TWI821550B - Manufacturing method of polyimide composite film for flexible metal foil substrate - Google Patents
Manufacturing method of polyimide composite film for flexible metal foil substrate Download PDFInfo
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- TWI821550B TWI821550B TW109110527A TW109110527A TWI821550B TW I821550 B TWI821550 B TW I821550B TW 109110527 A TW109110527 A TW 109110527A TW 109110527 A TW109110527 A TW 109110527A TW I821550 B TWI821550 B TW I821550B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 94
- 239000004642 Polyimide Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000011888 foil Substances 0.000 title claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 66
- 239000011737 fluorine Substances 0.000 claims abstract description 66
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 239000006185 dispersion Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims abstract description 19
- 229920002647 polyamide Polymers 0.000 claims abstract description 19
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- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 13
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- 239000010410 layer Substances 0.000 description 19
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- 238000002156 mixing Methods 0.000 description 6
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Abstract
本發明係指一種用於軟性覆金屬箔基板之聚醯亞胺複合膜製造方法,其包括下列步驟:提供一聚醯胺酸溶液;提供一氟素高分子粒子,將其與分散劑、與有機溶液混合,以製備一氟素高分子粒子分散液;將聚醯胺酸溶液製成膠態聚醯亞胺膜;將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜上,而後進行烘烤,以形成聚醯亞胺複合膜。 The invention refers to a method for manufacturing a polyimide composite film for a flexible metal foil substrate, which includes the following steps: providing a polyimide solution; providing a fluorine polymer particle, and combining it with a dispersant and The organic solution is mixed to prepare a fluorine polymer particle dispersion; the polyamide acid solution is made into a colloidal polyimide film; the fluorine polymer particle dispersion is coated on the colloidal polyimide film , and then baked to form a polyimide composite film.
Description
本發明係關於一種用於軟性覆金屬箔基板之聚醯亞胺複合膜製造方法,其係將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜上,再進行烘烤成膜,以達到提高聚醯亞胺複合膜生產良率之效果。 The invention relates to a method for manufacturing a polyimide composite film for a flexible metal foil substrate. The method involves coating a fluorine polymer particle dispersion on a colloidal polyimide film and then baking it to form a film. , in order to achieve the effect of improving the production yield of polyimide composite film.
可彎折之軟性印刷電路板已大幅應用於日常生活中各式電子產品,例如:行動電話、平板裝置、筆記型電腦等商品之彎折部分。此種軟性印刷電路板與其覆蓋基材必須考慮材料的電氣性、耐熱性、耐化學性及尺寸安定性,因此通常使用聚醯亞胺為軟性印刷電路板及覆蓋層之基材。 Flexible printed circuit boards have been widely used in various electronic products in daily life, such as the bending parts of mobile phones, tablet devices, notebook computers and other products. This kind of flexible printed circuit board and its covering base material must consider the electrical properties, heat resistance, chemical resistance and dimensional stability of the material. Therefore, polyimide is usually used as the base material of the flexible printed circuit board and the covering layer.
近年來伴隨著5G高頻傳輸應用的到來,高傳輸頻率與高資料傳輸量,傳輸的過程中可能發生訊號的損失。為了有效的降低訊號損失,聚醯亞胺膜的介電常數(dielectric constant,Dk)與介電損耗(dielectric loss,Df)的降低則格外的重要。藉由分子結構設計降低聚醯亞胺膜之Dk及Df,然而,目前的極限,於10GHz下Dk仍高於3.0、Df高於0.004。 In recent years, with the arrival of 5G high-frequency transmission applications, high transmission frequency and high data transmission volume, signal loss may occur during the transmission process. In order to effectively reduce signal loss, it is particularly important to reduce the dielectric constant (Dk) and dielectric loss (Df) of the polyimide film. The Dk and Df of the polyimide film can be reduced through molecular structure design. However, the current limit is that Dk is still higher than 3.0 and Df is higher than 0.004 at 10GHz.
