CN103374224A - Polyimide film, method for producing same, and polyimide film laminate comprising same - Google Patents
Polyimide film, method for producing same, and polyimide film laminate comprising same Download PDFInfo
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- CN103374224A CN103374224A CN2013100039420A CN201310003942A CN103374224A CN 103374224 A CN103374224 A CN 103374224A CN 2013100039420 A CN2013100039420 A CN 2013100039420A CN 201310003942 A CN201310003942 A CN 201310003942A CN 103374224 A CN103374224 A CN 103374224A
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- polyimide film
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- carbon powder
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- inorganic particle
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 153
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000010954 inorganic particle Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000002834 transmittance Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims 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 description 34
- 239000004642 Polyimide Substances 0.000 claims description 26
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229940059260 amidate Drugs 0.000 claims description 8
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
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- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
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- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 14
- 229920002647 polyamide Polymers 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 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
- 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 description 3
- 201000009310 astigmatism Diseases 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 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 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ADMRIZXRVIRWCR-UHFFFAOYSA-N 3-[(3-aminopropyl-methyl-phenylsilyl)oxy-methyl-phenylsilyl]propan-1-amine Chemical compound C=1C=CC=CC=1[Si](CCCN)(C)O[Si](C)(CCCN)C1=CC=CC=C1 ADMRIZXRVIRWCR-UHFFFAOYSA-N 0.000 description 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 2
- XRAAFZNZEZFTCV-UHFFFAOYSA-N 3-[[3-aminopropyl(diphenyl)silyl]oxy-diphenylsilyl]propan-1-amine Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CCCN)O[Si](CCCN)(C=1C=CC=CC=1)C1=CC=CC=C1 XRAAFZNZEZFTCV-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YQNJMCWNHBGABV-UHFFFAOYSA-N NC=1C=C(OC2=CC=C(C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical group NC=1C=C(OC2=CC=C(C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1.C1(=CC=CC=C1)C1=CC=CC=C1 YQNJMCWNHBGABV-UHFFFAOYSA-N 0.000 description 2
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 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 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Abstract
The invention discloses a matte black polyimide film, the film thickness of which ranges from 12 mu m to 250 mu m, and the film comprises carbon powder material with the weight percentage of about 1 to about 49 percent and inorganic particles with the weight percentage of about 1 to about 49 percent. The particle size of the carbon powder material and the inorganic particles is about 0.1 μm to about 10 μm. The polyimide film has a 60 DEG Gloss of 60GU (Gloss unit) or less, a thermal expansion coefficient of 30 ppm/DEG C or less, a light transmittance of 10% or less, and a thermal conductivity of 0.2W/m DEG C or more. The invention also discloses a method for manufacturing the polyimide film and a polyimide film laminated plate.
Description
Technical field
The invention relates to a kind of polyimide film, particularly about a kind of black polyamide film of high texture cloudy surface delustring low thermal coefficient of expansion and comprise the laminated plates of this black polyamide film.
Background technology
Polyimide (polyimide) belong to high mechanical strength, high temperature resistant and the insulation macromolecular material, nowadays be widely used in flexible printed wiring board (FPC) or other association area.For instance, the manufacture method of known flexible printed wiring board is after the flexible copper foil substrate of polyimide copper-clad (FCCL) is made desired circuit, and the polyimide film that will have again tackiness agent covers thereon.So polyimide film has become the indispensable material of electronic product that uses flexible printed wiring board.
Glue-free formula cover the base copper plate, it is the polyamic acid precursor with polyimide, usually prepared by the monomer chemical reaction of aromatic tetracarboxylic acid's dianhydride and aromatic diamine, the polyamic acid precursor is coated the surface of Copper Foil, heat again the solvent that removes polyamic acid, continue heating and makes the inferior amidation of polyamic acid generate the polyimide rete at copper foil surface with high temperature, it is characterized in that the polyimide rete need not be combined with adhesion agent layer between Copper Foil.Because known flexible printed wiring board needs in manufacturing processed through high-temperature step, but the substrate that polyimide film and Copper Foil form is because having different thermal expansion effects so that many material production curling, come off, can't contraposition or cause not good etc. the problem of degree of adhesion.
The problem of polyimide copper foil substrate on using is composition and the thickness thereof that is subject to polyimide material, make formed polyimide layer mostly be the colourity of yellow system or other tool high optical transmittance, when causing being used for soft board thereafter, so that the line design of the line layer of flexible printed wiring board distributes to be easy to understand by the same trade plagiarizes, and then the market sale and the company that affects product operate because of the light transmission of polyimide layer.Therefore, still need a kind of copper clad laminate that has the black screening effect and can reduce production costs.Circuit layout in the electronic product is real in recent years is key important and that must maintain secrecy, therefore sets up a kind of direct effectively time slot scrambling for circuit layout, also is problem necessary and that must solve.
So for above-mentioned problem, the current a solution that need to propose is maintained secrecy to solve thermal expansion effects, circuit, the problems such as appearance tactile impression or dazzle astigmatism.
Summary of the invention
People's livelihood consumption electronic products are because of dog-eat-dog in recent years, and mobile phone, pen electricity etc. is rolled one delustring look popular whirlwind, and black, gloss is soft and the delustring cloudy surface becomes the fashion pioneer who leads the taste trend simultaneously.So the outward appearance of product and inside and outside color all are emphasis demand projects, and because the polyimide pleurodiaphragmatic in terspace is the high glossiness product, for asking the texture of outward appearance, cloudy surface black polyamide film demand also in response to and give birth to.
