450 ℃ under a nitrogen atmosphere, and the average value of the dimensional change amount between 50 ℃ and 300 ℃ is obtained to obtain the thermal expansion coefficient. Generally, the copper foil has a thermal expansion coefficient of 17 ppm/deg.C, and a thermal expansion coefficient of 17 + -5 ppm/deg.C is considered to be similar to that of the copper foil.
Measurement of tensile Strength
The tensile strength was measured according to IPC-TM-6502.4.19. C. First, the polyimide films of examples 1 and 2 and comparative example were each prepared as a film material having a length and width of 76.20mm × 12.70 mm. Next, a tensile rate of 50.8mm/min was set using a universal tester (manufactured by Shimadzu scientific instruments, Inc. (Shimadzu) under the equipment name AG-1S), and the relationship between the tensile force and the elongation of the polyimide film was continuously recorded until the polyimide film was broken. The tensile strength of the polyimide film was determined by dividing the tensile force applied to the polyimide film at the time of breaking by the cross-sectional area of the original sample.
Tensile elongation
Tensile elongation was measured according to IPC-TM-6502.4.19. C. First, the polyimide films of examples 1 and 2 and comparative example were each prepared as a film material having a length and width of 76.20mm × 12.70 mm. Next, a tensile rate of 50.8mm/min was set using a universal tester (manufactured by Shimadzu scientific instruments, Inc. (Shimadzu) under the equipment name AG-1S), and the relationship between the tensile force and the elongation of the polyimide film was continuously recorded until the polyimide film was broken. The tensile elongation can be determined by subtracting the original length of the polyimide film from the length of the polyimide film at the time of breaking and dividing by the original length of the polyimide film.
Modulus of elasticity in tension
The tensile modulus was measured according to IPC-TM-6502.4.19. C. First, the polyimide films of examples 1 and 2 and comparative example were each prepared as a film material having a length and width of 76.20mm × 12.70 mm. Next, a tensile rate of 50.8mm/min was set using a universal tester (manufactured by Shimadzu scientific instruments, Inc. (Shimadzu) under the equipment name AG-1S), and the relationship between the tensile force and the elongation of the polyimide film was continuously recorded until the polyimide film was broken. The tensile modulus of elasticity is determined from the tensile force and the corresponding elongation to which the polyimide film is subjected before breaking.
Measurement of peeling Strength
The peel strength was tested according to IPC-TM-6502.4.9. First, the polyimide films disposed on the copper foils of examples 1 and 2 and comparative example were cut into test samples having a width of 3.2mm together with the copper foil. Then, the test specimens were stretched at a tensile rate of 50.8mm/min using a universal tester (manufactured by Shimadzu scientific instruments, Inc. (Shimadzu, under the equipment name AG-1S)) to a tensile elongation of 30mm, and the tensile values were continuously recorded to determine the peel strength at that time. Note that, when the adhesion between the polyimide film and the copper foil is larger, the interface therebetween is less susceptible to external force damage. That is, the higher the value of the peel strength shown in table 1, the greater the adhesion force between the polyimide film and the copper foil.
Measurement of solder Heat resistance
The solder heat resistance was tested by IPC-TM-6502.4.13 method, cutting the flexible copper foil substrate into 5cm × 5cm samples, floating on the surface of molten tin at 300 deg.C for 10-30 s, and observing whether the flexible copper foil substrate delaminated.
Measurement of warpage after copper foil etching
The copper foil was tested for warpage after etching by IPC-TM-6502.4.22 method. Cutting the flexible copper foil substrate into samples of 25cm multiplied by 25cm, pasting the samples on a rigid plane, measuring the distances of four corners of the sample to be warped by a ruler, adding the four obtained numerical values, and dividing the four numerical values to obtain a curl value so as to judge the warping condition, wherein the warping condition is judged to be flat when the number is less than 1 cm.
TABLE 1
| Example 1 | Example 2 | Comparative example | |
| ODA(mol%)* | 5 | 5 | 5 |
| PDA(mol%)* | 90 | 85 | 95 |
| DATA(mol%)* | 5 | 10 | 0 |
| PMDA(mol%)** | 18 | 18 | 18 |
| BPDA(mol%)** | 82 | 82 | 82 |
| Temperature of thermal cracking (. degree.C.) | 600 | 593 | 602 |
| Coefficient of thermal expansion (ppm/. degree.C.) | 12.05 | 12.51 | 12.28 |
| Tensile stress (MPa) | 348.67 | 353.10 | 350.59 |
| Tensile elongation (%) | 21.10 | 15.98 | 26.34 |
| Tensile modulus of elasticity (GPa) | 7.43 | 7.50 | 7.35 |
| Peel Strength (Kgf/cm) | 0.684 | 0.828 | 0.486 |
| Solder heat resistance | By passing | By passing | By passing |
| Warp after etching (cm) | ＜1 | ＜1 | ＜1 |
*: mol% based on the total moles of ODA, PDA and DATA
**: mol% based on the total moles of PMDA and BPDA
As can be seen from table 1, the polyimide films of examples 1 and 2 both had peel strengths greater than 0.6kgf/cm and at least 40% higher than that of the polyimide film of comparative example, showing that the polyimide films of examples 1 and 2 had good adhesion to the copper foil. In addition, because para-Phenylenediamine (PDA) is used as a main synthetic monomer in a diamine solution in the synthesis process of the polyimide, the corresponding polyimide can have a thermal expansion coefficient close to that of a copper foil and has higher tensile stress and tensile elastic modulus.