各式高分子材料中,氟素高分子是已知具有較低的Dk與Df材料,於10GHz下Dk<2.5及Df<0.001,因此相關開發者嘗試使用於覆金屬箔基板材料之中。例如將玻璃纖維布浛浸氟素高分子並與銅箔壓合製作成基板;又例如,將氟素高分子塗佈在聚醯亞胺膜上並與銅箔壓合。 Among various polymer materials, fluorine polymers are known to have lower Dk and Df materials, with Dk<2.5 and Df<0.001 at 10GHz. Therefore, relevant developers have tried to use them in metal foil-clad substrate materials. For example, glass fiber cloth is impregnated with fluorine polymer and pressed with copper foil to make a substrate; another example is that fluorine polymer is coated on a polyimide film and pressed with copper foil.
一種用於軟性覆金屬箔基板之聚醯亞胺複合膜製造方法,其係將氟素高分子粒子分散液塗佈於事先製備好的聚醯亞胺膜表面後將其乾燥,再使其於高溫烘箱中熔融而成膜。然而,在連續捲對捲的塗佈生產流程中,乾燥後的氟素高分子粒子與聚醯亞胺膜之表面能差異過大,兩者介面之親和性非常差,使氟素高分子粒子於聚醯亞胺膜表層容易發生脫落,造成膜面缺陷與產線汙染等問題,因而限制住該複合膜的使用與生產。且,氟素高分子塗佈於聚醯亞胺膜面後進入高溫烘烤,由於氟素高分子熔融時發生收縮,使複合膜發生捲曲或波浪狀之不平整影響良率。此外,上述複合膜之作法為先完成聚醯亞胺膜基材之製作後再行塗佈氟素高分子粒子分散液,如此需要兩道以上之塗佈製程與高溫製程,對於成本與良率上有相當程度的影響。 A method for manufacturing a polyimide composite film for a flexible metal foil substrate. The method involves coating a fluorine polymer particle dispersion on the surface of a previously prepared polyimide film, drying it, and then drying it. It is melted in a high-temperature oven to form a film. However, in the continuous roll-to-roll coating production process, the surface energy difference between the dried fluoropolymer particles and the polyimide film is too large, and the affinity of the interface between the two is very poor, causing the fluoropolymer particles to The surface layer of the polyimide membrane is prone to peeling off, causing problems such as membrane surface defects and production line pollution, thus limiting the use and production of the composite membrane. Moreover, the fluorine polymer is coated on the polyimide film surface and then baked at high temperature. Since the fluorine polymer shrinks when melted, the composite film will be curled or wavy, which will affect the yield. In addition, the above-mentioned composite film method is to first complete the production of the polyimide film base material and then apply the fluorine polymer particle dispersion. This requires more than two coating processes and high-temperature processes, which has a negative impact on cost and yield. have a considerable impact.
本發明中一種用於軟性覆金屬箔基板之聚醯亞胺膜製造方法,其特徵在於包括下列步驟:提供一聚醯胺酸溶液;提供一氟素高分子粒子,將其與分散劑、與有機溶液混合,以製備一氟素高分子粒子分散液;將聚醯胺酸溶液製成膠態聚醯亞胺膜;及將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜上,而後進行烘烤,以形成聚醯亞胺複合膜。 The present invention is a method for manufacturing a polyimide film for a flexible metal foil substrate, which is characterized by including the following steps: providing a polyimide solution; providing a fluorine polymer particle, and combining it with a dispersant; Mixing organic solutions to prepare a fluorine polymer particle dispersion; making the polyamide acid solution into a colloidal polyimide film; and coating the fluorine polymer particle dispersion on the colloidal polyimide film on the film, and then baked to form a polyimide composite film.
因此,本發明具有如下之功效:1.提高生產過程中,氟素高分子粒子層與膠體聚醯亞胺膜之接著性,進而防止生產中掉粉造成的膜面缺陷與產線汙染;2.可直接在聚醯亞胺膜生產過程中完成單面或雙面複合層塗佈,可縮短與簡化該複合膜之製造流程並避免捲曲發生;3.本發明可提升軟性覆金屬箔基板之中金屬箔與複合膜的接著力。 Therefore, the present invention has the following effects: 1. Improve the adhesion between the fluorine polymer particle layer and the colloidal polyimide film during the production process, thereby preventing film surface defects and production line pollution caused by powder falling off during production; 2. . Single-sided or double-sided composite layer coating can be completed directly during the polyimide film production process, which can shorten and simplify the manufacturing process of the composite film and avoid curling; 3. The present invention can improve the performance of flexible metal foil-clad substrates The bonding strength between metal foil and composite film.
