WO2023160563A1 - 用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法 - Google Patents

用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法 Download PDF

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WO2023160563A1
WO2023160563A1 PCT/CN2023/077543 CN2023077543W WO2023160563A1 WO 2023160563 A1 WO2023160563 A1 WO 2023160563A1 CN 2023077543 W CN2023077543 W CN 2023077543W WO 2023160563 A1 WO2023160563 A1 WO 2023160563A1
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mixed
temperature
transparent polyimide
dianhydride
polyimide film
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PCT/CN2023/077543
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English (en)
French (fr)
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冷劲松
肖鑫礼
刘彦菊
孔德艳
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哈尔滨工业大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to a high-temperature-resistant colorless and transparent polyimide film used for lead-free soldering reflow in the electronics industry and a preparation method thereof.
  • Colorless transparent polyimide can be widely used in high-tech fields such as microelectronics and optoelectronics.
  • it is used as optical waveguide material, optical filter, optical fiber, photoelectric packaging material, second-order nonlinear optical material, photorefractive material, photosensitive material and optoelectronic material in the field of optical communication.
  • it is used as alignment film material, negative compensation film, plastic substrate of flexible organic electroluminescent display, etc.
  • most of CPI cannot meet the long-term high-temperature manufacturing requirements of the electronics industry; and the existing preparation method requires nitrogen protection during thermal imidization treatment, which increases the manufacturing cost and equipment process difficulty.
  • the purpose of the present invention is to solve the problem that most colorless and transparent polyimides are difficult to withstand the high-temperature environment of lead-free soldering and reflow processing in the electronics industry, and provide a high-temperature-resistant colorless and transparent polyimide for electronic lead-free soldering and reflowing. Imine film and method for its preparation.
  • a kind of preparation method of the high-temperature colorless transparent polyimide film that is used for lead-free soldering and reflow in the electronic industry is as follows:
  • Step 1 Add the mixed diamine into the aprotic polar solvent, stir in nitrogen atmosphere until completely dissolved, and obtain the mixed diamine solution; the solid-liquid ratio of the mixed diamine and the aprotic polar solvent is: 11.0 ⁇ 18.0Kg : 150L; The mixed diamine is formed by mixing the following raw materials in molar ratio:
  • Step 2 Add the mixed dianhydride to the mixed diamine solution several times, and at the same time pass nitrogen gas, stir at room temperature, and perform polycondensation reaction to obtain the precursor polyamic acid solution; the mixed dianhydride is mixed by the following raw materials in molar ratio into:
  • Step 3 subjecting the precursor to thermal imidization treatment to obtain a self-supporting polyamic acid film
  • Step 4 performing thermal imidization and stretching of the self-supporting polyamic acid film, and further processing the obtained colorless and transparent polyimide film.
  • Step 1 Add the mixed diamine into the aprotic polar solvent, stir in nitrogen atmosphere until completely dissolved, and obtain the mixed diamine solution; the solid-liquid ratio of the mixed diamine and the aprotic polar solvent is: 11.0 ⁇ 18.0Kg : 150L; The mixed diamine is formed by mixing the following raw materials in molar ratio:
  • Step 2 Add the mixed dianhydride to the mixed diamine solution several times, and at the same time pass nitrogen gas, and conduct polycondensation reaction at room temperature and high-speed stirring for 6h to 30h to obtain the precursor polyamic acid solution;
  • the mixed dianhydride It is made by mixing the following raw materials in molar ratio:
  • the molar ratio of the added mixed dianhydride and mixed diamine is 0.9:1 to 1.1:1;
  • Step 3 degassing the precursor polyamic acid solution to obtain a uniform solution
  • Step 4 cast the precursor polyamic acid solution after defoaming with a casting machine, and bake at the same time to obtain a self-supporting polyamic acid film, and the content of the aprotic polar solvent in the polyamic acid film decreases to 18-38%;
  • Step 5 Entering the polyamic acid film into an imidization furnace, adopting synchronous or asynchronous biaxial stretching, and the stretching control temperature in the imidization furnace is 280-330°C;
  • Step 6 after stretching treatment, a colorless and transparent polyimide film is obtained.
  • aprotic polar solvent is N,N dimethylformamide, N,N dimethylacetamide or N-methylpyrrolidone.
  • step 4 the temperature upwind of the steel strip of the tape casting machine is 80-120°C, and the downwind temperature of the steel strip is 100-150°C.
  • synchronous biaxial stretching is: synchronous stretching in the longitudinal direction and transverse direction, the longitudinal stretching ratio of the synchronous biaxial stretching is 1.00-1.50, and the transverse stretching ratio is 1.00-1.30.
