CN101736329B - A polyimide film and the polyimide film was activated metallization process - Google Patents

A polyimide film and the polyimide film was activated metallization process Download PDF

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CN101736329B
CN101736329B CN 200810217841 CN200810217841A CN101736329B CN 101736329 B CN101736329 B CN 101736329B CN 200810217841 CN200810217841 CN 200810217841 CN 200810217841 A CN200810217841 A CN 200810217841A CN 101736329 B CN101736329 B CN 101736329B
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polyimide film
solution
ammonia
polyimide
activation solution
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CN101736329A (en )
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刘小云
宫清
林宏业
连俊兰
韦家亮
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比亚迪股份有限公司
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本发明公开了一种聚酰亚胺膜活化液及聚酰亚胺膜金属化的方法。 The present invention discloses a method of activation solution and a polyimide film metallized polyimide film. 该聚酰亚胺膜活化液含有金属离子、氨和聚酰亚胺膜润湿剂,所述聚酰亚胺膜活化液的pH为9-14,金属离子与氨的摩尔比1:4-8。 The polyimide film activation solution containing metal ions, ammonia and the polyimide film wetting agents, pH of the polyimide film activation solution is 9-14, the molar ratio of metal ion to ammonia 1: 4- 8. 聚酰亚胺膜金属化的方法包括:将聚酰亚胺膜与权利要求1所述的聚酰亚胺膜活化液接触;将与聚酰亚胺膜活化液接触后的聚酰亚胺膜进行热处理或者还原处理,得到表面金属化的聚酰亚胺膜。 Metallized polyimide film comprising: contacting the activating solution of the polyimide film and the polyimide film 1 as claimed in claim; polyimide film after contact with the polyimide film was activated heat treatment or reduction treatment to obtain a surface metallized polyimide film. 采用本发明公开的聚酰亚胺膜活化液对聚酰亚胺膜进行金属化能简化制备工艺,并且聚酰亚胺膜表面形成的金属层的附着力良好。 The polyimide film was activated using the present invention disclosed in the polyimide film can be metallized simplifying the manufacturing process and the adhesion of the metal layer is formed on the surface of the polyimide film was good.

Description

一种聚酰亚胺膜活化液及聚酰亚胺膜金属化的方法 A polyimide film and the polyimide film was activated metallization process

【技术领域】 TECHNICAL FIELD

[0001] 本发明涉及一种聚酰亚胺膜活化液及采用该聚酰亚胺膜活化液对聚酰亚胺膜表面金属化的方法,尤其是一种采用该聚酰亚胺膜活化液对聚酰亚胺薄膜进行金属化的方法。 [0001] The present invention relates to an activation solution of the polyimide film and the polyimide film using a polyimide film was activated surface metallization process, particularly to a use of the polyimide film was activated polyimide film metallization method.

【背景技术】 【Background technique】

[0002] 聚酰亚胺(PI)薄膜因耐酸、耐碱、耐高温、强度高、介电常数低、柔性好等优异性能成为了高性能电子、信息产业的首选基材,根据使用要求,通常需要对聚酰亚胺薄膜表面进行金属化处理,所以聚酰亚胺薄膜的金属化方法也倍受关注。 [0002] The polyimide (PI) film due to acid, alkali, high temperature, high strength, low dielectric constant, good flexibility, excellent performance has become the preferred substrate is a high-performance electronics, information industry, according to requirements, often require metallized polyimide film surface, the method of metallizing the polyimide film has attracted much attention.

[0003] 现有技术中对薄膜表面进行金属化的方法为:对薄膜表面进行粗化,然后活化、还原和化学镀。 [0003] The methods of the prior art metal thin film surface: The film surface is roughened, and then activated, and chemical reduction plating. 其中活化液通常为碱性,其中包括金属离子、PH调节剂、有机络合剂。 Wherein the activation solution is generally alkaline, which comprises a metal ion, PH adjusting agent, an organic complexing agent. 该方法需要对薄膜表面进行粗化处理,形成粗糙的表面,以利于金属离子与有机络合剂形成的络合物在该粗糙表面的吸附。 This method requires a thin film surface roughening treatment, a roughened surface, the adsorption of chelate metal ions and an organic complexing agent to facilitate formation of the rough surface. 并且在还原后,只能得到一些金属活性中心,还需进一步进行化学镀才能得到完整的金属层。 And after the reduction, to give some of the active metal center only needs further electroless plating metal layer to get complete.

【发明内容】 [SUMMARY]

[0004] 为了克服现有技术中在聚酰亚胺膜表面进行金属化时工艺较繁琐并且金属层附着力低的缺点,本发明公开了一种聚酰亚胺膜活化液及采用该聚酰亚胺膜活化液对聚酰亚胺膜表面进行金属化的方法,通过采用上述聚酰亚胺膜活化液对聚酰亚胺膜表面进行金属化能简化工艺,不需要进行化学镀,并且聚酰亚胺金属化膜表面金属层的附着力良好。 [0004] In order to overcome process performed when the metal is relatively complex and the low adhesion metal layer polyimide film surface disadvantages in the prior art, the present invention discloses a polyimide film and the use of the activation solution polyamic imide film was subjected to the activation process of metallizing the surface of the polyimide film, the polyimide film by using the activation solution to the surface of the polyimide film can be metallized a simplified process, does not require plating, and poly polyimide adhesion layer of the metal surface of the metal film is good.

[0005] 本发明公开的聚酰亚胺膜活化液,包括金属离子、氨和聚酰亚胺膜润湿剂,所述聚酰亚胺膜活化液的PH为9-14,金属离子与氨的摩尔比为1 :4-8。 [0005] The polyimide film of the present invention disclosed in activation solution, include metal ions, ammonia and a wetting agent, a polyimide film, PH said polyimide film activation solution is 9-14, the metal ions with ammonia molar ratio of 1: 4-8.

[0006] 本发明还公开了一种聚酰亚胺膜金属化的方法,包括:将聚酰亚胺膜与权利要求1所述的聚酰亚胺膜活化液接触;将与聚酰亚胺膜活化液接触后的聚酰亚胺膜进行热处理或者还原处理,得到表面金属化的聚酰亚胺膜。 [0006] The present invention also discloses a process for metallization of a polyimide film, comprising: a polyimide film in contact with said liquid activating a polyimide film with claim 1; a polyimide contacting the polyimide film after the film was subjected to heat treatment activation or reduction treatment to obtain a surface metallized polyimide film.