S1:提供一聚醯胺酸溶液 S1: Provide a polyamide solution
S2:製備一氟素高分子粒子分散液 S2: Preparation of monofluoropolymer particle dispersion
S3:將聚醯胺酸溶液製成膠態聚醯亞胺膜 S3: Make the polyamide acid solution into a colloidal polyimide membrane
S4:將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜之雙面上 S4: Coat the fluorine polymer particle dispersion on both sides of the colloidal polyimide film
S5:烘烤形成聚醯亞胺複合膜 S5: Bake to form polyimide composite film
10:氟素高分子粒子分散液 10: Fluorine polymer particle dispersion
12:膠態聚醯亞胺膜 12: Colloidal polyimide membrane
14:氟素高分子層 14: Fluorine polymer layer
16:聚醯亞胺膜 16:Polyimide membrane
第1圖為本發明用於軟性覆金屬箔基板之聚醯亞胺複合膜製造方法之流程圖。 Figure 1 is a flow chart of the manufacturing method of the polyimide composite film for flexible metal foil-clad substrates according to the present invention.
第2圖為本發明之第一示意圖。 Figure 2 is a first schematic diagram of the present invention.
第3圖為本發明之第二示意圖。 Figure 3 is a second schematic diagram of the present invention.
請參閱第一圖至第三圖示,本發明用於軟性覆金屬箔基板之聚醯亞胺複合膜製造方法,其包括下列步驟:提供一聚醯胺酸溶液(S1),其係由二胺及二酸酐混合與反應而得;提供一氟素高分子粒子,將其與分散劑、與有機溶液混合,以製備一氟素高分子粒子分散液10(S2);將聚醯胺酸溶液製成膠態聚醯亞胺膜12(S3);及將氟素高分子粒子分散液10塗佈於膠態聚醯亞胺膜12之雙面上(S4),而後進行烘烤,使氟素高分子粒子分散液10及膠態聚醯亞胺膜12分別形成氟素高分子層14及聚醯亞胺膜16,以形成一聚醯亞胺複合膜(S5)。
Please refer to the first to third figures. The manufacturing method of the polyimide composite film for flexible metal foil-clad substrates of the present invention includes the following steps: providing a polyimide solution (S1), which is composed of two Obtained by mixing and reacting amine and dianhydride; providing monofluoropolymer particles, mixing them with a dispersant and an organic solution to prepare a monofluoropolymer particle dispersion 10 (S2); adding the polyamide solution The
步驟S1:聚醯胺酸溶液製備Step S1: Preparation of polyamide solution
提供一種或一種以上二胺及一種或一種以上二酸酐單體進行混合與反應,以聚合成一聚醯胺酸溶液。 One or more diamines and one or more dianhydride monomers are provided for mixing and reaction to polymerize into a polyamide solution.
其中,二胺單體可以為:4,4'-二胺基二苯醚(4,4'-ODA)3,4'-二胺基二苯醚(3,4'-ODA)、間苯二胺(MPD)、對苯二胺(PPD)、2,2'-二(三氟甲基)二氨基聯苯(TFMB)、4,4'-二胺基二苯-2,2-丙烷、4,4'-二胺基二苯甲烷、4,4'-二氨基二苯胺、聯苯胺、4,4'-二胺基二苯硫醚、4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、4,4'-二氨基 -2,2'-二甲基-1,1'-聯苯、4,4'-二氨基-3,3'-1,1'-二甲基联苯、1,5-二胺基萘、3,3'-二甲氧基聯苯胺、1,4-雙-(p-胺基苯氧基)-苯、1,3-雙-(p-胺基苯氧基)-苯、或它們的任何混合物。 Among them, the diamine monomer can be: 4,4'-diaminodiphenyl ether (4,4' - ODA), 3,4'-diaminodiphenyl ether (3,4' - ODA), m-phenylene ether Diamine (MPD), p-phenylenediamine (PPD), 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFMB), 4,4'-diaminodiphenyl-2,2-propane , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Turine, 3,3'-diaminodiphenyl styrene, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diamino-3, 3'-1,1'-dimethylbiphenyl, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis-(p-aminophenoxy) -Benzene, 1,3-bis-(p-aminophenoxy)-benzene, or any mixture thereof.