  • asynchronous biaxial stretching is: first stretch the film longitudinally by controlling the width of the track, and then stretch it laterally.
  • the longitudinal stretch ratio of asynchronous biaxial stretching is 1.00 to 1.60; the transverse stretch ratio is 1.00 ⁇ 1.35.
  • the thickness of the wet film cast on the stainless steel belt is controlled by adjusting the slit distance of the extrusion die of the casting machine, and the obtained film has a thickness of 15-80 ⁇ m and a width of 260-1200 mm.
  • Another object of the present invention is to disclose a colorless and transparent polyimide film prepared by the above method, the light transmittance of which is not lower than 90%, and the thermal expansion and contraction ratio at 270°C is less than or equal to 0.20%
  • the present invention uses three kinds of diamine monomers with special structures to carry out copolymerization, wherein 9,9-bis-(4-aminophenyl)fluorene (FDA) is characterized in that two amino groups are para-positioned to connect polycyclic
  • FDA 9,9-bis-(4-aminophenyl)fluorene
  • the tert-butyl carbon atom of the aromatic hydrocarbon fluorene and the polycyclic aromatic hydrocarbon structure of fluorene make CPI have a higher glass transition temperature Tg; at the same time, the bulky side group of the tert-butyl carbon atom also destroys the coplanar structure and reduces the charge transfer complexation (CTC ) effect to reduce its color.
  • CTC charge transfer complexation
  • the strongly electronegative trifluoromethyl group in 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA) can absorb charges and reduce charge transfer complexation (CTC)
  • CTC charge transfer complexation
  • BAE 3,3'-diaminodiphenyl ether
  • CTC charge transfer complexation
  • ODA 4,4'-diaminodiphenyl ether
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride contains an aliphatic six-membered ring, and its alicyclic structure can effectively prevent the charge transfer complexation (CTC) effect, Thereby reducing the color;
  • 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) contains isopropyl bistrifluoromethyl group, its strong electronegativity and isopropyl structure can effectively It hinders the CTC effect and reduces the color of the obtained CPI; at the same time, the large hexafluoroisopropyl group can hinder the free movement of molecular chains, thereby maintaining a high glass transition temperature Tg.
  • the colorless transparent polyimide film prepared by the present invention has a thickness of 15-80 ⁇ m, which is suitable for processing electronic devices on the film and has excellent processing performance in practical applications; the present invention
  • the prepared colorless and transparent polyimide film has a light transmittance of not less than 90%, a thermal expansion ratio of less than or equal to 0.20% at 270°C, high dimensional stability, and a long service life. High temperature manufacturing requirements for industry lead-free soldering reflow.
  • Fig. 1 is the CPI infrared spectrogram that the embodiment of the present invention 5 prepares
  • Fig. 2 is the ultraviolet-visible spectrogram of CPI prepared in Example 5 of the present invention.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the windward steel belt is 80 °C, and the temperature of the downwind of the steel belt is 100 °C.
  • a self-supporting polyamic acid film is obtained after the steel strip is baked, wherein the content of N,N-dimethylacetamide solvent in the polyamic acid film is reduced to 38%.
  • the longitudinal stretch ratio is 1.0
  • the transverse stretch ratio is 1.0
  • the maximum stretching control temperature in the imidization furnace is 280°C.
  • the precursor polyamic acid after defoaming is evenly cast on the circulating stainless steel belt through the extrusion die.
  • a self-supporting polyamic acid film is obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent is reduced to 18%.
  • the asynchronous biaxial stretching is carried out step by step in the longitudinal and transverse directions.
  • the longitudinal stretching ratio is 1.6
  • the transverse stretching ratio is 1.35
  • the maximum control temperature of the stretching in the imidization furnace is 330°C.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the steel belt upwind is 90°C, and the temperature of the steel belt downwind is 120°C.
  • a self-supporting polyamic acid film is obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent is reduced to 28%.
  • the longitudinal stretch ratio is 1.25
  • the transverse stretch ratio is 1.20
  • the maximum stretching control temperature in the imidization furnace is 290°C.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the upwind of the steel belt is 110 °C
  • the temperature of the downwind of the steel belt is 150 °C.
  • a self-supporting polyamic acid film was obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent was 21%.
  • the longitudinal stretch ratio is 1.25
  • the transverse stretch ratio is 1.25
  • the maximum control temperature for stretching in the imidization furnace is 320°C.
  • the mixed diamine solution in the kettle is all pressed into a 300L resin kettle equipped with mechanical stirring and nitrogen gas inlet and outlet through a pressure pump, and nitrogen gas is passed into it.