[0007] 本发明中,聚酰亚胺膜活化液是pH为9-14的强碱性环境,在该环境中,通常情况下,金属离子都会生成不溶物沉淀下来。 [0007] In the present invention, a polyimide film activation solution is a strong alkaline pH of 9-14 environment, in the environment, usually, the metal ions are precipitated insoluble matters. 本发明的发明人发现,当上述强碱性环境中含有氨时,氨能与金属离子形成络合物,避免金属离子形成沉淀。 The present inventors found that, when the strong alkaline environment containing ammonia, forms a complex with metal ions, the metal ions to avoid formation of a precipitate.

[0008] 由于聚酰亚胺的结构中有酰亚胺结构,在碱性条件下易发生水解,当聚酰亚胺膜与本发明公开的聚酰亚胺膜活化液接触时,聚酰亚胺膜表面发生水解,形成聚酰胺酸。 [0008] Since the polyimide structure has an imide structure, easy to hydrolysis under alkaline conditions, when the polyimide film is a polyimide film and the activation solution according to the present invention is disclosed in contact, polyimides amine hydrolyzed membrane surface to form a polyamic acid. 由于NH3与金属离子形成的络合物不够稳定,在一定条件下,如加热,容易释放出金属离子。 Since the complexes formed with metal ions of NH3 is not stable enough, under certain conditions, such as heating, readily releasing a metal ion. 而聚酰胺酸能与金属离子生成的化合物,其稳定性相对较高。 The polyamic acid capable of forming compounds with a metal ion, its stability is relatively high. 经过聚酰亚胺膜润湿剂的作用,当金属离子的氨络合物与聚酰亚胺膜表面接触时,被氨释放出来的金属离子能与聚酰亚胺水解得到的聚酰胺酸形成比较稳定的化合物,即在聚酰亚胺膜表面得到金属化合物;然后通过还原将金属化合物中的金属离子还原为金属原子并不断累积,在聚酰亚胺膜表面形成一金属层,同时水解生成的聚酰胺酸发生环化反应,重新形成聚酰亚胺。 After the role of the polyimide film of a wetting agent, a metal ammine complex ions when in contact with the surface of the polyimide film, ammonia is released a metal ion capable of forming a polyimide polyamic acid obtained by hydrolyzing relatively stable compound, i.e., to obtain a polyimide film surface of a metal compound; followed by reduction of the metal ion in the reduction of the metal compound is a metal atom and accumulate, forming a metal layer on the polyimide film surface while hydrolysis the cyclization reaction of a polyamic acid, a polyimide is formed again. [0009] 采用本发明提供的聚酰亚胺膜活化液,在聚酰亚胺膜表面的聚酰亚胺水解后时, 金属离子能立即与聚酰亚胺水解得到的聚酰胺酸形成比较稳定的化合物,然后经还原即可得到表面附着有金属层的聚酰亚胺膜。 [0009] The polyimide film of the present invention provides activation solution, when the hydrolysis of the polyimide of the polyimide film surface, the metal ions can imide and polyamic acid hydrolysis stable polyethylene formed immediately the compound then can be obtained by reduction of the polyimide film adhered on the surface of the metal layer. 本发明通过金属离子与聚酰亚胺膜结合,经过还原后,得到的金属层附着于聚酰亚胺膜上,不需要进行化学镀,并且金属层的附着力良好。 The present invention is bonded by a metal ion and the polyimide film, after the reduction, the metal layer was adhered to a polyimide film, it does not require plating, and adhesion of the metal layer is good.

【具体实施方式】 【Detailed ways】

[0010] 本发明公开了一种聚酰亚胺膜活化液,包括金属离子、氨和聚酰亚胺膜润湿剂,所述聚酰亚胺膜活化液的PH为9-14,金属离子与氨的摩尔比为1 :4_8。 [0010] The present invention discloses a polyimide film activation solution, include metal ions, ammonia and a wetting agent, a polyimide film, PH said polyimide film is 9-14 activation solution, a metal ion the molar ratio of ammonia of 1: 4_8.

[0011] 本发明中,所述聚酰亚胺膜活化液优选为水溶液,所述金属离子为Cu2+、Ni2+、Ag+、 Co2+中的一种或几种。 [0011] In the present invention, the polyimide film activation solution is preferably an aqueous solution, the metal ion is Cu2 +, Ni2 +, Ag +, Co2 + one or more of. 所述金属离子可通过上述各种金属的可溶性盐类加入,例如:所述可溶性盐类可以为上述各种金属的硫酸盐、氯盐、硝酸盐中的一种或几种。 The metal ions can be obtained by the above-described soluble salts of various metals added to, for example: the soluble sulfate salt may be the above-mentioned various metals, chloride, nitrate of one or more.

[0012] 所述聚酰亚胺膜活化液中的氨可以由各种方式引入,如:以铵盐或者氨水。 [0012] The polyimide film ammonia activation solution may be introduced by various ways, such as: aqueous ammonia or an ammonium salt. 铵盐可以为氨的各种盐类,如(NH4) 2S04、NH4Cl、NH4NO3,当通过添加铵盐来引入氨时,铵盐必须处于碱性环境中,使铵盐中的NH4+转化成NH3。 Ammonium salts may be various salts of ammonia, such as (NH4) 2S04, NH4Cl, NH4NO3, when ammonia is introduced by adding an ammonium salt, an ammonium salt must be in an alkaline environment, the ammonium salt is converted into NH4 + NH3.

[0013] 在所述聚酰亚胺膜活化液中,金属离子与氨的摩尔比为1 :4_8,优选为1 :5_7。 [0013] In the polyimide film was activated, the molar ratio of metal ion to ammonia is 1: 4_8, preferably 1: 5_7.

[0014] 本发明中,当所述金属离子和氨的量满足上述关系时,聚酰亚胺膜活化液中的金属离子能更好的和氨形成络合物,如[Cu(NH3)4]2+,在碱性条件下保护金属离子,使金属离子避免与游离的氢氧根生成沉淀物质,保持整个聚酰亚胺膜活化液体系的稳定。 [0014] In the present invention, when the amount of the metal ions and ammonia satisfy the above relation, the metal ion activation of the polyimide film of liquid ammonia and can better form a complex, such as [Cu (NH3) 4 ] 2+, protected under basic conditions a metal ion, metal ion precipitation material and to avoid the formation of free hydroxide, to maintain stability of the entire system activation solution polyimide film. 避免上述金属离子在强碱性环境中大量形成沉淀,影响了还原形成的金属层的质量,导致得不到完整的金属层。 Prevent the metal ions are formed in the large amount of precipitate in a strong alkaline environment, affecting the quality of the metal layer is reduced to form, resulting in lack of a complete metal layer.