Because polyimide film can be applicable on the product camera lenses such as photographic camera or microscope, as working as photomask etc., if the polyimide film surface gloss is too large, tend to cause because of luminous reflectance the problem of dazzle or astigmatism, cloudy surface black polyamide film is just meeting demand.
The present invention provides a kind of manufacture method of polyimide film.According to one embodiment of the invention, at first simultaneously inorganic particle and carbon powder material are added in the solvent, disperse with 20 ~ 100Hz rapid stirring, be prepared into the aaerosol solution that contains inorganic particle and carbon powder material.Because disperseing simultaneously two or more particle powder, can reduce the gathering of particle oneself itself and produce mutual effect of disperseing, namely need and need not add dispersion agent through other grinding steps, can finish finely disseminated micron-sized dispersion liquid.Add again tetracarboxylic dianhydride's monomer after then in above-mentioned aaerosol solution, adding the diamine monomer dissolving, make diamine monomer and tetracarboxylic dianhydride's monomer carry out polyreaction, namely prepare the polyamic acid mixture that contains inorganic particle and carbon powder material.The above-mentioned polyamic acid mixture of dried coating film forms the polyamic acid blend films again.Heat at last above-mentioned polyamic acid blend films, make its inferior amidation form above-mentioned polyimide film.Above-mentioned polyimide film can be naked membranous type attitude, and the needs of visual application are disposed at the related application field again.Above-mentioned polyamic acid mixture can directly be coated on the metallic film, and the metallic film that will scribble polyamic acid solution places under the environment of nitrogen and carry out the stage heating, makes the laminated plates of making black polyamide.
According to one embodiment of the invention, in the step of above-mentioned preparation polyamic acid blend films, need to continue the polyamic acid mixture that Stirring device has inorganic particle and carbon powder material, inorganic particle and carbon powder material are scattered in the polyamic acid mixture, avoid causing demixing phenomenon because of sedimentation.When polyreaction is finished, can get high-viscosity polyamide acid mixture solution.And after the viscosity increased of polyamic acid mixture, can avoid inorganic particle and carbon powder material because stopping to stir the sedimentation layering.Therefore, the viscosity of polyamic acid mixture be 100poise to 1000poise (be 10,000cps to 100,000cps).And the polyamic acid mixture is coated on the base material, and dry polyamic acid mixture is to form the polyamic acid blend films.
According to one embodiment of the invention, the weight percent of inorganic particle is 1wt% to 49wt%, is preferably 20wt% to 40wt%.According to another embodiment of the present invention, the particle diameter of inorganic particle is 0.1 micron to 10 microns, is preferably 0.5 micron to 6 microns.According to an again embodiment of the present invention, inorganic particle is to be selected from by mica powder, silicon dioxide powder, talcum powder, ceramics powder, clay powder, silica gel sintered powder and the above-mentioned group that consists of that forms.
According to one embodiment of the invention, the weight percent of carbon powder material is 1wt% to 49wt%, is preferably 3wt% to 30wt%.According to another embodiment of the present invention, the particle diameter of carbon powder material is 0.1 micron to 10 microns, is preferably 0.5 micron to 6 microns.According to an again embodiment of the present invention, carbon powder material comprises by oil or charcoal or other organism fully or the incomplete combustion carbon black and carbon ash, graphite, carbon ball, carbon pipe and Graphene and the above-mentioned group that consists of that forms that produce.
According to one embodiment of the invention, solvent is to be selected from by dimethyl formamide (N, N-Dimethylformamide, DMF), N,N-DIMETHYLACETAMIDE (Dimethylacetamide; DMAc), dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide, DMSO), N-Methyl pyrrolidone (N-methyl-2-pyrrolidone; NMP) and the group that consists of of above-mentioned combination.。
According to one embodiment of the invention, the mol ratio of tetracarboxylic dianhydride's monomer and diamine monomer is 0.9:1 to 1.1:1.
According to an embodiment of the present invention, diamine monomer is to be selected from by Ursol D (1,4diaminobenzene), mphenylenediamine (1,3diamino benzene), 4,4 '-diaminodiphenyl ether (4,4 '-oxydianiline), 3,4 '-diaminodiphenyl ether (3,4 '-oxydianiline), 4,4 '-two amido hexichol alkane (4,4 '-methylenedianiline), DPD di p phenylenediamine (N, N '-Diphenylethylenediamine), two amido benzophenone (diaminobenzophenone), diamines sulfobenzide (diamino diphenyl sulfone), two naphthylene diamines (1,5-naphthalene diamine), two amido diphenyl sulfides (4,4 '-diamino diphenyl sulfide), 1, two (the 3-amido phenol oxygen base) benzene (1 of 3-, 3-Bis (3-aminophenoxy) benzene), 1, two (the 4-amido phenol oxygen base) benzene (1 of 4-, 4-Bis (4-aminophenoxy) benzene), 1, two (the 4-amido phenol oxygen base) benzene (1 of 3-, 3-Bis (4-aminophenoxy) benzene), 2, two [4-(the 4-amido phenol oxygen base) phenyl] propane (2 of 2-, 2-Bis[4-(4-aminophenoxy) phenyl] propane), 4,4 '-two (4-amido phenol oxygen base) biphenyl 4,4 '-bis-(4-aminophenoxy) biphenyl, 4,4 '-two (3-amido phenol oxygen base) biphenyl 4,4 '-bis-(3-aminophenoxy) biphenyl, 1,3-dipropyl amido-1,1,3,3-tetramethyl disiloxane (1,3-Bis (3-aminopropyl)-1,1,3,3-tetramethyldisiloxane), 1,3-dipropyl amido-1,1,3,3-tetraphenyl sily oxide (1,3-Bis (3-aminopropyl)-1,1,3,3-tetraphenyldisiloxane), 1,3-dipropyl amido-1,1-dimethyl-3, the 3-phenylbenzene sily oxide (group that 1,3-Bis (aminopropyl)-dimethyldiphenyldisiloxane) and above-mentioned combination consist of.