其中,二酸酐單體可以為:均苯四酸二酐(PMDA)、2,3,6,7-萘四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、1,2,5,6-萘四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、2,2-雙-(3,4-二羧基苯基)-丙烷二酐、雙-(3,4-二羧基苯基)-碸二酐、雙-(3,4-二羧基苯基)-醚二酐、2,2-雙-(2,3-二羧基苯基)-丙烷二酐、1,1-雙-(2,3-二羧基苯基)-乙烷二酐、1,1-雙-(3,4-二羧基苯基)-乙烷二酐、雙-(2,3-二羧基苯基)-甲烷二酐、雙-(3,4-二羧基苯基)-甲烷二酐、3,4,3',4'-二苯甲酮四羧酸二酐、或它們的任何混合物。 Among them, the dianhydride monomer can be: pyromellitic dianhydride (PMDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis-(3,4-dicarboxyphenyl )-propane dianhydride, bis-(3,4-dicarboxyphenyl)-terebic dianhydride, bis-(3,4-dicarboxyphenyl)-ether dianhydride, 2,2-bis-(2,3 -Dicarboxyphenyl)-propane dianhydride, 1,1-bis-(2,3-dicarboxyphenyl)-ethane dianhydride, 1,1-bis-(3,4-dicarboxyphenyl)- Ethane dianhydride, bis-(2,3-dicarboxyphenyl)-methane dianhydride, bis-(3,4-dicarboxyphenyl)-methane dianhydride, 3,4,3',4'-di benzophenone tetracarboxylic dianhydride, or any mixture thereof.
步驟S2:氟素高分子粒子分散液製備Step S2: Preparation of fluorine polymer particle dispersion
本發明可使用之氟素高分子包括:聚氯三氟乙烯(PCTFE)、氟化乙烯丙烯共聚物(FEP)、聚氟乙烯(PVF)、聚偏二氟乙烯(PVDF)、乙烯三氟氯乙烯共聚物(ECTFE)、四氟乙烯全氟醚的共聚物(PFA)、乙烯四氟乙烯共聚物(ETFE)之中之1種或2種以上之組成。氟素高分子為顆粒狀態分散於有機溶劑之中,其平均粒徑為1~20微米,優選為1~10微米,粒徑過小則不易分散,粒徑過大則易產生膜面不均勻之現象。該氟素高分子之熔點應介於260℃~350℃,以使該粒子同時於聚醯亞胺膠態膜製造過程中烘烤同時熔融且成膜。也確保後續於軟性基板高溫製程之可靠性。 Fluorine polymers that can be used in the present invention include: polychlorotrifluoroethylene (PCTFE), fluorinated ethylene propylene copolymer (FEP), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene trifluorochlorine It is composed of one or more of ethylene copolymer (ECTFE), tetrafluoroethylene perfluoroether copolymer (PFA), and ethylene tetrafluoroethylene copolymer (ETFE). Fluorine polymers are in the form of particles dispersed in organic solvents. The average particle size is 1 to 20 microns, preferably 1 to 10 microns. If the particle size is too small, it will be difficult to disperse, and if the particle size is too large, the film surface will be uneven. . The melting point of the fluorine polymer should be between 260°C and 350°C, so that the particles can be melted and formed into a film while being baked during the manufacturing process of the polyimide colloidal film. It also ensures the reliability of subsequent high-temperature processes for flexible substrates.