According to the above embodiments, since the polyimide has a certain proportion of nitrogen-containing heterocyclic rings, excellent adhesion can be generated between the corresponding polyimide film and the copper foil. In this case, even if an adhesive layer is not provided on the copper foil, excellent peel strength can be obtained between the polyimide film and the copper foil. In addition, since the step of coating the adhesive layer can be omitted, the process can be simplified, and the flexible copper foil substrate after patterning can not generate the problem of curling.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (18)
1. A polyimide comprising repeating units represented by the following formulae (I) and (II) in a block arrangement or a random arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
2. The polyimide of claim 1, wherein Ar comprises a tetravalent biphenyl group and a tetravalent phenyl group.
3. The polyimide of claim 2, wherein the mole ratio of tetravalent biphenyl groups to tetravalent phenyl groups is between 5: 1 to 4: 1.
4. The polyimide of claim 1, wherein the molar ratio of phenylene groups to phenylene ether groups is from 20: 1 to 16: 1.
5. The polyimide according to claim 1, wherein the polyimide is obtained by polymerization of a monomer solution, wherein the monomer solution comprises 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine, 4,4 ' -diaminodiphenyl ether, and 3, 5-diamino-1, 2, 4-triazole.
6. A polyimide film comprising a polyimide, wherein the polyimide comprises repeating units represented by the following formulae (I) and (II) in a block arrangement or a random arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
7. The polyimide film of claim 6, wherein Ar comprises a tetravalent biphenyl group and a tetravalent phenyl group.
8. The polyimide film of claim 7 wherein the mole ratio of tetravalent biphenyl groups to tetravalent phenyl groups is between 5: 1 to 4: 1.
9. The polyimide film of claim 6, wherein the molar ratio of phenylene groups to phenylene ether groups is between 20: 1 to 16: 1.
10. The polyimide film according to claim 6, wherein the polyimide is obtained by polymerization of a monomer solution, wherein the monomer solution comprises 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine, 4,4 ' -diaminodiphenyl ether, and 3, 5-diamino-1, 2, 4-triazole.
11. The polyimide film of claim 6, wherein the polyimide film has a thickness of from 12 mm to 22 mm.
12. A flexible copper foil substrate is characterized by comprising:
a copper foil; and
a polyimide film in direct contact with the copper foil, wherein the composition of the polyimide film comprises a polyimide, wherein the polyimide comprises repeating units represented by the following formulas (I) and (II), and the repeating units are in a block arrangement or a disordered arrangement:
(I)
(II)
wherein,
ar is a tetravalent organic radical derived from a compound containing aromatic groups;
d comprises phenylene and phenylene ether;
e is a divalent organic group including triazole; and
d and e represent the mole fraction of the repeating units represented by the formula (I) and the formula (II), wherein e/d is more than or equal to 5% and less than or equal to 10%.
13. The flexible copper foil substrate of claim 12, wherein Ar comprises tetravalent biphenyl and tetravalent phenyl.
14. The flexible copper foil substrate of claim 13 wherein the mole ratio of tetravalent biphenyl groups to tetravalent phenyl groups is between about 5: 1 to 4: 1.
15. The flexible copper foil substrate of claim 12 wherein the molar ratio of phenylene groups to phenylene ether groups is about 20: 1 to 16: 1.
16. The flexible copper clad laminate as claimed in claim 12, wherein the polyimide is obtained by polymerization of a monomer solution, wherein the monomer solution comprises 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine, 4,4 ' -diaminodiphenyl ether and 3, 5-diamino-1, 2, 4-triazole.
17. The flexible copper foil substrate of claim 12, wherein no adhesive layer is disposed between the copper foil and the polyimide film.
18. The flexible copper foil substrate of claim 12, wherein a peel strength between the polyimide film and the copper foil is between 0.4 kgf/cm and 0.9 kgf/cm.
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| TW105107703A TW201731918A (en) | 2016-03-14 | 2016-03-14 | Polyimide, polyimide film, and flexible copper clad laminate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540840A (en) * | 2016-06-23 | 2018-01-05 | 臻鼎科技股份有限公司 | Polyamide acid, copper-clad plate and circuit board |
| CN112239539A (en) * | 2019-07-16 | 2021-01-19 | 臻鼎科技股份有限公司 | Polyamide acid composition, polyimide copper-clad plate and circuit board |
| TWI742945B (en) * | 2020-11-27 | 2021-10-11 | 國立中興大學 | Low-dissipation flexible copper-coated laminate, manufacturing method thereof, and electronic device |
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| CN101356864A (en) * | 2006-02-06 | 2009-01-28 | Lg化学株式会社 | Copper clad laminate for pasting chip on flexible plate |
| CN105367794A (en) * | 2014-08-21 | 2016-03-02 | 台虹科技股份有限公司 | Soluble thermoplastic polyimide composition and laminate made therefrom |
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2016
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- 2016-04-01 CN CN201610199667.8A patent/CN107189066A/en not_active Withdrawn
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| CN101356864A (en) * | 2006-02-06 | 2009-01-28 | Lg化学株式会社 | Copper clad laminate for pasting chip on flexible plate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107540840A (en) * | 2016-06-23 | 2018-01-05 | 臻鼎科技股份有限公司 | Polyamide acid, copper-clad plate and circuit board |
| CN112239539A (en) * | 2019-07-16 | 2021-01-19 | 臻鼎科技股份有限公司 | Polyamide acid composition, polyimide copper-clad plate and circuit board |
| TWI742945B (en) * | 2020-11-27 | 2021-10-11 | 國立中興大學 | Low-dissipation flexible copper-coated laminate, manufacturing method thereof, and electronic device |
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