According to an embodiment of the present invention, tetracarboxylic dianhydride's monomer is to be selected from by pyromellitic acid anhydride (1,2,4,5Benzene tetracarboxylic dianhydride), biphenyl tetracarboxylic dianhydride (3,3 ' 4,4 '-Biphenyltetracarboxylic dian hydride), phenyl ether tetracarboxylic dianhydride (4,4 '-Oxydiphthalic anhydride), benzophenone tetracarboxylic dianhydride (Benzophenonetetracarboxylicdianhy dride), sulfobenzide tetracarboxylic dianhydride (3,3 ', 4,4 '-diphenyl sulfonetetracarboxylic dianhydride), naphthyl tetracarboxylic dianhydride (1,2,5,6-naphthalene tetracarboxylic dianhydride), naphthalene dicarboxylic anhydride (NaphthalenetetracarboxylicDianhydride), two-(3, the 4-phthalate anhydride) (bis (3 for dimethylsilane, 4-dicarboxypheny1) dimethylsilane dianhydride), 1,3-two (3,4-dicarboxyl phenyl)-1,1,3, the 3-tetramethyl disiloxane dianhydride (group that 1,3-bis (4 '-phthalic anhydride)-tetramethyldisiloxane) and above-mentioned combination consist of.
According to one embodiment of the invention, the viscosity of polyamic acid mixture is 100poise to 1000poise.
According to one embodiment of the invention, the drying temperature of polyamic acid mixture is 120 ℃ to 200 ℃.According to another embodiment of the present invention, the Heating temperature of polyamic acid mixture is 270 ℃ to 400 ℃.
According to one embodiment of the invention, the thickness of polyimide film is 12 microns to 250 microns.
In addition, the present invention provides more than one and states the made a kind of polyimide film of manufacture method.According to one embodiment of the invention, it comprises polyimide, inorganic particle and carbon powder material, and above-mentioned three is scattered in the film forming, forms above-mentioned polyimide film.
According to one embodiment of the invention, 60 ° of Guang Ze Du＜=60GU (gloss unit) of polyimide film.According to another embodiment of the present invention, the Re Peng of polyimide film is swollen Xi Shuo＜=30ppm/ ℃.According to an again embodiment of the present invention, the thermal expansivity of polyimide film is identical with the thermal expansivity of Copper Foil.According to still another embodiment of the invention, the transparence of polyimide film is 10% to 0%.According to one embodiment of the invention, the heat-conduction coefficient of polyimide film is more than or equal to 0.2W/m-℃.
The present invention provides a kind of polyimide film laminated plates, comprises the above-mentioned polyimide film of base material and covering substrates.
According to one embodiment of the invention, base material is metal base.
According to one embodiment of the invention, the intermembranous Bonding strength of metal base and polyimide is more than or equal to 0.6kgf/cm.
Description of drawings
Fig. 1 is the manufacturing flow chart that illustrates the polyimide film with inorganic particle and carbon powder material;
Fig. 2 is the synoptic diagram that illustrates the polyimide film laminated plates;
Wherein, main element nomenclature:
110,120,130 and 140: step
210: base material
220: polyimide film.
Embodiment
For making the reader more understand polyimide film provided by the present invention, below enumerate several embodiment of the present invention, and be illustrated.Yet these embodiment are the example of demonstration as an illustration only, does not constitute any limitation for scope of the present invention and application.On the contrary, these embodiments will make exposure of the present invention more thorough and complete, and give full expression to protection scope of the present invention for haveing the knack of this skill person.In graphic, in order to know expression, identical reference number will be used to specify same or analogous manufacturing step.
The manufacture method of polyimide film
Fig. 1 is the manufacture method schema of the polyimide film that illustrates according to an embodiment of the present invention.
In step 110 shown in Figure 1, at first simultaneously inorganic particle and carbon powder material are added in the solvent, disperse with 20 ~ 100Hz rapid stirring, be prepared into the aaerosol solution that contains inorganic particle and carbon powder material.Because disperseing simultaneously two kinds of inorganic particle powder, can reduce the gathering of particle oneself itself and produce mutual effect of disperseing, namely need and need not add dispersion agent through other grinding steps, can finish finely disseminated micron-sized dispersion liquid.It should be noted that any blending means that achieves the above object, all be applicable among the present invention.
Because the particle diameter of inorganic particle or carbon powder material is too large or too littlely all can cause bad impact for polyimide film.On the one hand, if the particle diameter of inorganic particle or carbon powder material during greater than 10 microns, then the surface of made polyimide film is too coarse, and is not suitable in the electronic product.On the other hand, if the particle diameter of inorganic particle or carbon powder material during less than 0.1 micron, then inorganic particle or carbon powder material produce the phenomenon of gathering easily, cause the inhomogeneous problem of dispersion in polyimide film, and wayward on process operations.According to one embodiment of the invention, the particle diameter of inorganic particle or carbon powder material is 0.1 micron to 10 microns, is preferably 0.5 micron to 6 microns.
According to one embodiment of the invention, inorganic particle is to be selected from the group that is made of mica powder, silicon dioxide powder, talcum powder, ceramics powder, clay powder, kaolin, silica gel sintered powder and aforesaid combination.Ceramics powder for example can be silicon carbide, boron nitride, aluminum oxide or aluminium nitride, but is not limited to this.