[0015] 优选情况下,所述聚酰亚胺膜活化液中金属离子浓度为0.03-0. 20mol/l,氨的浓度为0. 12-1.00mol/L·进一步优选为金属离子浓度为0. 05-0. 08mol/l,氨的浓度为0.25-0. 60mol/l。 [0015] Preferably, the polyimide film was activated metal ion concentration is 0.03-0. 20mol, concentration / l ammonia was 0. 12-1.00mol / L · more preferably a metal ion concentration 0 . 05-0. 08mol / l, the concentration of ammonia is 0.25-0. 60mol / l.

[0016] 当通过添加铵盐的方式引入氨时,由于在碱性环境下,氨离子会不断水解生成NH3,故只需铵盐中NH4+的量在上述范围内即可。 [0016] When the ammonia is introduced by adding an ammonium salt, since in an alkaline environment, ammonium ions constantly hydrolysis NH3, so just the amount of ammonium salt of NH4 + within the above range.

[0017] 当通过添加氨水来弓丨入氨时,所采用的氨水为化学领域常用的氨水,在本发明中, 聚酰亚胺膜活化液中的氨是指以氨分子NH3形式存在的成分,所述氨的浓度表示在所述聚酰亚胺膜活化液中NH3的浓度。 [0017] When the bow to the Shu by adding ammonia water, ammonia, aqueous ammonia is used as ammonia used in the chemical arts, in the present invention, the polyimide film ammonia activation solution refers to the constituents present in the form of ammonia molecules NH3 , the concentration represents the concentration of ammonia in the polyimide film activation solution of NH3. 在制备上述聚酰亚胺膜活化液时,通过添加氨水来引入NH3, 一般在水中NH3都会发生不同程度的水解,当向聚酰亚胺膜活化液中添加氨水时,NH3的水解程度发生变化,但是NH3的水解导致的NH3的浓度变化不大,在本发明中,可以忽略不计, 以氨水中含有的NH3的物质的量为准。 In the preparation of the polyimide film was activated by the addition of ammonia NH3 is introduced, different degrees of hydrolysis generally occurs in the water will NH3, when ammonia is added to the activation solution of the polyimide film, the degree of hydrolysis varies NH3 , but little change in the concentration of the hydrolysis of NH3 NH3 result, in the present invention, is negligible, the amount of the substance contained in aqueous ammonia NH3 prevail.

[0018] 所述聚酰亚胺膜活化液中聚酰亚胺膜润湿剂浓度为0. 5-8g/l,优选为l_5g/l。 [0018] The polyimide film of the polyimide film was activated wetting agent concentration of 0. 5-8g / l, preferably l_5g / l.

[0019] 所述聚酰亚胺膜润湿剂为甲酰胼、乙二醇、乙醇、三乙醇胺、甘油、山梨醇、丙二醇、 聚乙二醇中的一种或几种,优选为乙二醇,所述聚酰亚胺膜润湿剂浓度为0. 5-8g/l,优选为l_5g/l。 [0019] The polyimide film of the wetting agent is one or more of the corpus formyl, ethylene glycol, ethanol, triethanolamine, glycerine, sorbitol, propylene glycol, polyethylene glycol, preferably ethylene an alcohol, a wetting agent concentration of the polyimide film was 0. 5-8g / l, preferably l_5g / l. 所述聚酰亚胺膜润湿剂可用过商购得到,如广东省化学试剂工程技术研究开发中 The polyimide film had a wetting agent available commercially available, such as Guangdong Chemicals Research Development Engineering Technology

心生产的乙二醇。 Heart produce ethylene glycol.

[0020] 通过向本发明公开的聚酰亚胺膜活化液中添加聚酰亚胺膜润湿剂,降低聚酰亚胺膜表面的表面张力,聚酰亚胺膜表面的聚酰亚胺能被聚酰亚胺膜活化液良好浸润,氨与金属离子形成的络合物能更好的与水解得到的聚酰胺酸接触,从而得到比较稳定的聚酰胺酸 [0020] activated by a polyimide film disclosed in the present invention was added to the polyimide film wetting agent, reducing the surface tension of the surface of the polyimide film, the polyimide film surface of the polyimide can good wetting is a polyimide film activation solution, ammonium ions and metal complexes formed with better contact with the polyamic acid obtained by the hydrolysis, thereby obtaining a polyamic acid stable

4金属化合物。 4 metal compound. 通过上述聚酰亚胺膜润湿剂的作用,聚酰亚胺膜表面不需进行表面粗化,简化了工艺步骤,还原得到的金属层完整,并有利于提高聚酰亚胺膜表面金属层的附着力。 By the action of the wetting agent of the polyimide film, the polyimide film without performing a surface roughening, simplifying the process steps, the complete reduction of the metal layer obtained, and help to improve the surface of the metal layer of the polyimide film adhesion. [0021 ] 本发明所公开的聚酰亚胺膜活化液的pH为9-14,优选为10-13。 pH polyimide film disclosed in the activation solution [0021] The present invention is 9-14, preferably 10-13. 在本发明中,可通过添加pH调节剂来控制pH值,所述pH调节剂为本领域公知能影响溶液pH值的物质,如氢氧化钠,氢氧化钾,其添加量为使所述聚酰亚胺膜活化液的PH值落入上述范围内即可。 In the present invention, the pH can be controlled by adding a pH adjusting agent, a pH adjusting agent is well known to those of knowledge and ability Substances pH of the solution, such as sodium hydroxide, potassium hydroxide, which is added in an amount so that the poly PH value of the polyimide film activation solution falls within the above range. 可在添加pH调节剂前计算出对应pH值所需的pH调节剂的量。 Can calculate the amount corresponding to the desired pH value of the pH adjusting agent is added before the pH adjusting agent.

