CN1300251C - Polyimide film and its prepn process and use - Google Patents
Polyimide film and its prepn process and use Download PDFInfo
- Publication number
- CN1300251C CN1300251C CNB2004100313500A CN200410031350A CN1300251C CN 1300251 C CN1300251 C CN 1300251C CN B2004100313500 A CNB2004100313500 A CN B2004100313500A CN 200410031350 A CN200410031350 A CN 200410031350A CN 1300251 C CN1300251 C CN 1300251C
- Authority
- CN
- China
- Prior art keywords
- organic
- clay
- film
- kept
- organic clay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 5
- 239000004927 clay Substances 0.000 claims abstract description 61
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 38
- 239000004642 Polyimide Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000005357 flat glass Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- -1 siloxanes Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 13
- 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 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000002156 mixing Methods 0.000 description 16
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 13
- 238000010907 mechanical stirring Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 241000370738 Chlorion Species 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a composite polyimide film which comprises organic clay, a monomer or a mixture of aromatic diamine, a monomer or a mixture of organic dianhydride, organic solvent, a flatting agent, a molecular weight regulator and an aid adhesive. The preparation method of the present invention comprises the following steps: the organic clay is dispersed in polar non-protonic solvent under the action of a supersonic wave, and the aromatic diamine is dissolved in a suspension; the monomer of organic dianhydride, the molecular weight regulator / the aid adhesive and the flatting agent are added to the suspension in batches and stirred at a room temperature for reacting for 6 hours to obtain an organic clay / polyamic acid mixed resin solution; the organic clay / polyamic acid mixed resin solution is coated on the surface of a smooth substrate for complete subamination and is naturally cooled to the room temperature; then, a film is stripped from the substrate to obtain a composite polyimide film doped with the organic clay. The present invention improves the thermal expansion coefficient of the composite polyimide film, reduces the moisture absorption rate and has significant application values in a microelectronics field and an aerospace field.
Description
Technical field
The present invention relates to the adulterated Kapton of a kind of organic clay.
The invention still further relates to the preparation method of above-mentioned film.
The invention still further relates to the purposes of above-mentioned film.
Background technology
Many advantages such as high temperature resistant, low temperature resistant, corrosion-resistant, high insulation that Kapton has, low-dielectric loss, mechanical property excellence have obtained using widely at aspects such as Aeronautics and Astronautics, microelectronics, electric apparatus.In actual application, Kapton often combines the heterogeneous mixture of formation organic film/inorganic materials with inorganic materials such as metal, therefore reduce the thermal expansivity of Kapton, make it approaching with metallic substance as far as possible, with the internal stress that reduces not match and cause owing to both thermal expansivity.In addition, Kapton uses mainly as heat-stable electric insulating film, requires its moisture absorption low more good more.Therefore, the Kapton of research low thermal coefficient of expansion, low moisture absorption ratio is the emphasis that people pay close attention to always.
1993, and people such as K.Yano (Journal of Polymer Science, Part A, 1993,31,2493-2498) report adds the thermal expansivity that can reduce laminated film in the Kapton with clay, improves its gas-barrier coefficient.People such as Y.Yang report adopts different intercalation modifying agent modified clays and is added in the polyimide, prepared polyimide composite film mechanical property and thermal characteristics improve (Polymer, 1999,40,4407-4414).People such as H.Tyan report adopts 4, polyamino compound such as 4 '-diaminodiphenyl oxide have reactive organic clay (Chemistry ofMaterials, 2001,13,222-226).Though above-mentioned report has used multiple clay alteration agent, do not see and to contain the research report of siloxanes segmental organic amine introducing as the clay alteration agent.Simultaneously, do not see and to prepare the report and the patent of low-expansion coefficient, low water absorption polyimide composite film in the organosilicon segment modified clay adding polyimide.
Summary of the invention
The present invention is intended to disclose preparation method and the purposes by the adulterated polyimide composite film of clay of siliceous organic amine modification, and described preparation method can obviously improve the thermal expansivity of polyimide composite film, reduces moisture absorption ratio.