According to one embodiment of the invention, carbon powder material comprises by oil or charcoal or other organism fully or the incomplete combustion carbon black and carbon ash, graphite, carbon ball, carbon pipe and the Graphene that produce.
According to one embodiment of the invention, solvent is to be selected from the group that is made of dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-Methyl pyrrolidone (NMP) and aforesaid combination.
Except the particle diameter of inorganic particle or carbon powder material can affect its dispersiveness in polyimide film, the weight percent of inorganic particle or carbon powder material also exerts an influence.
With the weight percent of inorganic particle, if during greater than 49wt%, then can causing, it disperses inhomogeneous phenomenon; If but it is during less than 1wt%, then can be so that 60 ° of glossiness too high (greater than 60GU) of polyimide film cause atomized surface effect not good.Therefore, the weight percent of inorganic particle is 1wt% to 49wt%, is preferably 20wt% to 40wt%.
With the weight percent of carbon powder material, if during greater than 49wt%, then can causing, it disperses inhomogeneous phenomenon; If it is during less than 1wt%, then can be so that the transparence of polyimide film higher (greater than 10%), and can't avoid the possibility of having an X-rayed.Therefore, the weight percent of carbon powder material is 1wt% to 49wt%, is preferably 3wt% to 30wt%.
In step 120 shown in Figure 1, add again tetracarboxylic dianhydride's monomer after in the prepared aaerosol solution of step 110, adding the diamine monomer dissolving, make diamine monomer and tetracarboxylic dianhydride's monomer carry out polyreaction, and continue to stir to form the polyamic acid mixture, namely prepare the polyamic acid mixture that contains inorganic particle and carbon powder material.In step 120, in continuing stirring, add diamine monomer and tetracarboxylic dianhydride's monomer in above-mentioned aaerosol solution.Diamine monomer and tetracarboxylic dianhydride's monomer carry out polyreaction, produce polyamic acid (polyamic acid, PAA).
According to one embodiment of the invention, the mol ratio of tetracarboxylic dianhydride's monomer and diamine monomer is 0.9:1 to 1.1:1.
According to an embodiment of the present invention, diamine monomer is to be selected from by Ursol D (1,4diaminobenzene), mphenylenediamine (1,3diamino benzene), 4,4 '-diaminodiphenyl ether (4,4 '-oxydianiline), 3,4 '-diaminodiphenyl ether (3,4 '-oxydianiline), 4,4 '-two amido hexichol alkane (4,4 '-methylenedianiline), DPD di p phenylenediamine (N, N '-Diphenylethylenediamine), two amido benzophenone (diaminobenzophenone), diamines sulfobenzide (diamino diphenyl sulfone), two naphthylene diamines (1,5-naphthalene diamine), two amido diphenyl sulfides (4,4 '-diamino diphenyl sulfide), 1, two (the 3-amido phenol oxygen base) benzene (1 of 3-, 3-Bis (3-aminophenoxy) benzene), 1, two (the 4-amido phenol oxygen base) benzene (1 of 4-, 4-Bis (4-aminophenoxy) benzene), 1, two (the 4-amido phenol oxygen base) benzene (1 of 3-, 3-Bis (4-aminophenoxy) benzene), 2, two [4-(the 4-amido phenol oxygen base) phenyl] propane (2 of 2-, 2-Bis[4-(4-amino phenoxy) phenyl] propane), 4,4 '-two (4-amido phenol oxygen base) biphenyl 4,4 '-bis-(4-aminophenoxy) biphenyl, 4,4 '-two (3-amido phenol oxygen base) biphenyl 4,4 '-bis-(3-aminophenoxy) biphenyl, 1,3-dipropyl amido-1,1,3,3-tetramethyl disiloxane (1,3-Bis (3-aminopropyl)-1,1,3,3-tetramethyldisiloxane), 1,3-dipropyl amido-1,1,3,3-tetraphenyl sily oxide (1,3-Bis (3-aminopropyl)-1,1,3,3-tetraphenyldisiloxane), 1,3-dipropyl amido-1,1-dimethyl-3, the 3-phenylbenzene sily oxide (group that 1,3-Bis (aminopropyl)-dimethyldiphenyldisiloxane) and aforesaid combination consist of.
According to an embodiment of the present invention, tetracarboxylic dianhydride's monomer is to be selected from by pyromellitic acid anhydride (1,2,4,5Benzene tetracarboxylic dianhydride), biphenyl tetracarboxylic dianhydride (3,3 ' 4,4 '-Biphenyltetracarboxylic dian hydride), phenyl ether tetracarboxylic dianhydride (4,4 '-Oxydiphthalic anhydride), benzophenone tetracarboxylic dianhydride (Benzophenonetetracarboxylicdianhy dride), sulfobenzide tetracarboxylic dianhydride (3,3 ', 4,4 '-diphenyl sulfonetetracarboxylic dianhydride), naphthyl tetracarboxylic dianhydride (1,2,5,6-naphthalene tetracarboxylic dianhydride), naphthalene dicarboxylic anhydride (NaphthalenetetracarboxylicDianhydride), two-(3, the 4-phthalate anhydride) (bis (3 for dimethylsilane, 4-dicarboxypheny1) dimethylsilane dianhydride), 1,3-two (3,4-dicarboxyl phenyl)-1,1,3, the 3-tetramethyl disiloxane dianhydride (group that 1,3-bis (4 '-phthalic anhydride)-tetramethyldisiloxane) and aforesaid combination consist of.
