CN1654518A - Method for preparing polyimide film for flexible printed plate board - Google Patents
Method for preparing polyimide film for flexible printed plate board Download PDFInfo
- Publication number
- CN1654518A CN1654518A CN200510038294.8A CN200510038294A CN1654518A CN 1654518 A CN1654518 A CN 1654518A CN 200510038294 A CN200510038294 A CN 200510038294A CN 1654518 A CN1654518 A CN 1654518A
- Authority
- CN
- China
- Prior art keywords
- preparation
- kapton
- dianhydride
- softening agent
- kapton according
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000011889 copper foil Substances 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 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 19
- 239000004902 Softening Agent Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 229920005575 poly(amic acid) Polymers 0.000 claims description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 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 8
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 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 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-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
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000005357 flat glass Substances 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- -1 amido benzene Chemical compound 0.000 claims description 3
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 125000005498 phthalate group Chemical class 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical class [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 1
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical class C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000004642 Polyimide Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Abstract
The present invention relates to the preparation process of polyimide film for flexible printed circuit board. Diamine monomer and plasticizer are dissolved in polar non-proton solvent, and maleic anhydride in the same molar amount as the diamine is added and mixed for 2-20 hr to synthesize polyamido acid solution containing plasticizer; the polyamido acid solution is painted homogeneously onto glass plate and dried through programmed temperature raise to 200-400 deg.c to obtain polyimide film with thermal expansion coefficient approaching that of copper foil and stable size for printed circuit board.
Description
Affiliated technical field:
The present invention relates to a kind of preparation method of Kapton, especially relate to a kind of preparation method of polyimide film for flexible printed plate board.
Background technology:
Polyimide (PI) film has the excellent comprehensive performance, all is widely used at aspects such as electrician, electronics and aerospace.In recent years, there is tangible growth in the market of Kapton, and this mainly depends on the market of flexible print wiring board (FPC).
The application of FPC is changing always.Start from the seventies, mainly as the parts of photographic camera, be used for pick up camera the eighties, the application phenomenal growth of the FPC nineties aspect computer was mainly used in microelectronic industries such as mobile phone in 2000 later on.Along with constantly widening that FPC uses, the demand of fine circuit pattern FPC is constantly increased, the performance of Kapton is proposed requirements at the higher level.Present stage, dimensional stability becomes the key index of FPC with Kapton.
FPC is by the coated tackiness agent of Kapton, be covered with Copper Foil after curing at a certain temperature, through hot pressing or be composited; Also have directly on Copper Foil, to apply polyamic acid solution, through thermal treatment directly and Copper Foil bonding.In the manufacturing processed of FPC, Kapton and Copper Foil all will stand high temperature and high humidity environment effect.Different the making of the dimensional change degree of Kapton and Copper Foil made fine circuit pattern FPC generation difficulty.
In addition, when the PI resin was applied to copper-clad plate, its thermal expansivity was much larger than electronic devices and components.In the process of making and handling, because the difference of this coefficient of expansion, make to have very big internal stress in the product, occur that circuit is peeled off or seminess, when serious even rupture, greatly influenced PI base copper-clad plate product performance.
In order to improve and to widen the application of PI resin in copper-clad plate industry, research after this mainly concentrates on preparation low-thermal-expansion polyimide aspect.The low-thermal-expansion polyimide generally is to prepare with the monomer with special construction.The monomeric structure of this class has two characteristics: form by phenyl ring in the contraposition or nitrogen heterocyclic by being bonded in for (1) diamine structure, do not contain flexible keys such as ether or methylene radical; (2) structure of dianhydride is biphenyl type or equal benzene type.
U.S.Pat.No.4725484 has announced a kind of composition that can be used for preparing the Kapton of flexibility printed circuit board, its monomer dianhydride is a biphenyl type dianhydride 3,3 ' 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), the thermal expansivity of the Kapton that makes are 1～25ppm K between 50 ℃～300 ℃
-1Yet nearest patent U.S.Pat.No.2004/0126600 A1 points out that the composition that U.S.Pat.No.4725484 announces obviously all is the monomer of " rigidity ", and wherein the common relatively dianhydride of the price of rigidity dianhydride BPDA is very expensive.