[0022] 当本发明公开的聚酰亚胺膜活化液通过添加氨水来引入氨时,所述聚酰亚胺膜活化液的PH值可以通过添加pH调节剂来控制,也可以通过控制氨水本身的添加量来控制,优选情况下,通过控制氨水的添加量来调节PH值而不另外添加pH调节剂。 [0022] When the polyimide film of the present invention is disclosed in activation solution be introduced by the addition of ammonia, ammonia water, PH value of the polyimide film activation solution may be controlled by adding a pH adjusting agent, ammonia itself may be controlled by the amount of addition is controlled, preferably, by controlling the amount of ammonia added to adjust the pH value without further addition of a pH adjusting agent. 若采用氨水来调节聚酰亚胺膜活化液的PH值,当氨水的添加量使氨的浓度落入其范围内时,所制得的聚酰亚胺膜活化液的PH值即在上述范围内。 If ammonia water to adjust the PH value of the polyimide film was activated, when the amount of ammonia so that the ammonia concentration falls within its scope, the PH value of the obtained polyimide film was activated in the above-described range, i.e., Inside. 所述pH值可通过本领域公知的方法测得,如采用PH计(梅特勒-托利多生产的kvenEasy pH计-S20)直接测试得到。 The pH may be measured by methods known in the art, such as using PH meter (Mettler - Toledo production kvenEasy pH meter -S20) tested directly obtained.

[0023] 所述聚酰亚胺膜活化液的制备方法为本领域常用的方法,如:配制1升该聚酰亚胺膜活化液时,可将所需要的上述范围内的氨水和聚酰亚胺膜润湿剂加入到去离子水中, 然后在搅拌条件下缓慢加入金属盐,然后定容至1升即可。 [0023] The method of the polyimide film prepared activation solution of the present method commonly used in the art, such as: preparation 1 liter of the polyimide film was activated, aqueous ammonia may be within the above desired range and polyimide imide film wetting agent is added to the deionized water, then added slowly with stirring under a metal salt, then the volume to 1 liter can. 当通过添加铵盐引入氨时,可先计算出所需的铵盐和PH调节剂的量,然后先将pH调节剂、铵盐加入到去离子水中,然后在搅拌条件下缓慢加入金属盐,最后定容至1升即可。 When the ammonia is introduced by adding an ammonium salt, an ammonium salt may first calculate the amount desired and the PH adjusting agents, and pH adjusting agent first, an ammonium salt to deionized water and then added slowly with stirring under a metal salt, Finally, you can set the volume to 1 liter. 聚酰亚胺膜润湿剂可在各个阶段加入, 优选情况下,在其他组分添加完毕之后再加入所述聚酰亚胺膜润湿剂。 Polyimide film wetting agent can be added at various stages, Preferably, after the addition was complete and then added to the other components of the polyimide film wetting agent. 其中,加入金属盐的方式可以为直接加入金属盐固体,也可以将金属盐先溶解于一定量的去离子水中形成溶液,然后以溶液的形式加入。 Wherein, the metal salt may be added to the way metal salt is added directly to solid, the metal salt may be dissolved in an amount of deionized water to form a solution, and then added as a solution.

[0024] 本发明还公开了一种聚酰亚胺膜金属化的方法,包括:将聚酰亚胺膜与权利要求1所述的聚酰亚胺膜活化液接触;将与聚酰亚胺膜活化液接触后的聚酰亚胺膜进行热处理或者还原处理,得到表面金属化的聚酰亚胺膜。 [0024] The present invention also discloses a process for metallization of a polyimide film, comprising: a polyimide film in contact with said liquid activating a polyimide film with claim 1; a polyimide contacting the polyimide film after the film was subjected to heat treatment activation or reduction treatment to obtain a surface metallized polyimide film.

[0025] 所述热处理为将与聚酰亚胺膜活化液接触后的聚酰亚胺膜在250-320°C下保持20-60min或者将改性聚酰亚胺膜与还原溶液接触,所述还原溶液中含有还原物质。 [0025] The polyimide film is heat-treated after contact with the polyimide film was kept 20-60min contact activation or modified polyimide film with a reducing solution at 250-320 ° C, the said reducing solution contains a reducing substance.

[0026] 如本领域技术人员所公知的,当所述金属离子为银离子或铬离子时,采用热处理, 当金属离子为铜离子或镍离子时,可采用与还原溶液接触。 [0026] As the skilled person is well known, when the metal ion is a silver ion or chromium ion, thermal treatment, when the metal ion is a copper ion or nickel ion, can be contacted with a reducing solution.

[0027] 本发明所采用的聚酰亚胺膜为本领域常用的聚酰亚胺膜,可通过商购得到,如杜邦公司生产的Kapton-H型聚酰亚胺膜。 [0027] The polyimide film used in the present invention is commonly used in the art present a polyimide film, is commercially available through suppliers, such as DuPont's Kapton-H polyimide film.

[0028] 在上述方法中所采用的聚酰亚胺膜活化液为上述所公开的聚酰亚胺膜活化液,聚酰亚胺膜活化液的组成及配制方法如前所述,在此不再赘述。 [0028] The polyimide film was activated in the above method is employed in the polyimide film activation solution as disclosed, the composition and method of preparation of the polyimide film was activated as described above, which is not then repeat.

[0029] 所述聚酰亚胺膜与聚酰亚胺膜活化液接触的方法为:在30-80°C下,将聚酰亚胺膜浸入所述聚酰亚胺膜活化液中10-180min。 [0029] The method of the polyimide film in contact with the polyimide film was activated as follows: at 30-80 ° C, the polyimide film was immersed in the polyimide film was activated 10- 180min.

[0030] 由于采用本发明公开的聚酰亚胺膜活化液,在所述聚酰亚胺膜与聚酰亚胺膜活化液接触时,聚酰亚胺膜在上述PH条件下,表面的聚酰亚胺发生水解,形成聚酰胺酸。 [0030] As a result of the activation of the polyimide film of the present invention was disclosed, upon the polyimide film in contact with the polyimide film was activated, the polyimide film under the above conditions PH, the surface of the poly imide hydrolysis to form a polyamic acid. 由于NH3与上述金属离子形成的络合物的稳定常数不够高,在某些条件下,如加热,容易释放出金属离子。 Since the stability constant of a complex NH3 formed with said metal ion is not high enough, under certain conditions, such as heating, readily releasing a metal ion. 而聚酰胺酸与金属离子形成的化合物稳定性相对较高,所以聚酰亚胺膜活化液中的金属离子与聚酰亚胺水解后的聚酰胺酸形成化合物,此时在聚酰亚胺膜表面得到聚酰胺酸与金属离子的化合物,然后通过还原将该化合物中的金属离子还原为金属原子并不断累积,在聚酰亚胺膜表面形成一金属层,同时水解的聚酰胺酸发生环化反应,重新形成聚酰亚胺。 Stability of the compound and the polyamic acid formed with metal ions is relatively high, the metal ion activation of the polyimide film a polyamic acid solution with the hydrolyzed polyimide compound, in this case a polyimide film surface polyamic acid compound obtained with a metal ion, and then reducing the metal ions by reducing compound is a metal atom and accumulate, forming a metal layer on the surface of the polyimide film, the polyamic acid hydrolysis while cyclization The reaction again to form a polyimide.