Because contain inorganic particle and carbon powder material in the prepared aaerosol solution of step 110, thus in polyamic acid, also mix above-mentioned inorganic particle and carbon powder material, and form the polyamic acid mixture.And, when the described polyreaction of step 120 is finished, can get high-viscosity polyamide acid mixture solution.And after the viscosity increased of polyamic acid mixture, can avoid inorganic particle and carbon powder material because stopping to stir the sedimentation layering.Therefore, the viscosity of polyamic acid mixture be 100poise to 1000poise (be 10,000cps to 100,000cps).
In step 130 shown in Figure 1, the polyamic acid mixture of subsequent drying step 120 preparation is to form the polyamic acid blend films.In step 130, the polyamic acid mixture is placed hot environment, make the solvent vaporization in the polyamic acid mixture, and stay the polyamic acid blend films that is not vaporized.According to one embodiment of the invention, the drying temperature of step 130 is 120 ℃ to 200 ℃.
In step 140 shown in Figure 1, the polyamic acid blend films that final heating step 130 forms is to form polyimide film.In step 140, the polyamic acid blend films is placed more hot environment, make polyamide acid film under high temperature, carry out inferior amidate action (imidization), produce polyimide film.The polyimide film that obtains at last can be naked membranous type attitude, can depend on the needs, and is disposed at the related application field again.According to one embodiment of the invention, the Heating temperature of step 140 is 270 ℃ to 400 ℃.
Via the polyimide film that step 140 forms, can select applicable polyimide film thickness according to user demand.According to one embodiment of the invention, the thickness of polyimide film is 12 microns to 250 microns.
The manufacture method of polyimide film
According to one embodiment of the invention, the polyamic acid mixture of step 120 preparation can be coated on the base material, dry (being step 130) this polyamic acid mixture again is to form the polyamic acid blend films.In one embodiment, base material is metal base, for example the copper base material.Copper base material described herein can comprise other metal, such as palladium, aluminium, iron, nickel or other suitable metal.Certainly, the field knows that usually the knowledgeable also can select other suitable material as base material under the present invention, such as aluminium base etc.
Then, process the above-mentioned polyamic acid mixture of coating base material 210 with heating steps (being step 140) after, namely form polyimide film 220, as shown in Figure 2.Be among the embodiment of copper base material at base material 210, the polyimide film laminated plates of formation is polyimide copper-clad laminated plates (polyimide copper cladlaminate).
The composition of polyimide film
The polyimide film of the method according to this invention manufacturing wherein comprises pi, inorganic particle and carbon powder material.Inorganic particle and carbon powder material are to be scattered in the polyimide, and form polyimide film.According to one embodiment of the invention, in polyimide film, the weight percent of inorganic particle is 1wt% to 49wt%, is preferably 20wt% to 40wt%.According to another embodiment of the present invention, in polyimide film, the weight percent of carbon powder material is 1wt% to 49wt%, is preferably 3wt% to 30wt%.
The testing method of polyimide film below is provided, and wherein the mensuration project of polyimide film comprises 60 ° of glossiness tests, light transmittance test and thermal expansivity test.
The preparation of polyimide film
Embodiment 1: the polyimide film (25 microns) that contains inorganic particle and carbon powder material
The carbon powder material of 6.98 kilograms silicon dioxide powders and 0.977 kilogram added in 79.07 kilograms the N,N-DIMETHYLACETAMIDE (DMAc), stir and be mixed with aaerosol solution.Wherein silicon dioxide powder is as inorganic particle.
Then in above-mentioned aaerosol solution, adds 6.71 kilograms 4, the pyromellitic acid anhydride (PMDA) of 4 '-diaminodiphenyl ether (ODA) and 7.24 kilograms, in 20 ℃ to 30 ℃ lower stirring 6 hours that continue, polymerization becomes the polyamic acid mixture.Wherein 4,4 '-diaminodiphenyl ether (ODA) is as diamine monomer, and pyromellitic acid anhydride (PMDA) is as tetracarboxylic dianhydride's monomer.
Be coated with above-mentioned polyamic acid mixture on base material, and place dry environment, with 150 ℃ of dry polyamic acid mixtures.Can get the polyamic acid blend films subsequently, it is naked membranous type attitude.
At last the polyamic acid blend films is placed heating environment, under 300 ℃ of high temperature, make polyamic acid carry out inferior amidate action (imidization), produce polyimide.The thickness of the polyimide film of embodiment 1 is 25 microns.
According to aforesaid testing method, measure 60 ° of glossiness, light transmittance and thermal expansivity of embodiment 1.60 ° of glossiness of embodiment 1 are 7.5GU, and light transmittance is 0%, and thermal expansivity is 15ppm/ ℃.
Embodiment 2: the polyimide film (25 microns) that only contains carbon powder material
In the N,N-DIMETHYLACETAMIDE (DMAc) with 79.07 kilograms of 0.977 kilogram carbon powder material addings, stir and be mixed with aaerosol solution.
Then in above-mentioned aaerosol solution, adds 6.71 kilograms 4, the pyromellitic acid anhydride (PMDA) of 4 '-diaminodiphenyl ether (ODA) and 7.24 kilograms, in 20 ℃ to 30 ℃ lower stirring 6 hours that continue, polymerization becomes the polyamic acid mixture.Wherein 4,4 '-diaminodiphenyl ether (ODA) is as diamine monomer, and pyromellitic acid anhydride (PMDA) is as tetracarboxylic dianhydride's monomer.
