CN101168598B - Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient - Google Patents
Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient Download PDFInfo
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- CN101168598B CN101168598B CN2007101325250A CN200710132525A CN101168598B CN 101168598 B CN101168598 B CN 101168598B CN 2007101325250 A CN2007101325250 A CN 2007101325250A CN 200710132525 A CN200710132525 A CN 200710132525A CN 101168598 B CN101168598 B CN 101168598B
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Abstract
The invention relates to a preparation method for an extra thick polyimide film with high thermal conductance and low thermal expansion coefficient. The invention has the process steps that monomer diamine is dissolved in aprotic polar solvent, dianhydride having equal mol with diamine and nanometer thermal conductive material after surface treatment are added in the solvent, and the reaction is operated for 4 to 10 hours, thereby synthesizing polyamic acid resin including the nanometer thermal conductive material, wherein, the mass percent of the added amount of the nanometer thermal conductive material in the synthetic polyamic acid resin is 1 percent to 10 percent; the polyamic acid resin including the nanometer thermal conductive material casts on a stainless band, and through being dried at 100 to 200 DEG C, the dehydration and the imidization to an obtained casting film are performed under the high temperature at 300 to 480 DEG C, thereby preparing the extra thick polyimide film with the good thermal conductance and the low thermal expansion coefficient. The thermal conductance of the extra thick polyimide film prepared by the method of the invention is high, and the thermal expansion coefficient is low.
Description
Technical field
The present invention relates to a kind of preparation method who is applicable to the ultra-thick polyimide film of industries such as microelectronics, printed wiring, speech coil framework.Belong to the insulating polymeric material technical field.
Technical background
Ultra-thick polyimide film is outstanding over-all propertieies such as good heat resistance, chemical stability are good, good mechanical property, dielectric properties excellence because of having, and have been widely used in fields such as various motors, extraordinary electrical equipment, high-temperature flexible printed wiring base material, ffc and loudspeaker voice coil skeleton.Particularly the microelectronics of develop rapidly in recent years and IC industry have promoted the development of ultra-thick polyimide film.
Common thick polyimide film is because of poor thermal conductivity (0.18Wm
-1k
-1), thermal expansivity height (55ppmk
-1), make to be applied to microelectronic high-density and the heating of high speed emerged in operation circuit is difficult for dissipating, circuit working temperature rise phenomenon, influence stablizing of electronic devices and components and unicircuit; In addition, because the difference of thick polyimide film and electronic devices and components thermal expansivity causes electronic circuit warpage to occur, peel off or seminess, the product performance of microelectronic circuit have been had a strong impact on.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of method for preparing the ultra-thick polyimide film of high thermal conductivity, low thermal coefficient of expansion is provided.
The object of the present invention is achieved like this: the preparation method of the ultra-thick polyimide film of a kind of high thermal conductivity, low thermal coefficient of expansion, it is characterized in that: described method is to prepare on the basis of Kapton in two-step approach, control the cross-linking set and the orientation degree of film by regulating the amount of adding the nano heat-conductive material, finally make the ultra-thick polyimide film that thermal conductivity is good, thermal expansivity is low, its processing step is:
Step 1, the monomer diamines is dissolved in the aprotic polar solvent, adds dianhydride and surface treated nano heat-conductive material with mol ratio such as diamines, react 4～10 hours, synthesize the polyamic acid resin that contains the nano heat-conductive material.Wherein, to account for synthesizing polyamides acid resin mass percent be 1%～10% to the add-on of nano heat-conductive material; Preferred add-on is 3%～8% mass percent;
Step 2, with the above-mentioned polyamic acid resin hydrostomia of nano heat-conductive material that contains on Stainless Steel Band, through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, makes that thermal conductivity is good, the ultra-thick polyimide film of low thermal coefficient of expansion.
Wherein surface treated nano heat-conductive material is the two a mixture of aluminium nitride (AlN), silicon carbide (SiC) through coupling agent treatment or its, and the mixing quality ratio of the two is 1: 0.8～1.2.The coupling processing agent of using is silane coupling agent or titanate coupling agent.Diamines is a kind of in the following aromatic series: 4 (ODA), diaminodiphenylmethane (MDA), Ursol D (PDA).Dianhydride is a kind of in the following aromatic series: pyromellitic acid anhydride (PMDA), 3,3 '-4,4 ' bibenzene tetracarboxylic dianhydride (BPDA), benzophenone tetracarboxylic dianhydride (BTDA).Aprotic polar solvent is a kind of in following: N,N-dimethylacetamide (DMAC), N, dinethylformamide (DMF), N-methyl-pyrrolidone (NMP).
Ultimate principle of the present invention is to add surface treated nano heat-conductive material in polyamic acid resin, stable hybrid cross-linked by between the macromole of polyimide and nanoparticle, forming, the motion of limit polymerization thing molecular chain, thus give the low heat expansion property and the thermal conductivity of polyimide film excellence.