[0031] 所述还原溶液中还原物质的浓度可以在较大范围内变动,优选情况下,所述还原物质的浓度为0. 05-1. 00mol/l。 [0031] The concentration of the reducing substance in the reducing solution may vary over a wide range, preferably, the concentration of the reducing substance is 0. 05-1. 00mol / l.

[0032] 所述改性聚酰亚胺膜与还原溶液接触的方法为:在20-100°C下,将聚酰亚胺膜浸入所述还原溶液中10-180min。 The [0032] method modified polyimide film in contact with the reducing solution is: at 20-100 ° C, the polyimide film was immersed in reducing solution 10-180min.

[0033] 所述还原物质含有硼烷、磷酸二氢钠、乙醛酸中的一种或几种。 [0033] The reducing substance comprising a borane, sodium dihydrogen phosphate, one or more of glyoxylic acid. 所述硼烷为本领域常用的还原性硼烷,优选情况下,所述硼烷可以为:硼氢化钠、硼氢化钾、二甲胺基甲硼烷、 二乙基胺硼烷中的一种或几种。 The borane-based reducing commonly used in the art borane, Preferably, the borane can be: sodium borohydride, potassium borohydride, dimethylamino borane, diethylamine borane in a one or several.

[0034] 所述还原溶液可通过常规方法配制,如,将一定量的还原物质添加到去离子水中, 搅拌均勻即可。 [0034] The reducing solution can be formulated by a conventional method, such as the amount of reducing substance is added to the deionized water and mix well. 所述还原物质的添加量只需使其浓度在上述范围内即可。 The amount of reducing substance is added at a concentration just within the above range.

[0035] 将所述改性聚酰亚胺膜与还原溶液接触时,以化合物形式存在于聚酰亚胺膜表面的金属离子被还原为金属原子并附着于聚酰亚胺膜表面,还原得到的金属原子不断累积, 在聚酰亚胺膜表面形成一金属层,同时发生水解的聚酰亚胺发生环化反应,聚酰胺酸重新生成聚酰亚胺,从而在聚酰亚胺膜表面形成一金属层,得到表面附着有以金属层的改性聚酰亚胺膜。 [0035] The modified polyimide film in contact with the reducing solution, in the form of a metal ion compound is reduced to a polyimide film surface of a metal atom and is attached to the surface of the polyimide film, is reduced to give accumulating metal atoms, forming a metal layer on the polyimide film surface, while the hydrolyzed polyimide cyclization reaction to regenerate a polyimide polyamic acid, thereby forming a polyimide film surface a metal layer, to obtain a modified polyimide film adhered to the surface of the metal layer.

[0036] 本发明公开的聚酰亚胺膜金属化的方法还可以包括在所述聚酰亚胺膜与聚酰亚胺膜活化液接触前对聚酰亚胺膜进行除油。 [0036] The metallized polyimide film of the present invention, the method disclosed may also include a polyimide film is degreased before the polyimide film and the polyimide membrane active liquid contact. 所述除油的方法可以为本领域公知的方法,如: 将聚酰亚胺膜浸没于无水乙醇中,在超声波环境下清洗lOmin,然后用去离子水冲洗3min, 再将冲洗后的聚酰亚胺膜浸没于无机碱性除油液中,在超声波环境下清洗lOmin,最后用去离子水冲洗:3min即可。 The degreasing method may be a method known in the art, such as: a polyimide film was immersed in absolute ethanol, in an ultrasonic cleaning environment lOmin, then rinsed with deionized water 3min, then rinsing the poly polyimide film was immersed in an inorganic basic addition to oil, the cleaning lOmin under ultrasound environment, and finally rinsed with deionized water: 3min to. 所述在超声波环境下清洗可在上海生析超生仪器有限公司生产的超声波清洗机中进行。 The washing can be carried out in green resolution bounce Shanghai Instrument Co., Ltd. ultrasonic cleaner with ultrasonic environment. 所述无机碱性除油液为本领域公知的除油液,如含有20-30g/l碳酸钠、10-30g/l磷酸钠、10-20g/l氢氧化钠、2-5ml/l表面活性剂(十二烷基磺酸钠、十二烷基硫酸钠或正辛基硫酸钠)的碱性除油液。 The inorganic basic addition to oil known in the art other than oil, such as those containing 20-30g / l sodium carbonate, 10-30g / l sodium phosphate, 10-20g / l of sodium hydroxide, 2-5ml / l surface basic active agent (sodium dodecyl sulfate, sodium lauryl sulfate or n-octyl sulfate) in addition to oil.

[0037] 本发明公开的聚酰亚胺膜金属化的方法还可以包括在所述聚酰亚胺膜与聚酰亚胺膜活化液接触后用去离子水冲洗所述改性聚酰亚胺膜,以及在所述改性聚酰亚胺膜与还原溶液接触后用去离子水冲洗所述聚酰亚胺金属化膜。 [0037] The metallized polyimide film of the present invention disclosed method may further comprise, after the polyimide film is in contact with the polyimide film was rinsed with deionized water activation of the modified polyimide film, and after contact with deionized modified polyimide film of the solution with a reducing metal water rinse the polyimide film.

[0038] 根据本发明,改性聚酰亚胺膜与还原溶液接触,得到聚酰亚胺金属化膜后还可以将制得的聚酰亚胺金属化膜浸入保护液中3-lSOOs,所述保护液为本领域公知的保护液,如深圳市俄真科技有限公司生产的EZ202铜保护剂。 After [0038] According to the present invention, the modified polyimide film in contact with the reducing solution to obtain a polyimide film metallized polyimide also prepared a metal film may be immersed in the protection liquid 3-lSOOs, the said protection liquid present protection liquid known in the art, such as Shenzhen Main Technology Co EZ202 really copper protective agent. 然后用去离子水冲洗3min,在50-150°C 下烘30-120min即可。 And then rinsed with deionized water 3min, 30-120min to bake at 50-150 ° C.

[0039] 根据本发明公开的方法,在制备聚酰亚胺金属化膜的过程中,通过采用本发明公开的聚酰亚胺膜活化液,只需经过活化和还原两步,简化了生产工艺,并且不需要高温反应,制得的聚酰亚胺金属化膜表面金属层的附着力也得到提高。 [0039] The disclosed method of the present invention, during the preparation of the metallized polyimide film, the polyimide film by using the activation solution according to the present disclosure, only after activation and reduction of two steps, the production process is simplified , and does not require high temperature reaction, adhesion of the metallized polyimide film surface layer is made of a metal is also improved.