The preparation method of polyimide composite film of the present invention is characterized in that this compound system comprises following component: (1) organic clay; (2) aromatic diamine monomer or its mixture; (3) organic tetracarboxylic dianhydride monomer or its mixture; (4) organic solvent; (5) flow agent; (6) molecular weight regulator and adhesion promotor.The content of various compositions is as shown in table 1.
The composition and the content range thereof of table 1 polyimide composite system
| Component | Parts by weight |
| Organic clay | 1-40 |
| Organic tetracarboxylic dianhydride | 98-102 |
| Aromatic diamine | 98-102 |
| Organic solvent | 500-10000 |
| Flow agent | 1.0-10.0 |
| Molecular weight regulator and adhesion promotor | 0.01-10.0 |
Organic clay in the polyimide composite film of the present invention is by containing flexible siloxanes segmental organic amine and derivative modified clay thereof, and the preparation method of this organic clay is:
1) with the cationic exchange total volume is clay (as: polynite (MMT), mica (MICA) and lithium montmorillonite) high-speed stirring in the presence of water dispersion medium of 50～200meq/100g, forms the stable suspersion system;
2) will be equivalent to used clay ion-exchange total volume 1-2 doubly contain flexible siloxanes segmental organic amine and derivative stirs the protonated solution of formation in the presence of water dispersion medium and protonating agent (as: protonic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid, acetate), be injected in the above-mentioned slurry;
Describedly contain flexible siloxanes segmental organic amine and derivant structure is shown below:
Wherein, R
1, R
2Be the alkyl fatty chain, comprise-(CH
2)
m-,-(CH
2)
m-CF
2-, m=1-12, R
2With R
1Can be identical, also can be different.R
3=-CH
3,-C
6H
5,-CF
2-CHF-CF
3,-CH=CH
2,-(CH
2)
x-CF
3, x=0～10, R
3Can be above-mentioned wherein a kind of, also may be that wherein two or more group exists simultaneously.
Typically contain siloxanes segmental organic amine as:
3) with above-mentioned mixed solution at 2 hours after-filtration of 60～100 ℃ of following high-speed stirring, use the deionized water thorough washing, drying obtains the organic clay of siliceous organic amine modification after the pulverizing.
In the polyimide composite film of the present invention, organic tetracarboxylic dianhydride and composition thereof means the aromatic organic compounds that contains two acid anhydrides, comprises pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides (6FDA) etc. and composition thereof.These organic tetracarboxylic dianhydrides can use separately also can mix use by arbitrary proportion.
In the polyimide composite film of the present invention, aromatic diamine and composition thereof means the aromatic organic compounds that contains two amidos, comprises Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS), 4,4 '-diaminodiphenylmethane (MDA), 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane (DMDA), 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane (TMDA), 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide and composition thereof.These organic diamines can use separately also can mix use by arbitrary proportion.
In the polyimide composite film of the present invention, organic solvent comprises N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone and the mixture solution that forms by any mixed.
In the polyimide composite film of the present invention, flow agent means the organic solvent that can improve the resin flow leveling, comprises methylphenol, butyl glycol ether, butyl glycol ether acetic ester, ethyl cellosolve acetate and the solvent system that forms by any mixed thereof.
In the polyimide composite film of the present invention, molecular weight regulator and adhesion promotor mean adjustable polyimide polymer molecular chain length and increase the organic compound of its adhesiveproperties or silicoorganic compound and composition thereof comprise γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane and the mixture that forms by any mixed thereof.
The present invention prepares the method for above-mentioned polyimide composite film, is undertaken by following step:
1) organized clay is scattered under the ultrasonic wave effect in the polar aprotic solvent and (comprises N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE and N, N '-dimethyl formamide etc.).
2) aromatic diamine is dissolved in the above-mentioned suspension.