氟素高分子粒子分散液之組成包含:氟素高分子粒子占總分散
液之10~60重量%,優選為30~50重量%,以確保塗佈乾燥後粒子之間之結構緊密;分散劑2~7重量%,優選為2~5%,添加量過低無法使氟素高分子粒子均勻分散,過高則影響氟素層之特性;此外,亦可另額外添加聚醯胺酸溶液以增加氟素層之結構穩定性,其添加量應小於分散液總固體含量之20重量%,優選為10重量%以下,過高之添加量則使氟素層之介電特性降低。其配置方式為:將氟素高分子粒子加入分散劑與溶劑之混和溶劑之中,以均質機分散2小時。又一例,在完成上述分散液後,再加入20%聚醯胺酸溶液以均質機混合。
The composition of the fluorine polymer particle dispersion includes: fluorine polymer particles account for the
步驟S3:膠態聚醯亞胺膜基材之製備Step S3: Preparation of colloidal polyimide film substrate
在聚醯胺酸溶劑中混和脫水劑例如醋酸酐,和催化劑例如三乙胺、吡啶、異喹啉或甲基吡啶等,塗佈於支撐物之上,於50~150℃之溫度範圍烘烤使其轉化得膠態膜。其中膠態聚醯亞胺膜之溶劑含量控制係利用烘箱之烘烤溫度曲線調整,其烘烤溫度範圍為50~150℃。膠態聚醯亞胺膜之溶劑含量介於20~60重量%,高於60重量%溶劑含量於高溫段造成膜面缺陷,低於20重量%則無法與氟素高分子粒子有良好親和性。 Mix a dehydrating agent such as acetic anhydride and a catalyst such as triethylamine, pyridine, isoquinoline or picoline in a polyamide solvent, apply it on the support, and bake it at a temperature ranging from 50 to 150°C. Transform it into a colloidal film. The solvent content of the colloidal polyimide film is controlled by adjusting the baking temperature curve of the oven, and the baking temperature range is 50~150°C. The solvent content of colloidal polyimide membranes ranges from 20 to 60% by weight. A solvent content above 60% by weight will cause defects on the film surface at high temperatures. A solvent content below 20% by weight will not have good affinity with the fluorine polymer particles. .
步驟S4:氟素高分子粒子分散液塗佈Step S4: Coating with fluorine polymer particle dispersion
氟素高分子粒子分散液可塗佈於膠態聚醯亞胺膜之單面或雙面。塗佈的方法無限定,可利用狹縫流延法(slot die)、微凹版轉印法(micro gravure)、刮刀塗佈法(comma coating)、滾輪式塗佈法(roll coating)。 The fluorine polymer particle dispersion can be coated on one or both sides of the colloidal polyimide film. The coating method is not limited, and slot die, micro gravure, comma coating, and roll coating can be used.
步驟S5:烘烤形成聚醯亞胺複合膜Step S5: Bake to form polyimide composite film
氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜後進入高溫段烘烤,高溫烘箱溫度介於150~550℃之間,其最高溫度優選為350~550℃,以確保聚醯亞胺膜閉環完全及氟素高分子粒子熔融成膜,烘烤同時進行TD方向延伸,避免該收縮現象造成膜面不平整現象。 After the fluorine polymer particle dispersion is coated on the colloidal polyimide film, it is baked in the high-temperature section. The temperature of the high-temperature oven is between 150~550°C, and the maximum temperature is preferably 350~550°C to ensure that the polyimide film is The imine film is completely closed-looped and the fluorine polymer particles are melted to form a film. It is baked while extending in the TD direction to avoid the shrinkage phenomenon causing uneven film surface.
為了驗證本發明之功效,於200℃以下烘烤段取出氟素高分子粒子層已乾燥但尚未熔融成膜之半成品聚醯亞胺複合膜,依照ASTM D3359之規範進行百格接著力測試。 In order to verify the efficacy of the present invention, the semi-finished polyimide composite film whose fluorine polymer particle layer has been dried but has not yet been melted into a film was taken out from the baking section below 200°C, and a hundred-grid adhesion test was conducted in accordance with ASTM D3359 specifications.