In addition, the macromolecular chain that is become by " rigidity " monomer polymerization generally is club shaped structure, and rigidity is very strong, and snappiness is relatively poor, and is bad with the cementability of inorganic materials, also exists some defectives in actual applications.(model peace. printed wiring information 1997. (5): 17.)
Studies show that in addition, method such as blending and modifying, multi-component copolymer, interpolation filler, organic siloxane modified and nano particle hybridization can reduce the thermal expansivity of PI resin effectively.
Make PA solution with rigidity diamines and pyromellitic acid dianhydride among the Te Kaiping 2-150 451, use 4 again, 4 '-diaminodiphenyl oxide and pyromellitic acid anhydride prepare PA solution, and after both mixed stirring, it was 2ppmK that the curtain coating drying has made CTE
-1Film.
A.K.St.Clair is to add benzophenone tetracarboxylic dianhydride and 4 at 1: 4 with Lanthanum trichloride by the ratio of metal ion and polymer repeat unit, among the PI that 4 '-oxygen p-diaminodiphenyl is formed, addition is 11.3%～11.6% (quality) of film, and the CTE that makes E.I.Du Pont Company's film is from 35ppmK
-1Drop to 18ppmK
-1, the CTE of Seiko company film is from 39ppmK
-1Drop to 17ppmK
-1(Polym.Mater.Sci.Eng.，1996，71：725；Polym.Mater.Sci.Eng.，1997，76：185；J.Mater.Res.，1996，11：841)
Japan Chisso Corporation (JP) 6-32, Nakanoshima 3-chome, Kitaku, Osaka, Japan pyromellitic acid dianhydride, BPDA, diamines and the copolymerization of 4-aminophenyl Trimethoxy silane, the modification PI that obtains is excellent in adhesion, and CTE is low.(spy opens clear 64-6 025)
Japan Toyota research centre is with 4, and 4 '-diamines yl diphenyl ether and Pyromellitic Acid synthesize the PI/Clay hybrid material, and CTE is than not reducing about 50% before the hydridization.
The method of above-mentioned blending and modifying, multi-component copolymer is adopted by the producer that some produce Kapton, but it has still introduced the monomer with rigid structure at all, has increased the cost of raw material.In addition, the introducing chlorion has bad influence for the electrical property of film.Secondly, add essentially consist-polyimide that methods such as filler, organic siloxane modified and nano particle hybridization have all changed film, though thermal expansivity reduces, be used to prepare the excellent properties of flexible print wiring board but covered Kapton, and increased preparation technology difficulty, improved the cost of raw material.Add methods such as filler, organic siloxane modified and nano particle hybridization and also be not applied to industrialized production as yet.
In addition, two-way stretch is the effective ways of the Kapton of preparation high-dimensional stability, and the main manufacturer DuPont of external Kapton etc. has all adopted the technology of two-way stretch.Yet the stretch processes complexity, the equipment precision height.
Summary of the invention:
Technical problem to be solved by this invention: the purpose of this invention is to provide a kind of flexibility printed circuit board for preparing and use, have the method for the Kapton of high degree of dimensional stability.
Technical solution of the present invention is: prepare in two-step approach on the basis of Kapton, the degree of crystallinity and the orientation degree of the amount control film by regulate adding the high temperature plasticization agent, finally make close with Copper Foil CTE, the Kapton of dimensional stabilizing.
This prepares the method for Kapton, it is characterized in that, prepare in two-step approach on the basis of Kapton, by in the process of preparation polyamic acid, adding softening agent, enlarge the temperature range of molecular chain orientation, adjust the degree of crystallinity or the orientation degree of film, thus make close with Copper Foil CTE, the Kapton of dimensional stabilizing.The steps include:
(a) monomer diamines and softening agent are dissolved in the polar aprotic solvent, the dianhydride of mol ratios such as adding and diamines mixed the polyamic acid solution of synthetic plasticizer-containing 2-20 hour; Wherein, wherein to account for synthesizing polyamides acid mass percent be 0.05%-5% to the add-on of softening agent,
(b) polyamic acid solution with above-mentioned plasticizer-containing is uniformly coated on the sheet glass, puts into the loft drier program and is warmed up to 200 ℃～400 ℃, preferably is warmed up to 250 ℃～400 ℃.Obtain the Kapton that the flexibility printed circuit board of dimensional stabilizing is used.