Be coated with above-mentioned polyamic acid mixture on base material, and place dry environment, with 150 ℃ of dry polyamic acid mixtures.Can get the polyamic acid blend films subsequently, it is naked membranous type attitude.
At last the polyamic acid blend films is placed heating environment, under 300 ℃ of high temperature, make polyamic acid carry out inferior amidate action (imidization), produce polyimide.The thickness of the polyimide film of embodiment 2 is 25 microns.
According to aforesaid testing method, measure 60 ° of glossiness, light transmittance and thermal expansivity of embodiment 2.60 ° of glossiness of embodiment 2 are 55GU, and light transmittance is 10%, and thermal expansivity is 40ppm/ ℃.
Embodiment 3: the polyimide film (25 microns) that does not contain inorganic particle and carbon powder material
With 6.71 kilograms 4, the pyromellitic acid anhydride (PMDA) of 4 '-diaminodiphenyl ether (ODA) and 7.24 kilograms adds in 79.07 kilograms the N,N-DIMETHYLACETAMIDE (DMAc), stirred 6 hours in 20 ℃ to 30 ℃ lower continuing, polymerization becomes polyamic acid.Wherein 4,4 '-diaminodiphenyl ether (ODA) is as diamine monomer, and pyromellitic acid anhydride (PMDA) is as tetracarboxylic dianhydride's monomer.
Be coated with above-mentioned polyamic acid on base material, and place dry environment, with 150 ℃ of dry polyamic acids.Can get polyamide acid film subsequently, it is naked membranous type attitude.
At last polyamide acid film is placed heating environment, under 300 ℃ of high temperature, make polyamic acid carry out inferior amidate action (imidization), produce polyimide.The thickness of the polyimide film of embodiment 3 is 25 microns.
According to aforesaid testing method, measure 60 ° of glossiness, light transmittance and thermal expansivity of embodiment 3.60 ° of glossiness of embodiment 3 are 125GU, and light transmittance is 100%, and thermal expansivity is 40ppm/ ℃.
Table 1
Because 60 ° of glossiness are reflective degree of expression body surface, lower this body surface of expression of numerical value is more not reflective, and atomized surface effect better.As shown in Table 1, compared to the polyimide film that does not contain inorganic particle (asking for an interview the sample 3 that embodiment 3 makes), 60 ° of glossiness that contain the polyimide film of inorganic particle obviously reduce (asking for an interview the sample 1 that embodiment 1 makes).The surface of light will become cloudy surface because the doping inorganic particle will make originally, and cloudy surface can effectively reduce luminous reflectance, to solve the problem of dazzle astigmatism.The doping inorganic particle helps to promote the atomized surface effect of polyimide film.
By the transparence result of table 1 as can be known, the carbon powder material of doping 3wt% to 30wt% can obviously reduce the light transmittance (asking for an interview the sample 2 that sample 1 that embodiment 1 makes and embodiment 2 make) of polyimide film in polyimide film, minimumly reaches 0%.Because the doping carbon powder material can allow polyimide film be black, and can't have an X-rayed.An amount of carbon powder material of doping and inorganic particle only be 25 microns although it should be noted that the thickness of polyimide film, as long as also can reach 0% light transmittance.This result also provides an effective solution for the privacy problem of circuit layout.Cloudy surface black polyamide film has also promoted the high texture of outward appearance.
In addition, as shown in Table 1, compared to a polyimide film of doping carbon powder material (asking for an interview the sample 2 that embodiment makes), the thermal expansivity of the polyimide film of doping inorganic particle and carbon powder material (asking for an interview the sample 1 that embodiment 1 makes) is obviously lower.Because polyimide film is on using, often need to carry out from different materials the high temperature compacting, if the thermal expansion coefficient difference of the thermal expansivity of polyimide film and respective material is too large, can cause then that polyimide film is curling to come off, cause on the processing procedure greatly problem.Therefore by the content of adjusting inorganic particle and carbon powder material, above-mentioned polyimide film can cooperate the thermal expansivity of respective material, reaches suitable thermal expansivity scope.For instance, the thermal expansivity that does not contain the polyimide film (asking for an interview the sample 3 that embodiment 3 makes) of inorganic particle and carbon powder material is 40ppm/ ℃ to 50ppm/ ℃, and the thermal expansivity of Copper Foil is about 17ppm/ ℃, if without any adjustment, then polyimide film may be in use curling.According to one embodiment of the invention, the thermal expansivity of polyimide film can reach 17ppm/ ℃, can meet the thermal expansivity of Copper Foil, can solve in the use procedure and cause curling problem because of thermal expansion.
Embodiment 4: the polyimide film (75 microns) that contains inorganic particle and carbon powder material
The carbon powder material of 6.32 kilograms talcum powder and 2.107 kilograms added in 79.63 kilograms the N,N-DIMETHYLACETAMIDE (DMAc), stir and be mixed with aaerosol solution.Wherein talcum powder is as inorganic particle.
Then in above-mentioned aaerosol solution, add 4.45 kilograms 4,4 '-diaminodiphenyl ether (ODA), 1.6 kilograms Ursol D (PPDA) and 8 kilograms pyromellitic acid anhydride (PMDA), stirred 6 hours in 20 ℃ to 30 ℃ lower continuing, polymerization becomes the polyamic acid mixture.Wherein 4,4 '-diaminodiphenyl ether (ODA), Ursol D (PPDA) are as diamine monomer, and pyromellitic acid anhydride (PMDA) is as tetracarboxylic dianhydride's monomer.
Be coated with above-mentioned polyamic acid mixture on base material, and place dry environment, with 150 ℃ of dry polyamic acid mixtures.Can get the polyamic acid blend films subsequently, it is naked membranous type attitude.