可撓性金屬箔基板製作Flexible metal foil substrate production
本發明之可撓性金屬箔基板係藉由上述聚醯亞胺複合膜與金屬箔利用加熱金屬滾壓機或雙帶熱壓機進行連續壓合而成,亦可使用真空平板熱壓機以利評估聚醯亞胺複合膜實驗結果。其中金屬箔成分無特別限定,包含銅、鎳、鋁等金屬或合金,常用的為電解銅箔或壓延銅箔,厚度亦無特別限定。 The flexible metal foil substrate of the present invention is formed by continuously pressing the above-mentioned polyimide composite film and metal foil using a heated metal rolling machine or a double-belt hot press. A vacuum flat hot press can also be used. Evaluate the experimental results of polyimide composite membranes. The composition of the metal foil is not particularly limited, including copper, nickel, aluminum and other metals or alloys. Electrolytic copper foil or rolled copper foil is commonly used, and the thickness is not particularly limited.
實施例1Example 1
步驟S1:聚醯胺酸溶液製備Step S1: Preparation of polyamide solution
將10Kg(50mole%)之4,4'-二胺基二苯醚與5.4Kg(50mole%)之對苯二胺溶解於157Kg二甲基乙醯胺(DMAc)中,再取10.9Kg(50mole%)之均苯四甲酸二酸酐與約14.7Kg(50mole%)之3,3',4,4'-聯苯四羧酸二酐加入進行反應,獲得20%聚醯胺酸溶液。 Dissolve 10Kg (50mole%) of 4,4'-diaminodiphenyl ether and 5.4Kg (50mole%) of p-phenylenediamine in 157Kg of dimethylacetamide (DMAc), then take 10.9Kg (50mole) %) of pyromellitic dianhydride and about 14.7Kg (50 mole%) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were added for reaction to obtain a 20% polyamic acid solution.
步驟S2:氟素高分子粒子分散液製備Step S2: Preparation of fluorine polymer particle dispersion
將30Kg二甲基乙醯胺溶劑與0.4Kg分散劑混合後,20Kg之PFA粒子加入上述溶液之中,再以均質機5000rpm攪拌2小時,為40重量%之氟素高分子粒子分散液。 After mixing 30Kg of dimethylacetamide solvent and 0.4Kg of dispersant, 20Kg of PFA particles were added to the above solution, and then stirred with a homogenizer at 5000rpm for 2 hours to obtain a 40% by weight fluorine polymer particle dispersion.
步驟S3:膠態聚醯亞胺膜基材之製備Step S3: Preparation of colloidal polyimide film substrate
將聚醯胺酸溶液混合脫水劑及催化劑,添加比例為聚醯胺酸:脫水劑:催化劑之莫耳比為1:2:1塗佈於鋼板上,並進入烘箱烘烤,再於鋼板上剝離,得到溶劑含量為60%。之膠態聚醯亞胺膜。 Mix the polyamic acid solution with the dehydrating agent and the catalyst. The molar ratio of polyamic acid: dehydrating agent: catalyst is 1:2:1. Apply it on the steel plate, bake it in the oven, and then apply it on the steel plate. Peel off to obtain a solvent content of 60%. Colloidal polyimide film.
步驟S4:氟素高分子粒子分散液塗佈Step S4: Coating with fluorine polymer particle dispersion
將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜之雙面。 The fluorine polymer particle dispersion is coated on both sides of the colloidal polyimide film.
步驟S5:烘烤形成聚醯亞胺複合膜Step S5: Bake to form polyimide composite film
進入高溫烘箱段烘烤,高溫烘箱溫度介於150~550℃之間,得到雙面覆氟素高分子層之聚醯亞胺複合膜,厚度為氟素高分子層/聚醯亞胺膜/氟素高分子層=12微米/50微米/微米,並進行外觀評價。 Enter the high-temperature oven section for baking. The temperature of the high-temperature oven is between 150 and 550°C to obtain a polyimide composite film covered with a fluorine polymer layer on both sides. The thickness is fluorine polymer layer/polyimide film/ Fluorine polymer layer = 12 microns/50 microns/microns, and conduct appearance evaluation.
烘烤其間於200℃以下烘烤段取得氟素高分子粒子層已乾燥但尚未熔融成膜之半成品聚醯亞胺複合膜,進行百格測試。 During the baking process, the semi-finished polyimide composite film whose fluorine polymer particle layer has been dried but has not yet been melted into a film is obtained in the baking section below 200°C, and a hundred-grid test is carried out.