Wherein softening agent is a phthalate, terephthalate, diester class, alkyl sulfonic ester, epoxy ester, clorafin, phosphoric acid ester; Softening agent is preferably triphenylphosphate, triphenyl phosphite, triethyl phosphate, Tritolyl Phosphate, phenyl alkylsulf, dioctyl phthalate (DOP), dibutyl phthalate or terephthalic acid di-isooctyl; The add-on of softening agent accounts for the mass percent preferred 0.05%～2% of synthesizing polyamides acid.Diamines is a kind of in the following aromatic diamine, 4,4 '-diaminodiphenyl oxide (ODA), two (3-amino-benzene oxygen) sulfobenzides (BAPS), 1, two (3-amino-benzene oxygen) benzene (BAPB) of 3-, diaminodiphenylsulfone(DDS) (DDS), diaminobenzophenone (DABP), two amido benzene (PDA), methylene-dianiline (MDA); Dianhydride is a kind of of following aromatic series dianhydride, pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), dihydroxyphenyl propane dianhydride (BPADA), benzophenone tetracarboxylic dianhydride (BTDA).Polar aprotic solvent is N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) or N-methyl-pyrrolidone (NMP);
Beneficial effect of the present invention is: by add a certain amount of softening agent in the process of preparation polyamic acid, adjust the degree of crystallinity and the orientation degree of film, promptly control the order degree of molecular chain in the membrane structure by the amount of regulating the softening agent that adds, thereby make close with Copper Foil CTE, the Kapton of dimensional stabilizing.Compare with the Kapton of traditional method preparation, the Kapton of the present invention's preparation has: 1, the high feature of dimensional stability, its CTE is controlled at 10ppmK
-1～30ppmK
-12, the structural limitations to the monomer dianhydride is little; 3, raw materials cost is low, and technology is simple.
Embodiment:
Embodiment 1.
In the Erlenmeyer flask of a cleaning, add 4 of 2.4g, 4 '-diaminodiphenyl oxide (ODA), 0.67g triphenyl phosphite and 30mlN, N '-dimethyl formamide (DMF), be stirred to dissolving fully, the pyromellitic acid anhydride (PMDA) that in batches adds 2.62g by ratio of components, stirring reaction 4-5 hour, generate the faint yellow polyamic acid solution of heavy-gravity.Polymers soln is coated on the sheet glass equably, puts into baking oven, temperature programming is heat-treated: 130 ℃ 2 hours, 170 ℃ 0.5 hour, 200 ℃ 0.5 hour, 280 ℃ 1 hour, 350 ℃ finally obtained CTE in 2 hours is 24～28ppmK between 50 ℃～250 ℃
-1Kapton.
Embodiment 2.
In the Erlenmeyer flask of a cleaning, add 4 of 2.4g, 4 '-diaminodiphenyl oxide (ODA), 1.34g triphenyl phosphite and 30mlN, N '-dimethyl formamide (DMF) is stirred to dissolving fully, following preparation method is with embodiment 1, and finally obtaining CTE is 18～22ppmK between 50 ℃～250 ℃
-1Kapton.
Embodiment 3.
The diaminodiphenylsulfone(DDS) (DDS), 1.5g triphenyl phosphite and the 200mlN that in the Erlenmeyer flask of a cleaning, add 24.8g, N '-N,N-DIMETHYLACETAMIDE (DMAc), be stirred to dissolving fully, add 3 of 29.4g by ratio of components in batches, 3,4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), stirring reaction 5-6 hour, generate the heavy-gravity polyamic acid solution.Polymers soln is coated on the sheet glass equably, puts into baking oven, temperature programming is heat-treated: 100 ℃ 2 hours, 170 ℃ 1 hour, 200 ℃ 1 hour, 300 ℃ 1 hour, 400 ℃ finally obtained CTE in 2 hours is 14～18ppmK between 50 ℃～250 ℃
-1Kapton.