3) organic tetracarboxylic dianhydride monomer, molecular weight regulator/adhesion promotor and flow agent are joined in the above-mentioned solution in batches, at room temperature stirring reaction obtained organized clay/polyamic acid mixed resin solution after 6 hours.
4) above-mentioned organic clay/polyamic acid mixed resin solution is coated on the smooth substrate surface, comprises sheet glass, silicon single crystal, metallic aluminium, metallic copper; Ladder-elevating temperature method heating shown in the employing table 2 makes solvent evaporates and finishes the imide reaction process.After the imidization fully, naturally cool to room temperature, film is peeled off from substrate, obtain the adulterated polyimide composite film of organic clay.
The ladder-elevating temperature program of table 2 Kapton
| Temperature ℃ | 40 | 80 | 120 | 150 | 180 | 250 | 300 | 400 |
| The constant temperature treatment time, hour | 1-10 | 1-4 | 1-4 | 1-4 | 1-4 | 1-4 | 1-4 | 1-4 |
The polyimide composite film of the present invention's preparation has lower thermal expansivity and low moisture absorption performance (table 3), has important use in microelectronic, field of aerospace and is worth.
Thermal expansivity of table 3 Kapton (CTE) and water-intake rate
Embodiment 1
With cation exchange capacity is the polynite 40g of the about 50 μ m of 100meq/100g, particle diameter, adds water 800ml; Obtain stable montmorillonite suspension liquid behind the high-speed stirring 20min.Take by weighing concentrated hydrochloric acid 4.0g, add the dilution of 30ml water, be added dropwise to 10g and contain in the siloxanes segmental organic amine (1), stir and form protonated solution.The protonated drips of solution of gained is heated in 80 ℃ the montmorillonite suspension liquid, high-speed stirring 2hrs naturally cools to 25 ℃.Suction filtration is used deionized water wash, then with the chlorion in the 0.2% silver nitrate solution detection filtrate; Washing 80 ℃ of following vacuum-dryings, obtains organic clay after grinding to detecting less than till the chlorion.
Above-mentioned organic clay 0.7364g is scattered in 180g N under the ultrasonic wave effect, in N '-N,N-DIMETHYLACETAMIDE.Under nitrogen protection, add 11.3958g4,4 '-diaminodiphenyl oxide (4,4 '-ODA); After waiting it to dissolve fully, under mechanical stirring, add the 12.4134g pyromellitic acid dianhydride in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 30.1 * 10
-6Ppm/ ℃, water-intake rate is 2.21% (seeing Table 3).
Embodiment 2:
The organic clay 2.4546g of preparation among the embodiment 1 is scattered in 180g N under the ultrasonic wave effect, in N '-N,N-DIMETHYLACETAMIDE.Under nitrogen protection, add 10.5734g4,4 '-diaminodiphenyl oxide (4,4 '-ODA); After waiting it to dissolve fully, under mechanical stirring, add the 11.5176g pyromellitic acid dianhydride in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 27.4 * 10
-6Ppm/ ℃, water-intake rate is 2.12% (seeing Table 3).
Embodiment 3:
With cation exchange capacity is the synthetic mica 40g that 100meq/100g, particle diameter are about 50 μ m, adds water 1000ml; Obtain stable mica suspension behind the high-speed stirring 20min.Take by weighing concentrated hydrochloric acid 4.0g, add the dilution of 30ml water, be added dropwise to 10g and contain in the siloxanes segmental organic amine (1), stir and form protonated solution.Protonated drips of solution is heated in 80 ℃ the mica suspension, high-speed stirring 2hrs, naturally cool to 25 ℃, suction filtration, use deionized water wash, with the chlorion in the 0.2% silver nitrate solution detection filtrate, washing is to detecting less than till the chlorion then, 80 ℃ of following vacuum-dryings, obtain organic clay after grinding.