[0040] 下面通过实施例对本发明作进一步的说明。 [0040] The following examples further illustrate the present invention.

[0041] 实施例1 [0041] Example 1

[0042] 本实施例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0042] The present examples serve to illustrate the polyimide film was activated and the disclosure of the present invention, a polyimide film metallization method.

[0043] 采用杜邦公司生产的Kapton-H型,规格为50X50X0. 025mm的聚酰亚胺膜作为样品进行实验。 [0043] The production of DuPont Kapton-H type, specifications for the polyimide film 50X50X0. 025mm experiment as a sample.

[0044] 1、聚酰亚胺膜活化液的配制 [0044] 1, a polyimide film prepared activation solution of

[0045] 将20g硝酸铵(即0. 25mol硝酸铵)溶于750ml去离子水中,然后缓慢加入12g 氢氧化钠(即0. 30mol氢氧化钠),再加入Ig乙二醇(广东省化学试剂工程技术研究开发中心生产),最后在搅拌的条件下缓慢加入9. 2g硝酸镍(即0. 05mol硝酸镍),搅拌均勻, 然后定容至1000ml。 [0045] 20g of ammonium nitrate (ammonium nitrate i.e., 0. 25mol) was dissolved in 750ml deionized water, 12g of sodium hydroxide was then slowly added (i.e., 0. 30mol sodium hydroxide), ethylene glycol was added Ig (Guangdong Chemicals Engineering Research and development Center, Ltd.), and finally under stirring slowly added 9. 2g of nickel nitrate (i.e., 0. 05mol nickel nitrate), stir, and volume to 1000ml. 此时,镍离子与氨的摩尔比1 :5,聚酰亚胺膜活化液的pH值为12.8。 At this time, the molar ratio of ammonia to nickel ions 1: 5, pH of the polyimide film activation solution is 12.8.

[0046] 2、化学改性 [0046] 2, chemically modified

[0047] 在60°C下,将经过除油处理的聚酰亚胺膜浸入所述聚酰亚胺膜活化液中20min。 [0047] at 60 ° C, after degreasing the polyimide film was immersed in the activation solution in the polyimide film 20min. 然后取出,再用去离子水冲洗:3min。 Then removed, rinsed with deionized water: 3min. 得到改性聚酰亚胺膜。 To obtain a modified polyimide film.

[0048] 3、还原 [0048] 3, reducing

[0049] 将0. IOmol 二甲胺基甲硼烷溶于IOOOmL去离子水中,搅拌均勻即得还原溶液。 [0049] A 0. IOmol dimethylamino borane IOOOmL dissolved in deionized water and stir to obtain a reducing solution.

[0050] 在50°C下,将改性聚酰亚胺膜浸没于上述还原溶液中30min。 [0050] at 50 ° C, the modified polyimide film was immersed in the reducing solution 30min. 然后取出,用去离子水冲洗:3min。 Then removed, rinsed with deionized water: 3min. 在聚酰亚胺膜表面形成完整金属层,即得到聚酰亚胺金属化膜Al。 Forming a complete metal layer on the polyimide film surface, i.e., to obtain a polyimide film metal Al.

[0051] 实施例2 [0051] Example 2

[0052] 本实施例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0052] The present examples serve to illustrate the polyimide film was activated and the disclosure of the present invention, a polyimide film metallization method.

[0053] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例1,不同的是: [0053] Preparation of polyimide film of a metal film and a polyimide used in Example 1, except that:

[0054] 1、聚酰亚胺膜活化液的配制 [0054] 1, a polyimide film prepared activation solution of

[0055] 将28g硝酸铵(即0. 35mol硝酸铵)溶于750ml去离子水中,然后缓慢加入16g氢氧化钠(即0. 40mol氢氧化钠),再加入3g乙醇(广东省化学试剂工程技术研究开发中心生产),最后在搅拌的条件下缓慢加入12. Slg硝酸镍(即0. 07mol硝酸镍),搅拌均勻,然后定容至1000ml。 [0055] The ammonium nitrate 28g (i.e., ammonium nitrate 0. 35mol) was dissolved in 750ml deionized water, 16g of sodium hydroxide was then slowly added (i.e., 0. 40mol sodium), in ethanol was added 3g (Guangdong TECHNICAL Chemicals Research and development Center, Ltd.), and finally under stirring slowly added 12. Slg nickel nitrate (i.e., 0. 07mol nickel nitrate), stir, and volume to 1000ml. 此时,镍离子与氨的摩尔比1 :5,测得聚酰亚胺膜活化液的pH值为13。 At this time, the molar ratio of nickel ion to ammonia of 1: 5, the polyimide film was measured activation solution pH of 13.

[0056] 在采用聚酰亚胺膜活化液进行化学改性之前,还包括对聚酰亚胺膜进行除油,具体方法如下: [0056] Before using the polyimide film was chemically modified activated, further comprising a polyimide film is subjected to degreasing, as follows:

[0057] 2、除油 [0057] 2, degreasing

[0058] 将上述聚酰亚胺膜浸没于无水乙醇中,在超声波环境下清洗lOmin,然后用去离子水冲洗:3min,再将冲洗后的聚酰亚胺膜浸没于无机碱性除油液中,在超声波环境下清洗lOmin,最后用去离子水冲洗;3min即可。 [0058] The polyimide film was immersed in absolute ethanol, in an ultrasonic cleaning environment lOmin, then rinsed with deionized water: 3min, the polyimide film after rinsing and then immersed in an inorganic alkaline degreasing solution, washing with ultrasonic lOmin environment, and finally rinsed with deionized water; to 3min.

[0059] 3、化学改性 [0059] 3, chemically modified

[0060] 在50°C下,将经过除油处理的聚酰亚胺膜浸入所述聚酰亚胺膜活化液中20min。 [0060] at 50 ° C, after degreasing the polyimide film was immersed in the activation solution in the polyimide film 20min. 然后取出,再用去离子水冲洗:3min。 Then removed, rinsed with deionized water: 3min. 得到改性聚酰亚胺膜A20。 To obtain a modified polyimide film A20.