Claims (10)
1, a kind of preparation method of polyimide film for flexible printed plate board, it is characterized in that preparing on the basis of Kapton in two-step approach, by the preparation polyamic acid process in add softening agent, thereby make Kapton close with the Copper Foil thermal expansivity, dimensional stabilizing; Its concrete steps are:
(a) monomer diamines and softening agent are dissolved in the polar aprotic solvent, the dianhydride of mol ratios such as adding and diamines mixed the polyamic acid solution of synthetic plasticizer-containing 2-20 hour; Wherein to account for synthesizing polyamides acid mass percent be 0.05%-5% to the add-on of softening agent;
(b) polyamic acid solution with above-mentioned plasticizer-containing is uniformly coated on the sheet glass, puts into the vacuum drying oven program and is warmed up to 200 ℃～400 ℃, obtains the Kapton that the flexibility printed circuit board of dimensional stabilizing is used.
2, the preparation method of Kapton according to claim 1 is characterized in that softening agent is phthalate, terephthalate, diester class, alkyl sulfonic ester, epoxy ester, clorafin or phosphoric acid ester.
3, the preparation method of Kapton according to claim 1 is characterized in that softening agent is triphenylphosphate, triphenyl phosphite, triethyl phosphate, Tritolyl Phosphate, phenyl alkylsulf, dioctyl phthalate (DOP), dibutyl phthalate or terephthalic acid di-isooctyl.
4, the preparation method of Kapton according to claim 1, it is 0.05%-2% that the quality that it is characterized in that the softening agent that adds accounts for synthesizing polyamides acid quality percentage composition.
5, the preparation method of Kapton according to claim 1 is characterized in that temperature programming to 250 ℃～400 ℃.
6, the preparation method of Kapton according to claim 1 is characterized in that polar aprotic solvent is N, dinethylformamide, N,N-dimethylacetamide or N-methyl-pyrrolidone.
7, the preparation method of Kapton according to claim 1 is characterized in that diamines is an aromatic diamine.
8, the preparation method of Kapton according to claim 7, it is characterized in that aromatic diamine is 4,4 '-diaminodiphenyl oxide, two (3-amino-benzene oxygen) sulfobenzide, 1, two (3-amino-benzene oxygen) benzene of 3-, diaminodiphenylsulfone(DDS), diaminobenzophenone, two amido benzene or methylene-dianilines.
9, the preparation method of Kapton according to claim 1 is characterized in that dianhydride is the aromatic series dianhydride.
10, the preparation method of Kapton according to claim 9 is characterized in that the aromatic series dianhydride is a pyromellitic acid anhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, dihydroxyphenyl propane dianhydride or benzophenone tetracarboxylic dianhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510038294.8A CN1288194C (en) | 2005-01-31 | 2005-01-31 | Method for preparing polyimide film for flexible printed plate board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510038294.8A CN1288194C (en) | 2005-01-31 | 2005-01-31 | Method for preparing polyimide film for flexible printed plate board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654518A true CN1654518A (en) | 2005-08-17 |
| CN1288194C CN1288194C (en) | 2006-12-06 |
Family
ID=34894432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510038294.8A Active CN1288194C (en) | 2005-01-31 | 2005-01-31 | Method for preparing polyimide film for flexible printed plate board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1288194C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952511A (en) * | 2011-08-16 | 2013-03-06 | 通用电气公司 | Epoxy encapsulation and lamination adhesive and method of making same |
| CN103145985A (en) * | 2012-12-09 | 2013-06-12 | 上海飞凯光电材料股份有限公司 | Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof |
| CN103374130A (en) * | 2012-04-20 | 2013-10-30 | 达迈科技股份有限公司 | Aromatic polyimide film, preparation method and application thereof |
| CN103732405A (en) * | 2011-06-14 | 2014-04-16 | 宇部兴产株式会社 | Method for producing polyimide laminate, and polyimide laminate |
| WO2015080139A1 (en) * | 2013-11-27 | 2015-06-04 | 宇部興産株式会社 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
| CN106047373A (en) * | 2015-04-14 | 2016-10-26 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liqud crystal element |
| CN109401313A (en) * | 2018-10-31 | 2019-03-01 | 株洲时代新材料科技股份有限公司 | A kind of Kapton and preparation method thereof |
| CN110253904A (en) * | 2019-07-18 | 2019-09-20 | 桂林电器科学研究院有限公司 | A kind of thick polyimide film or super thick film and preparation method thereof |
| CN110343275A (en) * | 2019-07-18 | 2019-10-18 | 桂林电器科学研究院有限公司 | A kind of preparation method of polyimides ultrathin membrane |
| CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
| CN114026179A (en) * | 2019-06-24 | 2022-02-08 | 株式会社钟化 | Transparent polyimide film and method for producing same |
| CN114286835A (en) * | 2019-08-29 | 2022-04-05 | 聚酰亚胺先端材料有限公司 | Polyimide film and preparation method thereof |
| CN114616269A (en) * | 2019-11-07 | 2022-06-10 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric and preparation method thereof |
-
2005
- 2005-01-31 CN CN200510038294.8A patent/CN1288194C/en active Active
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732405A (en) * | 2011-06-14 | 2014-04-16 | 宇部兴产株式会社 | Method for producing polyimide laminate, and polyimide laminate |
| CN102952511A (en) * | 2011-08-16 | 2013-03-06 | 通用电气公司 | Epoxy encapsulation and lamination adhesive and method of making same |
| CN103374130B (en) * | 2012-04-20 | 2016-01-20 | 达迈科技股份有限公司 | Aromatic polyimide film, preparation method and application thereof |
| CN103374130A (en) * | 2012-04-20 | 2013-10-30 | 达迈科技股份有限公司 | Aromatic polyimide film, preparation method and application thereof |
| CN103145985A (en) * | 2012-12-09 | 2013-06-12 | 上海飞凯光电材料股份有限公司 | Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof |
| CN105764990B (en) * | 2013-11-27 | 2018-03-20 | 宇部兴产株式会社 | Polyimide precursor composition, the manufacture method of polyimides, polyimides, polyimide film and substrate |
| KR20160091935A (en) * | 2013-11-27 | 2016-08-03 | 우베 고산 가부시키가이샤 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
| JPWO2015080139A1 (en) * | 2013-11-27 | 2017-03-16 | 宇部興産株式会社 | Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate |
| WO2015080139A1 (en) * | 2013-11-27 | 2015-06-04 | 宇部興産株式会社 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
| CN105764990A (en) * | 2013-11-27 | 2016-07-13 | 宇部兴产株式会社 | Polyimide precursor composition, method of manufacturing polyimide, the polyimide, polyimide film, and substrate |
| KR102188483B1 (en) | 2013-11-27 | 2020-12-08 | 우베 고산 가부시키가이샤 | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate |
| CN106047373B (en) * | 2015-04-14 | 2020-10-09 | Jsr株式会社 | Liquid crystal aligning agent |
| CN106047373A (en) * | 2015-04-14 | 2016-10-26 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liqud crystal element |
| CN109401313A (en) * | 2018-10-31 | 2019-03-01 | 株洲时代新材料科技股份有限公司 | A kind of Kapton and preparation method thereof |
| CN109401313B (en) * | 2018-10-31 | 2021-06-15 | 株洲时代华鑫新材料技术有限公司 | Polyimide film and preparation method thereof |
| CN114026179A (en) * | 2019-06-24 | 2022-02-08 | 株式会社钟化 | Transparent polyimide film and method for producing same |
| CN114026179B (en) * | 2019-06-24 | 2023-11-24 | 株式会社钟化 | Transparent polyimide film and method for producing same |
| CN110343275A (en) * | 2019-07-18 | 2019-10-18 | 桂林电器科学研究院有限公司 | A kind of preparation method of polyimides ultrathin membrane |
| CN110253904A (en) * | 2019-07-18 | 2019-09-20 | 桂林电器科学研究院有限公司 | A kind of thick polyimide film or super thick film and preparation method thereof |