  • the mixed dianhydride 1,2,4,5 cyclohexane tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and bisphenol A diether dianhydride Add it to the resin tank several times, and the ratio of the amount of the substances is 1:2:1.
  • the polymerization reaction was carried out for 15 hours under room temperature and high-speed stirring to obtain a precursor polyamic acid solution; the molar ratio of the added mixed dianhydride and mixed diamine was 0.95:1.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the upwind of the steel belt is 110 °C
  • the temperature of the downwind of the steel belt is 150 °C.
  • a self-supporting polyamic acid film was obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent was 26%.
  • the longitudinal stretch ratio is 1.10
  • the transverse stretch ratio is 1.18
  • the maximum control temperature for stretching in the imidization furnace is 310°C.
  • Fig. 1 shows the infrared spectrum of CPI prepared in this example, and these characteristic absorption peaks indicate that the CPI prepared in Example 1 has been highly imidized.
  • Fig. 2 shows the ultraviolet-visible spectrogram of the CPI prepared in this embodiment, and it can be seen from Fig. 2 that the average light transmittance of the colorless and transparent polyimide film with a thickness of 75 ⁇ m is 90.2%.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the steel belt is 100 °C, and the temperature of the steel belt is 130 °C.
  • a self-supporting polyamic acid film is obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent is reduced to 22%.
  • Asynchronous biaxial stretching is carried out step by step in the longitudinal and transverse directions, and the longitudinal stretch ratio is 1.20.
  • the transverse stretching ratio is 1.20, and the maximum stretching control temperature in the imidization furnace is 300°C.
  • the film After biaxial stretching treatment at high temperature, the film is cooled, trimmed, and rolled up to finally produce a colorless and transparent polyimide film with a width of 550mm and a thickness of 75 ⁇ m.
  • the colorless and transparent polyimide film with a thickness of 75 ⁇ m prepared in this example has an average light transmittance of 90.3%.
  • This film is reflowed at 270°C for 300s at a high temperature of 270°C for lead-free soldering in the electronics industry and then cooled to room temperature.
  • the thermal expansion and contraction ratio is 0.15 %.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the steel belt is 100 °C, and the temperature of the steel belt is 130 °C.
  • a self-supporting polyamic acid film was obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent was 21%.
  • Asynchronous biaxial stretching is carried out step by step in the longitudinal and transverse directions.
  • the longitudinal stretch ratio is 1.26
  • the transverse stretch ratio is 1.35
  • the maximum control temperature of stretching in the imidization furnace is 320°C.
  • the colorless and transparent polyimide film with a thickness of 75 ⁇ m prepared in this example has an average light transmittance of 90.5%.
  • the film is reflowed at 270°C for 300 seconds at a high temperature of 270°C for lead-free soldering in the electronics industry and then cooled to room temperature.
  • the thermal expansion and contraction ratio is 0.17 %.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the upwind of the steel belt is 90 °C, and the temperature of the downwind of the steel belt is 130 °C.
  • a self-supporting polyamic acid film was obtained after steel strip baking, wherein the content of N,N-dimethylacetamide solvent was 22%.
  • the longitudinal stretch ratio is 1.16
  • the transverse stretch ratio is 1.28
  • the maximum control temperature for stretching in the imidization furnace is 310°C.
  • the average light transmittance of the colorless and transparent polyimide film prepared in Example 4 with a thickness of 75 ⁇ m is 90.1%.
  • the film is reflowed at 270° C. for 300 seconds at a high temperature of 270° C. for lead-free soldering in the electronics industry and then cooled to room temperature. %.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the upwind of the steel belt is 80 °C, and the temperature of the downwind of the steel belt is 120 °C.
  • a self-supporting polyamic acid film is obtained after steel strip baking, wherein the content of N,N-dimethylformamide solvent is 25%.
  • the asynchronous biaxial stretching is carried out step by step in the longitudinal and transverse directions.
  • the longitudinal stretch ratio is 1.26
  • the transverse stretch ratio is 1.38
  • the maximum control temperature of stretching in the imidization furnace is 300°C.
  • the colorless and transparent polyimide film with a thickness of 75 ⁇ m prepared in this example has an average light transmittance of 90.8%. This film is reflowed at a high temperature of 270°C for 300s in the electronics industry and then cooled to room temperature. %.
  • the degassed precursor polyamic acid solution is evenly cast on the circulating stainless steel belt through the extrusion die head.
  • the temperature of the steel belt is 100 °C, and the temperature of the steel belt is 130 °C.
  • a self-supporting polyamic acid film is obtained after steel strip baking.