Embodiment
Embodiment 1:
In the reactor that stirring is housed, drop into 11843 gram N, N-N,N-DIMETHYLACETAMIDE (DMAC), drop into 1000 grams 4 again, 4 '-the diaminodiphenyl oxide dissolving, dissolving back fully adds 1090 gram pyromellitic acid anhydride reactions 4 hours, add gram again, continue reaction 4 hours, make the polyamic acid resin solution that high viscosity contains the nano heat-conductive material through the nanometer AlN62.7 of coupling agent treatment.The polyamic acid resin solution hydrostomia that this high viscosity is contained the nano heat-conductive material is on Stainless Steel Band, and through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, and making thickness is 175 microns, and thermal conductivity is 0.65Wm
-1k
-1, thermal expansivity is 26～31ppmk 150～250 ℃ times
-1The ultra-thick polyimide film.
Embodiment 2:
In the reactor that stirring is housed, drop into 11843 gram N, the N-N,N-DIMETHYLACETAMIDE, drop into 1000 grams 4 again, 4 '-the diaminodiphenyl oxide dissolving, dissolving back fully adds 1090 gram pyromellitic acid anhydride reactions 4 hours, add again through the nanometer AlN31.35 of coupling agent treatment gram, nano SiC 31.35 grams, continue reaction 4 hours, make the polyamic acid resin solution that high viscosity contains the nano heat-conductive material.The polyamic acid resin solution hydrostomia that this high viscosity is contained the nano heat-conductive material is on Stainless Steel Band, and through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, and making thickness is 175 microns, and thermal conductivity is 0.61Wm
-1k
-1, thermal expansivity is 25～30ppmk 150～250 ℃ times
-1The ultra-thick polyimide film.
Embodiment 3:
In the reactor that stirring is housed, drop into 14053 gram N, dinethylformamide, drop into 1000 grams 4 again, 4 '-the diaminodiphenyl oxide dissolving, dissolving back fully adds 1480 grams 3,3 '-4,4 ' bibenzene tetracarboxylic dianhydride reaction 4 hours, add nano SiC 124 grams again, continue reaction 4 hours, make the polyamic acid resin solution that high viscosity contains the nano heat-conductive material through coupling agent treatment.The polyamic acid resin solution hydrostomia that this high viscosity is contained the nano heat-conductive material is on Stainless Steel Band, and through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, and making thickness is 175 microns, and thermal conductivity is 0.76Wm
-1k
-1, thermal expansivity is 21～26ppmk 150～～250 ℃ times
-1The ultra-thick polyimide film.
Embodiment 4:
In the reactor that stirring is housed, drop into 12716 gram N-methyl-pyrrolidone (NMP), drop into 600 gram Ursol D dissolvings again, dissolving back fully adds 1644 grams 3,3 '-4,4 ' bibenzene tetracarboxylic dianhydride reaction 4 hours, add gram again, continue reaction 4 hours, make the polyamic acid resin solution that high viscosity contains the nano heat-conductive material through the nanometer AlN123.4 of coupling agent treatment.The polyamic acid resin solution hydrostomia that this high viscosity is contained the nano heat-conductive material is on Stainless Steel Band, and through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, and making thickness is 175 microns, and thermal conductivity is 0.81Wm
-1k
-1, thermal expansivity is 20～24ppmk 150～250 ℃ times
-1The ultra-thick polyimide film.
Comparative example 5 (not adding surface treated nano heat-conductive material):
In the reactor that stirring is housed, drop into 11843 gram N,N-DIMETHYLACETAMIDEs, drop into again 1000 grams 4,4 '--diaminodiphenyl oxide dissolving, dissolving back fully add 1090 gram pyromellitic acid anhydrides reactions 4 hours, make high-viscosity polyamide acid resin solution.On Stainless Steel Band, through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations with this polyamic acid resin solution hydrostomia, and making thickness is 175 microns polyimide films, and surveying its thermal conductivity is 0.18Wm
-1k
-1, thermal expansivity is 55～60ppmk 150～250 ℃ times
-1
The coupling processing agent of using in the foregoing description is silane coupling agent or titanate coupling agent; Diamines 4 or Ursol D also can change with diaminodiphenylmethane and replace; Dianhydride pyromellitic acid anhydride or 3,3 '-4,4 ' bibenzene tetracarboxylic dianhydride also can be changed with benzophenone tetracarboxylic dianhydride and replace, and can obtain the ultra-thick polyimide film of high thermal conductivity, low thermal coefficient of expansion equally.