| CN110437614A (en) * | 2019-07-26 | 2019-11-12 | 宁波今山新材料有限公司 | The preparation method of formable polyimide film |
| CN114286835A (en) * | 2019-08-29 | 2022-04-05 | 聚酰亚胺先端材料有限公司 | Polyimide film and preparation method thereof |
| CN114616269A (en) * | 2019-11-07 | 2022-06-10 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric and preparation method thereof |
| CN114616269B (en) * | 2019-11-07 | 2024-02-13 | 聚酰亚胺先端材料有限公司 | Polyimide film with low dielectric property and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288194C (en) | 2006-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1288194C (en) | Method for preparing polyimide film for flexible printed plate board | |
| CN101407590B (en) | Preparation of high modulus, low thermal expansion coefficient polyimide hybridization film | |
| US7101619B2 (en) | Laminate | |
| US7425371B2 (en) | Thermosetting resin composition for high performance laminates | |
| CN101942092A (en) | Polyamide imide, film and preparation method thereof | |
| TW201739889A (en) | Adhesive composition using polyamideimide resin | |
| CN101407589A (en) | Preparation of low thermal expansion coefficient thermoplastic polyimide film | |
| CN103012821B (en) | Polyimide film | |
| TW201311765A (en) | Polyimide film | |
| KR20130003358A (en) | Polyamic acid and polyamic acid solution, polyimide protecive layer, polyimide film | |
| CN101787126A (en) | Polyamide acid composition, method for manufacturing two-layer process flexible copper-clad plates by use of same, and obtained two-layer process flexible copper-clad plate | |
| CN114651036B (en) | Polyimide film with improved dimensional stability and method for preparing same | |
| CN112920602A (en) | High-modulus low-thermal-expansion-coefficient polyimide film and preparation method thereof | |
| CN111704735A (en) | Ultralow-thermal-expansion-coefficient high-strength polyimide optical film material and preparation method thereof | |
| CN111454452B (en) | Polyamic acid, polyimide film and flexible circuit board material | |
| KR20190003394A (en) | Polyimide-based block copolymers and polyimide-based film comprising the same | |
| CN111925543A (en) | Low-humidity low-thermal expansion coefficient polyimide composite film material and preparation method thereof | |
| JP3653499B2 (en) | Poly (imide-benzoxazole) copolymer | |
| CN109054018B (en) | Polyamide acid solution and preparation method thereof | |
| CN113307971B (en) | Polyimide precursor and application thereof | |
| CN107722272B (en) | Preparation method of polyimide film | |
| CN111479395B (en) | Preparation method of glue-free flexible copper-clad plate | |
| CN113396176B (en) | Polyamide-imide block copolymer, method for preparing the same, and polyamide-imide film comprising the same | |
| CN111499864B (en) | Polyimide film with low thermal expansion coefficient and preparation method thereof | |
| KR101231941B1 (en) | Polyimide film and metal-Clad Laminates |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Kunshan Dingxin Electronics Co.,Ltd. Assignor: Nanjing University of Technology Contract fulfillment period: 2007.1.1 to 2011.12.31 Contract record no.: 2008990000573 Denomination of invention: Method for preparing polyimide film for flexible printed plate board Granted publication date: 20061206 License type: Exclusive license Record date: 2008.10.7 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.1 TO 2011.12.31; CHANGE OF CONTRACT Name of requester: KUNSHAN DINGXIN ELECTRONICS CO., LTD. Effective date: 20081007 |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20190828 Address after: 222042 No. 275 Shanxi Road, Lianyungang District, Jiangsu Province Patentee after: Lianyungang Dasheng New Material Technology Co., Ltd. Address before: 210009 Zhongshan North Road, Jiangsu, No. 200, Patentee before: Nanjing University of Technology |
|
| TR01 | Transfer of patent right |