  • the longitudinal stretch ratio is 1.22
  • the transverse stretch ratio is 1.36
  • the maximum control temperature for stretching in the imidization furnace is 310°C.
  • the colorless and transparent polyimide film with a thickness of 75 ⁇ m prepared in this example has an average light transmittance of 90.1%. This film is reflowed at 270° C. for lead-free soldering in the electronics industry, and its thermal expansion and contraction ratio after being cooled to room temperature for 300 s is 0.10%.
  • the dimensional stability of the colorless transparent polyimide film prepared by the present invention is characterized by the thermal shrinkage ratio. That is, first draw two lines with a laser on the colorless transparent polyimide film, measure the distance between the inner sides of the two lines, and mark them. Then put the colorless transparent polyimide film into a preheated 270°C reflow oven for 300s, and measure the distance optically. Measure different areas and angle directions, and finally perform statistical analysis on the measurement value variation error. When the thickness is 75 ⁇ m, the light transmittance is ⁇ 90%, and the thermal expansion and contraction ratio is ⁇ 0.20% at 270°C.

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Abstract

本发明涉及一种用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法。本发明的目的是要解决绝大部分CPI无法满足电子行业270℃的长期高温制造要求。方法如下：采用9,9-双-(4-氨基苯基)芴，3,3'-二氨基二苯醚和2,2'-双(三氟甲基)-4,4'-二氨基苯基醚制成混合二胺溶液；再添加1,2,4,5-环己烷四甲酸二酐，4,4'-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐，进行共聚，制备前驱聚酰胺酸溶液；在流延机钢带上烘烤，获得自支撑薄膜；热亚胺化处理同时拉伸完成薄膜的酰亚胺化；冷却，机械处理制得CPI薄膜。制得的耐高温CPI膜在75μm厚时透光率≥90％、270℃下冷热伸缩比≤0.20％。

Description

用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法 技术领域
本发明涉及一种用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法。
背景技术
无色透明聚酰亚胺(CPI)可广泛应用于微电子以及光电子等高技术领域。例如在光通讯领域中用作光波导材料、滤光片、光纤、光电封装材料、二阶非线性光学材料、光折变材料、光敏材料以及光电材料等。在液晶显示领域用作取向膜材料，负性补偿膜、柔性有机电致发光显示器的塑料基板等。但是绝大部分CPI无法满足电子行业的长期高温制造要求；并且现有的制备方法热亚胺化处理时需要氮气保护，增加了制造成本及设备工艺难度。
发明内容
本发明的目的是要解决大多数无色透明聚酰亚胺难以承受电子行业无铅焊造回流加工的高温环境，而提供一种用于电子无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法。
本发明所采用的技术方案如下：一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，如下：
步骤一、将混合二胺加入到非质子极性溶剂中，在氮气氛围中搅拌至完全溶解，得到混合二胺溶液；混合二胺与非质子极性溶剂的固液比为：11.0～18.0Kg∶150L；所述的混合二胺由以下原料按摩尔比混合而成：
9，9-双-(4-氨基苯基)芴∶3，3’-二氨基二苯醚∶2，2’-双(三氟甲基)-4，4’-二氨基苯基醚＝1-18∶1-10∶1-18；
步骤二、分多次将混合二酐添加到混合二胺溶液中，同时通入氮气，室温搅拌，缩聚反应，得到前驱体聚酰胺酸溶液；所述的混合二酐由以下原料按摩尔比混合而成：
1，2，4，5-环己烷四甲酸二酐∶4，4’-(六氟异亚丙基)二邻苯二甲酸酐∶双酚A型二醚二酐＝1-18∶1-10∶1-18；添加的所述的混合二酐和混合二胺的摩尔比为0.9∶1～1.1∶1；
步骤三、将前驱体经热亚胺化处理获得自支撑的聚酰胺酸薄膜；
步骤四、将自支撑聚酰胺酸薄膜进行热亚胺化和拉伸，进一步处理制得的无色透明聚酰亚胺膜。
进一步的，制备方法具体如下：
步骤一、将混合二胺加入到非质子极性溶剂中，在氮气氛围中搅拌至完全溶解，得到混合二胺溶液；混合二胺与非质子极性溶剂的固液比为：11.0～18.0Kg∶150L；所述的混合二胺由以下原料按摩尔比混合而成：
9，9-双-(4-氨基苯基)芴∶3，3’-二氨基二苯醚∶2，2’-双(三氟甲基)-4，4’-二氨基苯基醚＝1-18∶1-10∶1-18；
步骤二、分多次将混合二酐添加到混合二胺溶液中，同时通入氮气，在室温和高速搅拌条件下缩聚反应6h～30h，得到前驱体聚酰胺酸溶液；所述的混合二酐由以下原料按摩尔比混合而成：