At last the polyamic acid blend films is placed heating environment, under 350 ℃ of high temperature, make polyamic acid carry out inferior amidate action (imidization), produce polyimide.The thickness of the polyimide film of embodiment 4 is 75 microns.
According to aforesaid testing method, measure 60 ° of glossiness, light transmittance and thermal expansivity of embodiment 4.60 ° of glossiness of embodiment 4 are 7.0GU, and light transmittance is 0%, and thermal expansivity is 17ppm/ ℃.
Embodiment 5: the polyimide film (75 microns) that does not contain inorganic particle and carbon powder material
With 4.45 kilograms 4, the pyromellitic acid anhydride (PMDA) of 4 '-diaminodiphenyl ether (ODA), 1.6 kilograms Ursol D (PPDA) and 8 kilograms adds in 79.63 kilograms the N,N-DIMETHYLACETAMIDE (DMAc), stirred 6 hours in 20 ℃ to 30 ℃ lower continuing, polymerization becomes polyamic acid.Wherein 4,4 '-diaminodiphenyl ether (ODA), Ursol D (PPDA) are as diamine monomer, and pyromellitic acid anhydride (PMDA) is as tetracarboxylic dianhydride's monomer.
Be coated with above-mentioned polyamic acid on base material, and place dry environment, with 150 ℃ of dry polyamic acids.Can get polyamide acid film subsequently, it is naked membranous type attitude.
At last polyamide acid film is placed heating environment, under 350 ℃ of high temperature, make polyamic acid carry out inferior amidate action (imidization), produce polyimide.The thickness of the polyimide film of embodiment 5 is 75 microns.
According to aforesaid testing method, measure 60 ° of glossiness, light transmittance and thermal expansivity of embodiment 5.60 ° of glossiness of embodiment 5 are 120GU, and light transmittance is＞50%, and thermal expansivity is 25ppm/ ℃ to 40ppm/ ℃.
Table 2
As shown in Table 2, compared to the polyimide film that does not contain inorganic particle and carbon powder material (asking for an interview the sample 5 that embodiment 5 makes), 60 ° of glossiness, light transmittance and thermal expansivity containing the polyimide film (asking for an interview the sample 4 that embodiment 4 makes) of inorganic particle and carbon powder material all obviously descend.In addition, by the weight ratio of adjusting inorganic particle and carbon powder material, although the thickness of the polyimide film that table 2 provides is 75 microns, also can reach the character performance close with table 1.
Embodiment 6: the polyimide copper-clad laminated plates
With 4 of different ratios, 4 '-diaminodiphenyl ether (ODA), Ursol D (PPDA), biphenyl tetracarboxylic dianhydride (BPDA), phenyl ether tetracarboxylic dianhydride (ODPA) join in 168 kilograms the N-Methyl pyrrolidone (NMP), stirred 6 hours in 20 ℃ to 40 ℃ lower continuing, polymerization becomes polyamic acid.
Be coated with above-mentioned polyamic acid and in thickness be on 35 microns the copper base material, and place and carry out the stage heating under 80 to 400 ℃, make polyamic acid carry out inferior amidate action (imidization), and form the polyimide copper-clad laminated plates.The thickness of polyimide film is 25 microns.Then, the polyimide film that obtains after the etching is measured 60 ° of glossiness, light transmittance and heat-conduction coefficient, as shown in table 3.
Table 3
As shown in Table 3, compared to the polyimide film that does not contain inorganic particle and carbon powder material (asking for an interview sample 6 and 9), the 60 ° of glossiness (58GU is following) that contain the polyimide film (asking for an interview sample 7,8,10) of inorganic particle and carbon powder material are lower with light transmittance (0%), and heat-conduction coefficient higher (more than the 0.22W/mK).And when the addition of inorganic particle is higher, 60 ° of glossiness of polyimide film are lower.
In addition, the Bonding strength between test polyimide film and copper base material and the size changing rate before and after the etching, as shown in table 4.
Table 4
| Sample | Bonding strength (kgf/cm) | Size changing rate (%) |
| 6 | 0.95 | 0.06 |
| 7 | 1.02 | 0.05 |
| 8 | 0.95 | 0.04 |
| 9 | 0.8 | 0.07 |
| 10 | 1.12 | 0.04 |
As shown in Table 4, compared to the polyimide film that does not contain inorganic particle and carbon powder material (asking for an interview sample 6 and 9), the Bonding strength slightly high (more than the 0.95kgf/cm) that contains the polyimide film (asking for an interview sample 7,8,10) of inorganic particle and carbon powder material, and size changing rate lower (below 0.05%).Hence one can see that, add inorganic particle and carbon powder material and can make and has better then characteristic and lower size changing rate between polyimide film and copper base material, and can avoid in making circuit card generation curling, come off, can't contraposition etc. problem.
Sum up above-mentioned experimental data, by the doping inorganic particle, can increase the surface gloss of mist degree, minimizing polyimide film, to solve dazzle and astigmatic problem.And reduce the thermal expansivity of polyimide film, with the base material of fit applications in different heat expansion coefficient.By the doping carbon powder material, then can reduce light transmittance and reach 0%, block light penetration fully, to reach the secret purpose of electronic circuit or classified papers.The high texture of outward appearance, cloudy surface black polyamide film have been finished.
For the disappearance of known polyimide film, polyimide film provided by the present invention because having inorganic particle and carbon powder material, and can reduce simultaneously glossiness, solves the problem of dazzle, light transmittance and thermal expansion.And, because polyimide film provided by the present invention has multiple excellent properties, can directly apply to the industry category of multiple high additive value, to promote the development of industry.