Above-mentioned organic clay 0.7364g is scattered in 180g N under the ultrasonic wave effect, in N '-N,N-DIMETHYLACETAMIDE.Under nitrogen protection, add 11.3958g4,4 '-diaminodiphenyl oxide (4,4 '-ODA); After waiting it to dissolve fully, under mechanical stirring, add the 12.4134g pyromellitic acid dianhydride in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 28.7 * 10
-6Ppm/ ℃, water-intake rate is 2.07% (seeing Table 3).
Embodiment 4:
With among the embodiment 3 preparation organic clay 2.4546g ultra-sonic dispersion in 180g N, N '-N,N-DIMETHYLACETAMIDE.Under nitrogen protection, add 4,4 '-diaminodiphenyl oxide 10.5734g through in the system of dispersion treatment to above-mentioned; After waiting it to dissolve fully, under mechanical stirring, add 11.5 176g pyromellitic acid dianhydrides in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 26.1 * 10
-6Ppm/ ℃, water-intake rate is 1.97% (seeing Table 3).
Embodiment 5:
With among the embodiment 1 preparation organic clay 0.2455g ultra-sonic dispersion in the 180g N-Methyl pyrrolidone.Under nitrogen protection, to above-mentioned through adding 4 in the system of dispersion treatment, 4 '-diaminodiphenyl oxide 9.7332g and Ursol D 1.3141g, wait it to dissolve fully after, under mechanical stirring, add the 13.2528g pyromellitic acid dianhydride in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 21.7 * 10
-6Ppm/ ℃, water-intake rate is 2.35% (seeing Table 3).
Embodiment 6:
With among the embodiment 3 preparation organic clay 0.2455g ultra-sonic dispersion in the 180g N-Methyl pyrrolidone.Under nitrogen protection, to above-mentioned through adding 4 in the system of dispersion treatment, 4 '-diaminodiphenyl oxide 9.7332g and Ursol D 1.3141g, wait it to dissolve fully after, under mechanical stirring, add the 13.2528g pyromellitic acid dianhydride in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 18.9 * 10
-6Ppm/ ℃, water-intake rate is 2.21% (seeing Table 3).
Embodiment 7:
With the organic clay 1.2273g ultra-sonic dispersion of gained among the embodiment 1 in the 180g N-Methyl pyrrolidone.Under nitrogen protection, add 4,4 '-diaminodiphenyl oxide 7.0620g and Ursol D 2.5426g through in the system of dispersion treatment to above-mentioned; After treating that aromatic diamines dissolves fully, under mechanical stirring, add pyromellitic acid dianhydride 10.2571g and 3 in batches, 3 ', 4,4 '-BPDA (BPDA) 3.4565g.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 17.8 * 10
-6Ppm/ ℃, water-intake rate is 2.17% (seeing Table 3).
Embodiment 8:
With the organic clay 1.2273g ultra-sonic dispersion of gained among the embodiment 3 in the 180g N-Methyl pyrrolidone.Under nitrogen protection, add 4,4 '-diaminodiphenyl oxide 7.0620g and Ursol D 2.5426g through in the system of dispersion treatment to above-mentioned; After treating that aromatic diamines dissolves fully, under mechanical stirring, add pyromellitic acid dianhydride 10.2571g and 3 in batches, 3 ', 4,4 '-BPDA (BPDA) 3.4565g.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains organic clay/polyamic acid mixing solutions.
Organic clay/polyamic acid mixing solutions evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the polyimide composite film of self-supporting, its thermal expansivity is 16.4 * 10
-6Ppm/ ℃, water-intake rate is 1.91% (seeing Table 3).
Comparative Examples 1:
Under nitrogen protection, with 4, (4,4 '-ODA) 11.7482g adds 180g N, N '-N,N-DIMETHYLACETAMIDE to 4 '-diaminodiphenyl oxide; After treating that aromatic diamines dissolves fully, under mechanical stirring, add pyromellitic acid dianhydride 12.7973g in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains polyamic acid solution.