1，2，4，5-环己烷四甲酸二酐∶4，4’-(六氟异亚丙基)二邻苯二甲酸酐∶双酚A型二醚二酐＝1-18∶1-10∶1-18；
添加的所述的混合二酐和混合二胺的摩尔比为0.9∶1～1.1∶1；
步骤三、将前驱体聚酰胺酸溶液脱泡得到均匀的溶液；
步骤四、将脱泡后的前驱体聚酰胺酸溶液采用流延机流延，同时烘烤，获得自支撑的聚酰胺酸薄膜，所述的聚酰胺酸薄膜中非质子极性溶剂的含量下降至18～38％；
步骤五、将所述的聚酰胺酸薄膜进入亚胺化炉，采用同步或异步的双向拉伸，亚胺化炉中拉伸的控制温度为280～330℃；
步骤六、经过拉伸处理后制得无色透明聚酰亚胺膜。
进一步的，如上所述的非质子极性溶剂为N，N二甲基甲酰胺、N，N二甲基乙酰胺或N-甲基吡咯烷酮。
进一步的，步骤四，流延机钢带上风温度为80～120℃，钢带下风温度为100～150℃。
进一步的，步骤五，同步双向拉伸为：纵向和横向方向的同步进行拉伸，同步双向拉伸的纵向拉伸比为1.00～1.50，横向拉伸比为1.00～1.30。
进一步的，步骤五，异步双向拉伸为：先通过控制轨道宽度对薄膜进行纵向拉伸，然后进行横向拉伸，异步双向拉伸的纵向拉伸比为1.00～1.60；横向拉伸比为1.00～1.35。
进一步的，通过调整流延机的挤出模头的狭缝距离来控制流延在不锈钢带上湿膜的厚度，制得膜厚度在15～80μm，宽幅为260～1200mm。
本发明的另一目的是公开通过如上方法制得的无色透明聚酰亚胺膜，其透光率不低于90％、270℃下冷热伸缩比小于等于0.20％
本发明的原理如下：本发明采用三种特殊结构的二胺单体进行共聚，其中9，9-双-(4-氨基苯基)芴(FDA)结构特征为两个氨基对位连接多环芳烃芴的叔丁基碳原子，芴的多环芳烃结构使CPI有较高玻璃化转变温度Tg；同时叔丁基碳原子的大体积侧基也破坏共平面结构，降低电荷转移络合(CTC)效应从而使其颜色降低。2，2’-双(三氟甲基)-4，4’-二氨基苯基醚(6FODA)中强电负性的三氟甲基基团能够吸附电荷，降低电荷转移络合(CTC)效应而使颜色变浅；三氟甲基在氨基间位比在临位和间位更能阻碍电荷转移，从而进一步降低颜色；同时苯环间的柔性醚键也有助于降低颜色。3，3’-二氨基二苯醚(BAE)中氨基在醚键间位，比常见4，4’-二氨基二苯醚(ODA)有更弱的电荷转移络合(CTC)效应，从而降低颜色；同时其结构中仅有一个醚键，有助于保持较高的玻璃化转变温度Tg。所用的三种二酐单体中1，2，4，5-环己烷四甲酸二酐(HPMDA)含有脂肪族六元环，其脂环结构能有效阻止电荷转移络合(CTC)效应，从而降低颜色；4，4’-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)中含有异丙基双三氟甲基，其强电负性和异丙基结构能有有效阻碍CTC效应，使所得CPI颜色降低；同时六氟异丙基大基团能够阻碍分子链的自由运动，从而保持较高玻璃化转变温度Tg。双酚A型二醚二酐(BPADA)中两个醚键和异丙基基团均能有效阻碍电荷转移络合(CTC)效应，从而降低颜色。上述具有特殊结构的三种二酐和三种二胺单体进行无规共聚，无规共聚导致的 无规结构比均聚能更好降低CPI颜色。因此，本发明中9，9-双-(4-氨基苯基)芴、2，2’-双(三氟甲基)4，4’-二氨基苯基醚、3，3’-二氨基二苯醚三种二酐，与1，2，4，5环己烷四甲酸二酐(HPMDA)、4，4’-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)、双酚A型二醚二酐(BPADA)三种二胺的无规共聚CPI既能耐受电子行业无铅焊造回流长时间高温，又能保持良好的尺寸稳定性和优异透明度，在电子行业有重要应用前景。
本发明的优点及有益效果：本发明制备的无色透明聚酰亚胺膜厚度在15～80μm，这样的厚度适合在膜上进行电子器件加工，在实际应用中具有优异的加工性能；本发明制备的无色透明聚酰亚胺膜透光率不低于90％，在270℃时的冷热伸缩比小于等于0.20％，尺寸稳定性高，使用寿命长，可用于高端电子行业，满足电子行业无铅焊造回流的高温制造要求。
附图说明
图1是本发明实施例5制备的CPI红外光谱图；
图2是本发明实施例5制备的CPI紫外-可见光谱图。
具体实施方式
下面举例对本发明做进一步的说明：
实施例1
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的溶剂：N，N-二甲基乙酰胺，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为1∶1∶18；搅拌至完全溶解，得到混合二胺溶液；混合二胺与N，N-二甲基乙酰胺的固液比为11Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为1∶1∶18。在室温和高速搅拌条件下聚合反应6h，得到前驱体聚酰胺酸溶液。添加的所述的混合二酐和混合二胺的摩尔比为0.9∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液。
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为80℃，钢带下风温度为100℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中所述的聚酰胺酸薄膜中N，N-二甲基乙酰胺溶剂的含量下降至38％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.0，横向拉伸比为1.0，亚胺化炉中拉伸的最高控制温度为280℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在 260mm、厚度在15μm的无色透明聚酰亚胺膜。
实施例2
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚的混合物加入溶解釜中，其物质的量摩尔比为18∶1∶1；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与N，N-二甲基乙酰胺溶剂的体积比为18.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为18∶1∶1。在室温和高速搅拌条件下聚合反应30h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.1∶1；
三、将前驱体聚酰胺酸通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液。