[0061] 4、还原 [0061] 4, the reduction

[0062] 还原得到金属层的方法同实施例1。 [0062] The method of reducing the metal layer obtained in Example 1. 在聚酰亚胺膜表面形成完整金属层,得到聚酰亚胺金属化膜A2。 Forming a complete metal layer on the surface of the polyimide film, a polyimide metal film A2.

[0063] 最后,还包括对得到的聚酰亚胺金属化膜A2进行保护,具体方法如下: [0063] Finally, further comprising a metallized polyimide film obtained were protected A2, as follows:

[0064] 5、保护 [0064] 5, protected

[0065] 将聚酰亚胺金属化膜A2浸入保护液(深圳市俄真科技有限公司生产的EZ202铜保护剂)中3min,在100°C下烘30min即可。 [0065] The metallized polyimide film was immersed in the protection liquid A2 (Shenzhen Main Technology Co EZ202 really copper protective agents) in 3min, 30min to bake at 100 ° C.

[0066] 实施例3[0067] 本实施例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0066] Example 3 [0067] The polyimide film according to the present embodiment described activation solution of the present invention disclosed and metalized polyimide film for a method embodiment.

[0068] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例2,不同的是: [0068] Preparation of polyimide film, metallized polyimide film and the method employed in Example 2, except that:

[0069] 1、聚酰亚胺膜活化液的配制 [0069] 1, a polyimide film prepared activation solution of

[0070] 将28. 3g浓度为30%的氨水(NH3的量为0. 5mol)溶于700ml去离子水中,然后缓慢加入5g乙二醇(广东省化学试剂工程技术研究开发中心生产),最后在搅拌的条件下缓慢加入16g硫酸铜(即0. Imol硫酸铜),搅拌均勻,然后定容至1000ml。 [0070] The concentration of 28. 3g of 30% aqueous ammonia (NH3 amount is 0. 5mol) was dissolved in 700ml of deionized water, 5g of ethylene glycol was then slowly added (Chemicals Production Engineering Research and Development Center, Guangdong Province), and finally under stirring slowly added to 16g of copper (i.e. copper sulfate 0. Imol), stir, and volume to 1000ml. 此时,铜离子与氨的摩尔比1 :5,聚酰亚胺膜活化液的pH值为11.3。 At this time, the copper ions to ammonia molar ratio of 1: 5, pH of the polyimide film activation solution is 11.3.

[0071] 在聚酰亚胺膜表面形成完整金属层,得到聚酰亚胺金属化膜A3。 [0071] forming a complete metal layer on the surface of the polyimide film, a polyimide metal film A3.

[0072] 实施例4 [0072] Example 4

[0073] 本实施例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0073] The present examples serve to illustrate the polyimide film was activated and a method of the present invention is disclosed a metallized polyimide film.

[0074] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例3,不同的是:用17g硝酸银(即0. Imol硝酸银)替换硫酸铜。 [0074] Preparation of polyimide film of a metal film and a polyimide used in Example 3, except that: copper sulfate replaced with 17g of silver nitrate (silver nitrate i.e. 0. Imol). 得到改性聚酰亚胺膜A40。 To obtain a modified polyimide film A40.

[0075] 将制备好的改性聚酰亚胺膜A40在300°C热处理40min。 [0075] The modified polyimide film prepared A40 heat treatment at 300 ° C 40min.

[0076] 在聚酰亚胺膜表面形成完整金属层,得到聚酰亚胺金属化膜A4。 [0076] forming a complete metal layer on the surface of the polyimide film, a polyimide film metal A4.

[0077] 对比例1 [0077] Comparative Example 1

[0078] 本对比例用于说明现有技术中的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0078] This comparative example for explaining the polyimide film was activated prior art and the polyimide film metallization method.

[0079] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例3,不同的是:聚酰亚胺膜活化液组成为:三乙醇胺0. lmol/1,硫酸铜0. 02mol/l,氢氧化钠16g,pH为13。 [0079] Preparation of polyimide film of a metal film and a polyimide used in Example 3, except that: a polyimide film activation solution consisting of: triethanolamine 0. lmol / 1, sulfuric acid copper 0. 02mol / l, sodium hydroxide, 16g, pH 13.

[0080] 得到聚酰亚胺金属化膜Dl。 [0080] The metallized polyimide film Dl.

[0081] 对比例2 [0081] Comparative Example 2

[0082] 本对比例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0082] This comparative example illustrates a method for the activation of the polyimide film of the present invention was disclosed and a film metallized polyimide.

[0083] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例3,不同的是:聚酰亚胺膜活化液中不含有乙二醇。 [0083] Preparation of polyimide film and the polyimide film of the metal used in the method described in Example 3, except that: a polyimide film activation solution does not contain ethylene glycol.

[0084] 得到聚酰亚胺金属化膜D2。 [0084] The metallized polyimide film D2.

[0085] 对比例3 [0085] Comparative Example 3

[0086] 本对比例用于说明本发明公开的聚酰亚胺膜活化液以及聚酰亚胺膜金属化的方法。 [0086] This comparative example for explaining the polyimide film was activated and the disclosure of the present invention, a polyimide film metallization method.

[0087] 所采用的聚酰亚胺膜及制备聚酰亚胺金属化膜的方法同实施例3,不同的是:聚酰亚胺膜活化液中含有5. 7g浓度为30%的氨水(即NH3的量为0. Imol), Sg硫酸铜(即0. 05mol硫酸铜),此时,铜离子与氨的摩尔比1 :2。 [0087] Preparation of polyimide film and the polyimide film of the metal used in the method described in Example 3, except that: 5. 7g containing polyimide concentration of 30% aqueous ammonia solution membrane active ( i.e., the amount of NH3 is 0. Imol), Sg copper (i.e. copper sulfate 0. 05mol), in this case, the molar ratio of copper ions and ammonia 1: 2. 测得聚酰亚胺膜活化液的pH值为9. 8。 Polyimide film was measured activation solution pH of 9.8.

[0088] 得到聚酰亚胺金属化膜D3。 [0088] The metallized polyimide film D3.