The polyamic acid solution that makes evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the Kapton of self-supporting, its thermal expansivity is 37.3 * 10
-6Ppm/ ℃, water-intake rate is 2.78% (seeing Table 3).
Comparative Examples 2:
Under nitrogen protection, with 4,4 '-diaminodiphenyl oxide 9.7332g and Ursol D 1 .3141g add the 180g N-Methyl pyrrolidone; After treating that aromatic diamines dissolves fully, under mechanical stirring, add pyromellitic acid dianhydride 13.2528g in batches.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains polyamic acid solution.
The polyamic acid solution that makes evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the Kapton of self-supporting, its thermal expansivity is 26.8 * 10
-6Ppm/ ℃, water-intake rate is 3.01% (seeing Table 3).
Comparative Examples 3:
Under nitrogen protection, with 4,4 '-diaminodiphenyl oxide 7.4337g and Ursol D 2.6764g add the 180g N-Methyl pyrrolidone; After treating that aromatic diamines dissolves fully, under mechanical stirring, add pyromellitic acid dianhydride 10.7969g and 3 in batches, 3 ', 4,4 '-BPDA 3.6384g.Temperature of reaction is controlled at＜30 ℃, stirring reaction 6hrs obtains polyamic acid solution.
The polyamic acid solution that makes evenly is coated on the clean sheet glass, kept 5 hours in 40 ℃ then, 80 ℃ kept 2 hours down, and 120 ℃ kept 1 hour, and 150 ℃ kept 1 hour, and 250 ℃ kept 1 hour, and 300 ℃ kept 1 hour; After being cooled to room temperature, polymeric film is peeled off from sheet glass, obtained the Kapton of self-supporting, its thermal expansivity is 21.1 * 10
-6Ppm/ ℃, water-intake rate is 2.89% (seeing Table 3).
Claims (9)
1. polyimide composite film, this film comprises by weight: organic clay 1-40 part, organic tetracarboxylic dianhydride 98-102 part, aromatic diamine 98-102 part, organic solvent 500-10000 part, flow agent 1.0-10.0 part, molecular weight regulator and adhesion promotor 0.01-10.0 part;
Described organic clay is served as reasons and is contained flexible siloxanes segmental organic amine and derivative modified clay thereof, wherein contains flexible siloxanes segmental organic amine and derivative thereof and is shown below:
Wherein, R
1, R
2Be the alkyl fatty chain, comprise-(CH
2)
m-,-(CH
2)
m-CF
2-, m=1-12, R
2With R
1Can be identical, also can be different; R
3=-CH
3,-C
6H
5,-CF
2-CHF-CF
3,-CH=CH
2,-(CH
2)
x-CF
3, x=0～10, R
3Can be above-mentioned wherein a kind of, also may be that wherein two or more group exists simultaneously;
Described organic tetracarboxylic dianhydride means the organic compound that contains two acid anhydrides;
Described aromatic diamine means the organic compound that contains two amino;
Described flow agent means the organic solvent that can improve the resin flow leveling;
Described molecular weight regulator and adhesion promotor mean adjustable polyimide polymer molecular chain length and increase the organic compound of its adhesiveproperties or silicoorganic compound and composition thereof.
2. film as claimed in claim 1 is characterized in that described clay comprises polynite, mica and lithium montmorillonite.
3. film as claimed in claim 1 is characterized in that, described organic tetracarboxylic dianhydride is: pyromellitic acid dianhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides or arbitrary proportion mixture more than two kinds.
4. film as claimed in claim 1, it is characterized in that, described aromatic diamine is: Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane, 4,4 '-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) sulfobenzides or the arbitrary proportion mixture more than two kinds.
5. film as claimed in claim 1, it is characterized in that, described organic solvent is: N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone and the mixture solution that is formed by any mixed by above-mentioned solvent.
6. film as claimed in claim 1 is characterized in that, described flow agent is: methylphenol, butyl glycol ether, butyl glycol ether acetic ester, ethyl cellosolve acetate and the solvent system that forms by any mixed thereof.