四、将脱泡后的前驱体聚酰胺酸通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为120℃，钢带下风温度为150℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量下降至18％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸分步进行的异步双向拉伸，纵向拉伸比在为1.6，横向拉伸比为1.35，亚胺化炉中拉伸的最高控制温度为330℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1200mm、厚度在80μm的无色透明聚酰亚胺膜。
实施例3
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为3∶3∶4；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为12Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为4∶1∶5。在室温和高速搅拌条件下聚合反应10h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.08∶1；
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为90℃，钢带下风温度为120℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量下降至28％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.25，横向拉伸比为1.20，亚胺化炉中拉伸的最高控制温度为290℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在550mm、厚度在80μm的无色透明聚酰亚胺膜。
实施例4
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为2∶2∶6；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为16.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为3∶2∶5。在室温和高速搅拌条件下聚合反应6h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为0.92∶1；
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为110℃，钢带下风温度为150℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量为21％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.25，横向拉伸比为1.25，亚胺化炉中拉伸的最高控制温度为320℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。
实施例5
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为1∶2∶1；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为15.0Kg∶150L。二、将溶解 釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为1∶2∶1。在室温和高速搅拌条件下聚合反应15h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为0.95∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为110℃，钢带下风温度为150℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量为26％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.10，横向拉伸比为1.18，亚胺化炉中拉伸的最高控制温度为310℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。其中，图1所示为本实施例制备的CPI红外光谱，这些特征吸收峰说明实施例一制备的CPI已经高度酰亚胺化。图2所示为本实施例制备的CPI的紫外-可见光谱图，从图2中可见厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.2％。
实施例6
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为2∶1∶7；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为16.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为2∶1∶7。在室温和高速搅拌条件下聚合反应20h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.06∶1；
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为100℃，钢带下风温度为130℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量降至22％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸分步进行的异步双向拉伸，纵向拉伸比在为1.20， 横向拉伸比为1.20，亚胺化炉中拉伸的最高控制温度为300℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在550mm、厚度在75μm的无色透明聚酰亚胺膜。
本实施例制备的厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.3％，该膜在电子行业无铅焊造回流270℃高温300s然后冷却到室温的冷热伸缩比为0.15％。
实施例7