[0089] 附着力测试 [0089] Adhesion test

[0090] 用划格器在上述聚酰亚胺金属化膜A1-A4及D1-D3的金属层上划100个1毫米X 1 毫米的正方形格。 [0090] designated by the cross-hatch 100 is 1 mm X 1 mm square grid metal on the polyimide film and the metal layer A1-A4 of D1-D3. 用美国3M公司生产的型号为600的透明胶带平整粘结在方格上,不留一丝空隙,然后以最快的速度60°角揭起,观察划痕边缘处是否有金属脱落。 With the American company 3M Model 600 transparent tape adhered to the box flat, without leaving a trace of the gap, then the fastest lift angle of 60 °, if observed at the edges of the scratch off metal. 如没有任何脱落为5B,脱落量在0-5%之间为4B,5-15%之间为3B,15-35%之间为2B,35-65%之间为1B, 65%以上为OB0 As for the no off 5B, the amount of between 0-5% off between 4B, 5-15% of 3B, between 15-35% 2B, 35-65% of 1B, to 65% OB0

[0091] 测试结果见表1。 [0091] The test results are shown in Table 1.

[0092] 表1 [0092] TABLE 1

[0093] [0093]

样品 Al A2 A3 A4 Dl D2 D3 无金属 无金属 无金属附着力 4B 4B 4B 5B 层 层 层 Samples Al A2 A3 A4 Dl D2 D3 metal-metal-metal-layer adhesion layer 4B 4B 4B 5B layer

[0094] 从表1的测试结果可以看出,采用本发明公开的聚酰亚胺膜活化液能在聚酰亚胺膜表明形成完整的金属层,并且金属层与聚酰亚胺膜的附着力良好。 [0094] As can be seen from the test results shown in Table 1, were activated using the polyimide film of the present invention disclosed in the polyimide film can show a complete metal layer and the metal layer and the polyimide film is attached focus on the good. 另一方面,相比于现有技术,由于采用本发明公开的聚酰亚胺膜活化液,在保证金属层附着力的前提下能使制作工艺更简化。 On the other hand, compared to the prior art, since the polyimide film of the present invention disclosed in activation solution, in the production process can ensure the adhesion of the metal layer provided more simplified.

Claims (8)

  1. 1. 一种聚酰亚胺膜活化液,含有金属离子、氨和聚酰亚胺膜润湿剂,所述聚酰亚胺膜活化液的PH为9-14,金属离子与氨的摩尔比1 : 4-8,所述聚酰亚胺膜活化液中金属离子浓度为0. 03-0. 20mol/l,所述氨的浓度为0. 12-1. OOmol/Ι,所述聚酰亚胺膜活化液中的金属离子选自Cu2+、Ni2+、Ag+、Co2+。 1. A polyimide film activation solution, containing metal ions, ammonia and a wetting agent, a polyimide film, PH said polyimide film activation solution is 9-14, the molar ratio of metal ion to ammonia 1: 4-8, the polyimide film was activated metal ion concentration is 0. 03-0 20mol / l, the ammonia concentration is 0. 12-1 OOmol / Ι, said polyamide. imine membrane active metal ion solution is selected from Cu2 +, Ni2 +, Ag +, Co2 +.
  2. 2.根据权利要求1所述的聚酰亚胺膜活化液,其特征在于:聚酰亚胺膜润湿剂浓度为0.5-8g/l。 The polyimide film activation solution according to claim 1, wherein: a polyimide film of a wetting agent concentration 0.5-8g / l.
  3. 3.根据权利要求1所述的聚酰亚胺膜活化液,其特征在于,所述聚酰亚胺膜润湿剂为甲酰胼、乙二醇、乙醇、三乙醇胺、甘油、山梨醇、丙二醇、聚乙二醇中的一种或几种。 The polyimide film according to claim activation solution according to claim 1, wherein said polyimide film is a carboxamido corpus wetting agent, ethylene glycol, ethanol, triethanolamine, glycerine, sorbitol, propylene glycol, polyethylene glycol, one or more.
  4. 4. 一种聚酰亚胺膜金属化的方法,包括:将聚酰亚胺膜与权利要求1所述的聚酰亚胺膜活化液接触;将与聚酰亚胺膜活化液接触后的聚酰亚胺膜进行热处理或者还原处理,得到表面金属化的聚酰亚胺膜。 After contact with the polyimide film was activated; activation solution polyimide film in contact with the polyimide film of claim 1 and claim: 4. A metallized polyimide film comprising the polyimide film is subjected to heat treatment or reduction treatment to obtain a surface metallized polyimide film.
  5. 5.根据权利要求4所述的方法,其特征在于,所述热处理为将与聚酰亚胺膜活化液接触后的聚酰亚胺膜在250-320°C下保持20-60min ;所述还原处理为将改性聚酰亚胺膜与还原溶液接触,所述还原溶液中含有还原物质。 The method according to claim 4, characterized in that the heat treatment is to keep 20-60min polyimide film after the contact with the polyimide film was activated at 250-320 ° C; the the reduction treatment is modified polyimide film contacting with the reducing solution, the reducing solution contains a reducing substance.
  6. 6.根据权利要求5所述的方法,其特征在于,所述还原物质含有硼烷、磷酸二氢钠、乙醛酸中的一种或几种;还原物质的浓度为0. 05-1. OOmol/1。 6. The method according to claim 5, wherein said reducing substance comprising a borane, sodium dihydrogen phosphate, one or more of glyoxylic acid; reducing substance concentration of 0. 05-1. OOmol / 1.
  7. 7.根据权利要求4、5或6中所述的方法,其特征在于,所述聚酰亚胺膜与聚酰亚胺膜活化液接触的方法为:在30-80°C下,将聚酰亚胺膜浸入所述聚酰亚胺膜活化液中10-180min。 The method according to claim 5 or claim 6, characterized in that the method of the polyimide film is a polyimide film in contact with the activation solution is: at 30-80 ° C, poly polyimide film of the polyimide film was immersed in the activation solution 10-180min.
  8. 8.根据权利要求5或6所述的方法,其特征在于,所述改性聚酰亚胺膜与还原溶液接触的方法为:在20-100°C下,将聚酰亚胺膜浸入所述还原溶液中10-180min。 8. The method of claim 5 or claim 6, wherein the modified polyimide film and method for reducing contact with a solution of: at 20-100 ° C, the polyimide film was immersed in the said reducing solution 10-180min.
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US3736170A (en) 1971-06-28 1973-05-29 Ibm Process for improved adhesion of electroless copper to a polyimide surface
EP0400349A1 (en) 1989-05-04 1990-12-05 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
CN1858301A (en) 2006-06-08 2006-11-08 上海交通大学 Method for chemical plating polyimide film surface

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3736170A (en) 1971-06-28 1973-05-29 Ibm Process for improved adhesion of electroless copper to a polyimide surface
EP0400349A1 (en) 1989-05-04 1990-12-05 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
CN1858301A (en) 2006-06-08 2006-11-08 上海交通大学 Method for chemical plating polyimide film surface

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