Preferred forms of the present invention discloses as mentioned above.Yet above-mentioned cited manufacture method is not limited to embodiments of the invention, anyly has the knack of in the technical field of the invention this operator, is not departing from outside spirit of the present invention and the scope, all can carry out various modifications or conversion.So protection scope of the present invention should be as the criterion with the scope that following appending claims was defined.
Claims (21)
1. the manufacture method of a polyimide film comprises the following step:
A plurality of inorganic particles and a plurality of carbon powder material are scattered in the solvent, and preparation one contains the aaerosol solution of inorganic particle and carbon powder material;
Diamine monomer and tetracarboxylic dianhydride's monomer are added in the described aaerosol solution, carry out polyreaction, preparation one contains the polyamic acid mixture of inorganic particle and carbon powder material;
Dry described polyamic acid mixture is to form a polyamic acid blend films; And
Heat described polyamic acid blend films, carry out inferior amidate action, to form polyimide film.
2. the manufacture method of polyimide film as claimed in claim 1 wherein adds diamine monomer and tetracarboxylic dianhydride's monomer that step also comprises in the described aaerosol solution:
Lasting Stirring device has the polyamic acid mixture of inorganic particle and carbon powder material, avoiding described inorganic particle and carbon powder material sedimentation, and causes demixing phenomenon; And
Described polyamic acid mixture is coated on the base material.
3. the manufacture method of polyimide film as claimed in claim 2, wherein said base material is metal base.
4. the manufacture method of polyimide film as claimed in claim 1, the weight percent of wherein said inorganic particle is 1wt% to 49wt%.
5. the manufacture method of polyimide film as claimed in claim 1, the weight percent of wherein said inorganic particle is 20wt% to 40wt%.
6. the manufacture method of polyimide film as claimed in claim 1, the particle diameter of wherein said inorganic particle is 0.1 micron to 10 microns.
7. the manufacture method of polyimide film as claimed in claim 1, the particle diameter of wherein said inorganic particle is 0.5 micron to 6 microns.
8. the manufacture method of polyimide film as claimed in claim 1, wherein said inorganic particle is to be selected from the group that is made of mica powder, silicon dioxide powder, talcum powder, ceramics powder, clay powder, kaolin, silica gel sintered powder and aforesaid combination.
9. the manufacture method of polyimide film as claimed in claim 1, the weight percent of wherein said carbon powder material is 1wt% to 49wt%.
10. the manufacture method of polyimide film as claimed in claim 1, the weight percent of wherein said carbon powder material is 3wt% to 30wt%.
11. the manufacture method of polyimide film as claimed in claim 1, the particle diameter of wherein said carbon powder material are 0.1 micron to 10 microns.
12. the manufacture method of polyimide film as claimed in claim 1, the particle diameter of wherein said carbon powder material are 0.5 micron to 6 microns.
13. the manufacture method of polyimide film as claimed in claim 1, wherein said carbon powder material are to be selected from by oil, charcoal or other organism fully or the group that consists of of the carbon black that produces of incomplete combustion and carbon ash, graphite, carbon ball, carbon pipe, Graphene and aforesaid combination.
14. the manufacture method of polyimide film as claimed in claim 1,60 ° of glossiness of wherein said polyimide film are less than or equal to 60GU.
15. the manufacture method of polyimide film as claimed in claim 1, the thermal expansivity of wherein said polyimide film are less than or equal to 30ppm/ ℃.
16. the manufacture method of polyimide film as claimed in claim 1, the light transmittance of wherein said polyimide film is less than or equal to 10%.
17. the manufacture method of polyimide film as claimed in claim 1, Shuo＞=0.2W/m-℃ of the heat conduction Xi of wherein said polyimide film.
18. a polyimide film, it is by made such as each described manufacture method of claim 1 to 17, comprises:
Polyimide;
Inorganic particle; And
Carbon powder material,
Wherein said inorganic particle and described carbon powder material are to be scattered in the described polyimide, to form polyimide film.
19. a polyimide film laminated plates comprises:
One base material; And
The polyimide film that manufacture method as claimed in claim 2 is made covers described base material.
20. polyimide film laminated plates as claimed in claim 19, wherein said base material are metal base.
21. polyimide film laminated plates as claimed in claim 20, the intermembranous Bonding strength of wherein said metal base and described polyimide is more than or equal to 0.6kgf/cm.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101113272 | 2012-04-13 | ||
| TW101113272 | 2012-04-13 | ||
| TW101143455 | 2012-11-21 | ||
| TW101143455A TWI510529B (en) | 2012-04-13 | 2012-11-21 | Polyimide film, method for manufacturing the same and polyimide film laminate including the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103374224A true CN103374224A (en) | 2013-10-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100039420A Pending CN103374224A (en) | 2012-04-13 | 2013-01-07 | Polyimide film, method for producing same, and polyimide film laminate comprising same |
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| CN (1) | CN103374224A (en) |
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|---|---|---|---|---|
| CN104023505A (en) * | 2014-06-13 | 2014-09-03 | 江苏悦达新材料科技有限公司 | Method for preparing high thermal conductivity graphite film |
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| CN105385159A (en) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | Black matte polyimide thin film and preparation method thereof |
| CN107356989A (en) * | 2016-05-10 | 2017-11-17 | 住友化学株式会社 | Optical film, the flexible apparatus component and resin combination for possessing the optical film |
| CN114679837A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Black glue-free flexible copper-clad plate and preparation method and application thereof |
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