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为5∶2∶3；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为17.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为4∶3∶3。在室温和高速搅拌条件下聚合反应10h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.04∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为100℃，钢带下风温度为130℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量为21％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸分步进行的异步双向拉伸，纵向拉伸比在为1.26，横向拉伸比为1.35，亚胺化炉中拉伸的最高控制温度为320℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。
本实施例制备的厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.5％，该膜在电子行业无铅焊造回流270℃高温300s然后冷却到室温的冷热伸缩比为0.17％。
实施例8
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基乙酰胺溶剂，通入氮气。将9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为5∶3∶2；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为13.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异 亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为4∶5∶1。在室温和高速搅拌条件下聚合反应8h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.02∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为90℃，钢带下风温度为130℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基乙酰胺溶剂的含量为22％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.16，横向拉伸比为1.28，亚胺化炉中拉伸的最高控制温度为310℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。
实施例四制备的厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.1％，该膜在电子行业无铅焊造回流270℃高温300s然后冷却到室温的冷热伸缩比为0.13％。
实施例9
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N，N-二甲基甲酰胺，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为3∶3∶4；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为16.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为5∶3∶2。在室温和高速搅拌条件下聚合反应18h，得到前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为0.97∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液；
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为80℃，钢带下风温度为120℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜，其中N，N-二甲基甲酰胺溶剂的含量为25％。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸分步进行的异步双向拉伸，纵向拉伸比在为1.26，横向拉伸比为1.38，亚胺化炉中拉伸的最高控制温度为300℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。
本实施例制备的厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.8％，该膜在电子行业无铅焊造回流270℃高温300s然后冷却到室温的冷热伸缩比为0.12％。
实施例10
本实施方式的用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜是按照如下步骤完成的：
一、在配有机械搅拌和氮气出入口的300L溶解釜中加入150L的N-甲基吡咯烷酮溶剂，通入氮气。将混合二胺：9，9-双-(4-氨基苯基)芴、3，3’-二氨基二苯醚和2，2’-双(三氟甲基)-4，4’-二氨基苯基醚加入溶解釜中，其物质的量摩尔比为3∶4∶3；搅拌至完全溶解，得到混合二胺溶液；混合二胺重量与非质子极性溶剂的体积比为17.0Kg∶150L。
二、将溶解釜中的混合二胺溶液通过加压泵全部压入配有机械搅拌和氮气出入口的300L树脂釜中，通入氮气。然后将混合二酐：1，2，4，5-环己烷四甲酸二酐、4，4’-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐分多次添加到树脂釜中，其物质的量之比为5∶4∶1。在室温和高速搅拌条件下聚合反应28h，得到前驱体聚酰胺酸前驱体聚酰胺酸溶液；添加的所述的混合二酐和混合二胺的摩尔比为1.02∶1。
三、将前驱体聚酰胺酸溶液通过加压泵全部压入400L的脱泡釜中，经过过滤、静置、脱泡得到均匀的溶液。
四、将脱泡后的前驱体聚酰胺酸溶液通过挤出模头均匀流延在循环运转的不锈钢带上，钢带上风温度为100℃，钢带下风温度为130℃。经过钢带烘烤后获得自支撑聚酰胺酸薄膜。
五、将自支撑聚酰胺酸薄膜从钢带上剥离下来，采用不锈钢夹具进行固定，然后通过导引辊进入亚胺化炉。