7. film as claimed in claim 1, it is characterized in that described molecular weight regulator and adhesion promotor are: γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetramethyl-polysiloxane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-aminopropyl) tetraphenyl polysiloxane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl polysiloxane or the mixture that forms by any mixed.
8. method for preparing the described film of claim 1, key step is:
A) with the cationic exchange total volume be clay high-speed stirring in the presence of water dispersion medium of 50～200meq/100g, form the stable suspersion system;
B) will be equivalent to used clay ion-exchange total volume 1-2 doubly contain flexible siloxanes segmental organic amine and derivative stirs the protonated solution of formation in the presence of water dispersion medium and protonating agent, be injected in the slurry that step a makes;
C) mixed solution that step b is made is used the deionized water thorough washing at 2 hours after-filtration of 60～100 ℃ of following high-speed stirring, and drying obtains the organic clay of siliceous organic amine modification after the pulverizing;
D) organized clay that step c is made is scattered in the organic solvent under the ultrasonic wave effect;
E) aromatic diamine is dissolved in the suspension that steps d makes;
F) organic tetracarboxylic dianhydride monomer, molecular weight regulator/adhesion promotor and flow agent are joined in the solution that step e makes in batches, at room temperature stirring reaction 1-20 hour, obtain organized clay/polyamic acid mixed resin solution;
G) organic clay that step f is made/polyamic acid mixed resin solution is coated on the smooth substrate surface, makes solvent evaporates and finishes the imide reaction process with the heating of table ladder-elevating temperature method; After the imidization fully, naturally cool to room temperature, film is peeled off from substrate, obtain the adulterated polyimide composite film of organic clay.
9. as preparation method as described in the claim 8, it is characterized in that described substrate is sheet glass, silicon single crystal, metallic aluminium or metallic copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100313500A CN1300251C (en) | 2004-03-25 | 2004-03-25 | Polyimide film and its prepn process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100313500A CN1300251C (en) | 2004-03-25 | 2004-03-25 | Polyimide film and its prepn process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1673277A CN1673277A (en) | 2005-09-28 |
| CN1300251C true CN1300251C (en) | 2007-02-14 |
Family
ID=35046064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100313500A Expired - Lifetime CN1300251C (en) | 2004-03-25 | 2004-03-25 | Polyimide film and its prepn process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300251C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4771071B2 (en) * | 2006-01-24 | 2011-09-14 | 信越化学工業株式会社 | Resin composition for screen printing |
| CN101420820B (en) * | 2008-12-02 | 2011-10-26 | 广东生益科技股份有限公司 | Double side flexible copper coated board and manufacturing method thereof |
| CN102786688A (en) * | 2012-08-06 | 2012-11-21 | 江苏南方贝昇光电材料有限公司 | Preparation method for aureole resistant polyimide film |
| KR20150118527A (en) * | 2014-04-14 | 2015-10-22 | 제이엔씨 주식회사 | Liquid crystal aligning agents, liquid crystal alignment films and liquid crystal display devices |
| CN106146866B (en) * | 2015-03-31 | 2019-06-21 | 中国科学院过程工程研究所 | A kind of polyimide composite film and preparation method thereof |
| CN107565082A (en) * | 2017-07-11 | 2018-01-09 | 中国第汽车股份有限公司 | A kind of composite diaphragm |
| CN112851982B (en) * | 2020-12-29 | 2022-04-29 | 南京精工新材料有限公司 | Polyimide film and preparation method thereof |
| CN115058037A (en) * | 2022-07-04 | 2022-09-16 | 江西师范大学 | Nano montmorillonite/polyimide composite film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238637A (en) * | 1991-06-07 | 1993-08-24 | Rhone-Poulenc Fibres | Process for obtaining polyamide yarns with better output efficiency |
| CN1258690A (en) * | 2000-01-05 | 2000-07-05 | 浙江大学 | Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient |
| CN1055706C (en) * | 1996-06-05 | 2000-08-23 | 中国科学院化学研究所 | Polyamide and clay nm composite and its prepn. |
-
2004
- 2004-03-25 CN CNB2004100313500A patent/CN1300251C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238637A (en) * | 1991-06-07 | 1993-08-24 | Rhone-Poulenc Fibres | Process for obtaining polyamide yarns with better output efficiency |
| CN1055706C (en) * | 1996-06-05 | 2000-08-23 | 中国科学院化学研究所 | Polyamide and clay nm composite and its prepn. |
| CN1258690A (en) * | 2000-01-05 | 2000-07-05 | 浙江大学 | Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1673277A (en) | 2005-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101289542B (en) | Spherical silica/polyimides composite membrane, preparation thereof and applications | |
| CN106750435B (en) | A kind of preparation method of the ordered porous Kapton of low-k | |
| CN1831034A (en) | Method for preparing polyimide/silicon dioxide nanometer hybridized film | |
| CN104892968A (en) | Preparation method of high-heat-conduction hexagonal boron nitride/polyimide composite material | |
| CN108530628A (en) | A kind of preparation method of fire resistant polyimide film | |
| WO2007016516A2 (en) | Heteropolymeric polyimide polymer compositions | |
| CN111040450A (en) | Low-dielectric fluorine-containing polyimide composite film and preparation method thereof | |
| KR100676331B1 (en) | Polyimide Hybrid Adhesives | |
| CN1300251C (en) | Polyimide film and its prepn process and use | |
| CN109251334B (en) | Preparation method of high-light-transmittance and low-dielectric fluorinated graphene/polyimide composite film | |
| CN103554533A (en) | Corona-resistant polyimide/silica nano composite film and preparation method thereof | |
| CN109942848A (en) | The preparation method of surface texture hydrophobic type polyimide aerogels film | |
| CN105601923B (en) | Fluorine-containing soft or hard block Kapton and preparation method, purposes | |
| KR20130031052A (en) | Polyamic acid-silca hybrid composition, polyimide-silaca hybrid film and method for preparing the sames | |
| CN113667120B (en) | Polyimide and preparation method thereof | |
| CN114349962A (en) | Low-dielectric-constant polyimide film and preparation method thereof | |
| CN116218357B (en) | Cyanate in-situ modified polyimide high-temperature-resistant coating and preparation method thereof | |
| CN112143000B (en) | Preparation method of all-organic PI/PVDF film composite material | |
| KR20130031051A (en) | Polyamic acid-silca hybrid composition, polyimide-silaca hybrid film and method for preparing the sames | |
| CN115612097B (en) | Low-dielectric and high-strength nanocomposite and preparation method thereof | |
| WO2020238029A1 (en) | Modified polyamide acid and preparation method therefor, and preparation method for composite film layer | |
| CN110387041A (en) | A kind of polyimide composite film and preparation method thereof | |
| CN108727587B (en) | Heat-resistant polyimide containing imidazolyl aromatic ring structure and preparation method thereof | |
| CN114230791B (en) | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof | |
| CN106751823B (en) | A kind of heat-insulated laminated film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN RUIHUATAI MEMBRANE TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: INST.OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20140106 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100080 HAIDIAN, BEIJING TO: 518105 SHENZHEN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20140106 Address after: 518105 Huamei Industrial Park, Songgang street, Shenzhen, Guangdong, Baoan District Patentee after: SHENZHEN RAYITEK FILM TECHNOLOGY CO.,LTD. Address before: 100080 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Patentee before: Institute of Chemistry, Chinese Academy of Sciences |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518105 Huamei Industrial Park, Songgang Street, Baoan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Ruihuatai Film Technology Co.,Ltd. Address before: 518105 Huamei Industrial Park, Songgang Street, Baoan District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN RAYITEK FILM TECHNOLOGY CO.,LTD. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20070214 |
|
| CX01 | Expiry of patent term |