Claims (2)
1. the preparation method of the Kapton of a high thermal conductivity, low thermal coefficient of expansion, it is characterized in that: the processing step of described method is:
Step 1, the monomer diamines is dissolved in the aprotic polar solvent, adds dianhydride and surface treated nano heat-conductive material with mol ratio such as diamines, react 4～10 hours, synthesize the polyamic acid resin that contains the nano heat-conductive material.Wherein, to account for synthesizing polyamides acid resin mass percent be 1%～10% to the add-on of nano heat-conductive material;
Step 2, with the above-mentioned polyamic acid resin hydrostomia that contains the nano heat-conductive material on Stainless Steel Band, through 100～200 ℃ of dryings, the salivation film that obtains is again through 300～480 ℃ of high temperature dehydration imidizations, makes that thermal conductivity is good, the polyimide film of low thermal coefficient of expansion,
Wherein surface treated nano heat-conductive material is through the two mixture of the aluminium nitride of coupling agent treatment and silicon carbide; The coupling processing agent of using is silane coupling agent or titanate coupling agent; Diamines is a kind of in the following aromatic series: 4, diaminodiphenylmethane, Ursol D; Dianhydride is a kind of in the following aromatic series: pyromellitic acid anhydride, 3,3 '-4,4 ' bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride; Aprotic polar solvent is a kind of in following: N,N-dimethylacetamide, N, and dinethylformamide, N-methyl-pyrrolidone,
The two mixing quality ratio of described aluminium nitride and silicon carbide is 1: 0.8～1.2.
2. require the preparation method of the ultra-thick polyimide film of 1 described high thermal conductivity, low thermal coefficient of expansion according to claim, it is characterized in that: it is 3%～8% that the add-on of described nano heat-conductive material accounts for synthesizing polyamides acid resin mass percent.
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| CN2007101325250A CN101168598B (en) | 2007-10-08 | 2007-10-08 | Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient |
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| CN2007101325250A CN101168598B (en) | 2007-10-08 | 2007-10-08 | Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient |
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| CN101168598B true CN101168598B (en) | 2010-06-02 |
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| CN102219918B (en) * | 2011-05-13 | 2014-03-12 | 王利平 | Thermal imidization method for polymide film |
| CN102493015A (en) * | 2011-12-05 | 2012-06-13 | 江西先材纳米纤维科技有限公司 | Preparation method for high-strength, high temperature-resistant polyimide crude fibre |
| WO2013147009A1 (en) * | 2012-03-29 | 2013-10-03 | 宇部興産株式会社 | Method for producing polyimide film, and polyimide film |
| CN102936341A (en) * | 2012-09-27 | 2013-02-20 | 宁波今山电子材料有限公司 | Polyimide resin synthesis method |
| CN103395153B (en) * | 2013-07-26 | 2016-02-03 | 常州大学 | A kind of method of low-temperature growth hard elastic polypropylene cast film |
| CN104752371A (en) * | 2013-12-27 | 2015-07-01 | 中芯国际集成电路制造(上海)有限公司 | Polyimide photosensitive layer and preparation method and packaging method thereof |
| CN104211973B (en) * | 2014-04-01 | 2015-06-17 | 无锡顺铉新材料有限公司 | Polyimide film |
| CN103889196B (en) * | 2014-04-11 | 2016-06-22 | 江苏悦达新材料科技有限公司 | A kind of preparation method of high heat conduction electrographite film |
| CN103923330A (en) * | 2014-04-30 | 2014-07-16 | 山东中天华德科技发展有限公司 | Method for preparing high-thermal conductivity polyimide/magnesium oxide composite film |
| CN105331103A (en) * | 2015-08-28 | 2016-02-17 | 昆山斯格威电子科技有限公司 | Preparation method of high-heat conduction and high temperature-resistance polyimide composite material |
| CN105111739A (en) * | 2015-09-14 | 2015-12-02 | 苏州嘉银绝缘材料有限公司 | High thermal conductivity polyimide film and preparation method thereof |
| CN106220847A (en) * | 2016-04-26 | 2016-12-14 | 安徽鑫柏格电子股份有限公司 | A kind of Kapton of high heat conduction and preparation method thereof |
| CN106206543A (en) * | 2016-08-04 | 2016-12-07 | 上海交通大学 | Based on nano aluminum nitride/composite polyimide material keyset and preparation method thereof |
| CN106496611A (en) * | 2016-09-26 | 2017-03-15 | 安徽国风塑业股份有限公司 | A kind of preparation method of high heat conduction Kapton |
| TWI634141B (en) * | 2016-11-30 | 2018-09-01 | 達勝科技股份有限公司 | Method for manufacturing polyimide film and polyimide film |
| TW201829645A (en) * | 2017-02-08 | 2018-08-16 | 台虹科技股份有限公司 | Nanoparticles and Polyimide Resin Composition |
| CN106832280A (en) * | 2017-02-27 | 2017-06-13 | 华烁科技股份有限公司 | A kind of thermoplasticity conducting liquid crystal Kapton and preparation method thereof |
| CN107312447A (en) * | 2017-06-28 | 2017-11-03 | 徐昌霞 | A kind of polyimide-based copper-clad plate of heat conduction Good Heat-resistance and preparation method thereof |
| CN107652432A (en) * | 2017-09-28 | 2018-02-02 | 无锡顺铉新材料有限公司 | A kind of heat conduction Kapton |
| CN109776826B (en) * | 2019-01-21 | 2020-09-29 | 深圳丹邦科技股份有限公司 | Polyimide thick film, quantum carbon-based film and preparation method thereof |
| CN110885556B (en) * | 2019-11-07 | 2022-05-10 | 安徽国风新材料股份有限公司 | Heat-conducting cross-linked polyimide film and preparation method thereof |
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