六、采用纵向和横向方向的拉伸同步进行的同步双向拉伸，纵向拉伸比在为1.22，横向拉伸比为1.36，亚胺化炉中拉伸的最高控制温度为310℃。
七、经过高温下的双向拉伸处理后，薄膜经过冷却、切边、收卷，最终制得宽幅在1100mm、厚度在75μm的无色透明聚酰亚胺膜。
本实施例制备的厚度为75μm的无色透明聚酰亚胺膜平均透光率为90.1％，该膜在电子行业无铅焊造回流270℃，高温300s然后冷却到室温的冷热伸缩比为0.10％。
从实际应用出发，本发明制备的无色透明聚酰亚胺膜的尺寸稳定性用冷热收缩比来进行表征。即先在无色透明聚酰亚胺膜上用激光器划出两条线，测出两条线内侧之间的距离，并做标记。然后将无色透明聚酰亚胺膜放进预热好270℃的回流炉内300s，再光学测量间距。测量不同区域和角度方向，最后对测量值变化误差进行统计分析。75μm厚时透光率≥90％、270℃下冷热伸缩比≤0.20％。
冷热伸缩比试验数据表

Claims (10)

  1. 一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：方法如下：
    步骤一、将混合二胺加入到非质子极性溶剂中，在氮气氛围中搅拌至完全溶解，得到混合二胺溶液；混合二胺与非质子极性溶剂的固液比为：11.0～18.0Kg:150L；所述的混合二胺由以下原料按摩尔比混合而成:
    9,9-双-(4-氨基苯基)芴：3,3’-二氨基二苯醚：2,2’-双(三氟甲基)-4,4’-二氨基苯基醚＝1-18：1-10：1-18；
    步骤二、分多次将混合二酐添加到混合二胺溶液中，同时通入氮气，室温搅拌，缩聚反应，得到前驱体聚酰胺酸溶液；所述的混合二酐由以下原料按摩尔比混合而成:
    1,2,4,5-环己烷四甲酸二酐：4,4'-(六氟异亚丙基)二邻苯二甲酸酐：双酚A型二醚二酐＝1-18：1-10：1-18；添加的所述的混合二酐和混合二胺的摩尔比为0.9：1～1.1：1；
    步骤三、将前驱体经热亚胺化处理获得自支撑的聚酰胺薄膜；
    步骤四、将自支撑聚酰胺薄膜进行热亚胺化和拉伸，进一步处理制得的无色透明聚酰亚胺膜。
  2. 根据权利要求1所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：方法具体如下：
    步骤一、将混合二胺加入到非质子极性溶剂中，在氮气氛围中搅拌至完全溶解，得到混合二胺溶液；混合二胺与非质子极性溶剂的固液比为：11.0～18.0Kg:150L；所述的混合二胺由以下原料按摩尔比混合而成:
    9,9-双-(4-氨基苯基)芴：3,3’-二氨基二苯醚：2,2’-双(三氟甲基)-4,4’-二氨基苯基醚＝1-18：1-10：1-18；
    步骤二、分多次将混合二酐添加到混合二胺溶液中，同时通入氮气，在室温和高速搅拌条件下缩聚反应6h～30h，得到前驱体聚酰胺酸溶液；所述的混合二酐由以下原料按摩尔比混合而成：
    1,2,4,5-环己烷四甲酸二酐：4,4'-(六氟异亚丙基)二邻苯二甲酸酐：双酚A型二醚二酐＝1-18：1-10：1-18；
    添加的所述的混合二酐和混合二胺的摩尔比为0.9：1～1.1：1；
    步骤三、将前驱体聚酰胺酸溶液脱泡得到均匀的溶液；
    步骤四、将脱泡后的前驱体聚酰胺酸溶液采用流延机流延，同时烘烤，获得自支撑的聚酰胺薄膜，所述的聚酰胺薄膜中非质子极性溶剂的含量下降至18～38％；
    步骤五、将所述的聚酰胺薄膜进入亚胺化炉，采用同步或异步的双向拉伸，亚胺化炉中拉伸的控制温度为280～330℃；
    步骤六、经过拉伸处理后制得无色透明聚酰亚胺膜。
  3. 根据权利要求1或2所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：所述的非质子极性溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮。
  4. 根据权利要求3所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：步骤四，流延机钢带上风温度为80～120℃，钢带下风温度为100～150℃。
  5. 根据权利要求4所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：步骤五，同步双向拉伸为：纵向和横向方向的同步进行拉伸，同步双向拉伸的纵向拉伸比为1.00～1.50，横向拉伸比为1.00～1.30。
  6. 根据权利要求4所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：步骤五，异步双向拉伸为：先通过控制轨道宽度对薄膜进行纵向拉伸，然后进行横向拉伸，异步双向拉伸的纵向拉伸比为1.00～1.60；横向拉伸比为1.00～1.35。
  7. 根据权利要求5或6所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，其特征在于：通过调整流延机的挤出模头的狭缝距离来控制流延在不锈钢带上湿膜的厚度，制得膜厚度在15～80μm，宽幅为260～1200mm。
  8. 根据权利要求7所述的一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法制备的无色透明聚酰亚胺膜。
  9. 根据权利要求8所述的无色透明聚酰亚胺膜透光率不低于90％，在270℃时的冷热伸缩比小于等于0.20％。
  10. 一种用于电子行业无铅焊造回流的高温无色透明聚酰亚胺膜的制备方法，该制备方法包括以下步骤：
    步骤一、将混合二胺完全溶解在非质子极性溶剂中，得到混合二胺溶液；其中所述混合二胺由以下原料混合而成：9,9-双-(4-氨基苯基)芴和3,3’-二氨基二苯醚：2,2’-双(三氟甲基)-4,4’-二氨基苯基醚；
    步骤二、将混合二酐添加到混合二胺溶液中以进行缩聚反应，得到前驱体聚酰胺酸溶液；其中所述混合二酐由以下原料混合而成：1,2,4,5-环己烷四甲酸二酐、4,4'-(六氟异亚丙基)二邻苯二甲酸酐和双酚A型二醚二酐；
    步骤三、将前驱体经热亚胺化处理，获得自支撑的聚酰胺薄膜；
    步骤四、将所述自支撑聚酰胺薄膜进行热亚胺化和拉伸，得到无色透明聚酰亚胺膜。
PCT/CN2023/077543 2022-02-22 2023-02-22 用于电子行业无铅焊造回流的耐高温无色透明聚酰亚胺膜及其制备方法 WO2023160563A1 (zh)

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