軟性覆銅基板製作Soft copper-clad substrate production
取大小為20cm×30cm之上述聚醯亞胺複合膜,與銅箔(三井金屬TQ-M4-VSP 12um,Rz:0.6微米)使用真空平板熱壓機進行壓合。壓合條件為由室溫每分鐘5℃昇至340℃,並於340℃恆溫10min,壓力為30Kgf/cm2,完成後進行銅箔接著力測試。 Take the above-mentioned polyimide composite film with a size of 20cm×30cm and laminate it with copper foil (Mitsui Metal TQ-M4-VSP 12um, Rz: 0.6 micron) using a vacuum flat plate hot press. The lamination conditions are as follows: temperature rise from room temperature to 340°C at 5°C per minute, and constant temperature at 340°C for 10 minutes. The pressure is 30Kgf/cm 2 . After completion, the copper foil adhesion strength test is performed.
膠態聚醯亞胺膜溶劑含量測試Solvent content test of colloidal polyimide membrane
膠態膜溶劑含量=(膠態膜重量-乾膜重量)×100/膠態膜重量 Colloidal film solvent content = (colloidal film weight - dry film weight) × 100/colloidal film weight
乾膜重量為將膠態聚醯亞胺膜於200℃烘箱烘烤12分鐘後之重量。 The dry film weight is the weight of the colloidal polyimide film after baking it in an oven at 200°C for 12 minutes.
百格測試Hundred grid test
依照ASTM D3359將百格測試結果分為5B:無脫落;4B:小於5%脫落;3B:5~15%脫落;2B:15~35%脫落;1B:35~65%脫落;0B:高於65%脫落。 According to ASTM D3359, the hundred-grid test results are divided into 5B: no shedding; 4B: less than 5% shedding; 3B: 5~15% shedding; 2B: 15~35% shedding; 1B: 35~65% shedding; 0B: higher than 65% fell off.
手觸測試Hand touch test
以手指直接按壓接觸半成品聚醯亞胺複合膜之氟素高分子層,觀察是否有剝落、掉粉等現象發生。 Use your fingers to directly press and contact the fluorine polymer layer of the semi-finished polyimide composite film to observe whether there is peeling, powder loss, etc.
外觀評價Appearance evaluation
以目視確認聚醯亞胺複合膜20cm×30cm的面積中,是否有因氟素層剝落造成之外觀缺陷,分為A:無缺陷;B:小於3處;C:大於3處。 Visually confirm whether there are any appearance defects caused by peeling of the fluorine layer in the area of 20cm×30cm of the polyimide composite film. It is divided into A: no defects; B: less than 3 defects; C: more than 3 defects.
銅箔接著力測試Copper foil adhesion test
測試方法依照IPC-TM-650 2.4.9之標準,測試銅箔與聚醯亞胺複合膜之剝離強度。 The test method is in accordance with the standard of IPC-TM-650 2.4.9 to test the peel strength of the copper foil and polyimide composite film.
實施例2Example 2
重複實施例1之步驟,惟步驟S3控制烘烤溫度,得膠態聚醯亞胺膜溶劑含量為30%。 Repeat the steps of Example 1, but control the baking temperature in step S3 to obtain a colloidal polyimide film with a solvent content of 30%.
實施例3Example 3
重複實施例1之步驟,惟步驟S3控制烘烤溫度,得膠態聚醯亞胺膜溶劑含量為20%。 Repeat the steps of Example 1, but control the baking temperature in step S3 to obtain a colloidal polyimide film with a solvent content of 20%.
實施例4Example 4
重複實施例2之步驟,惟步驟S2製作之氟素高分子粒子分散液中添加相對於總固體組成物之20重量%聚醯胺酸,如步驟B。 Repeat the steps of Example 2, except that 20% by weight of polyamide relative to the total solid composition is added to the fluorine polymer particle dispersion produced in step S2, as in step B.
步驟B 氟素高分子粒子分散液製備Step B: Preparation of fluorine polymer particle dispersion
將17.5Kg二甲基乙醯胺溶劑與0.4Kg分散劑混合後,加入25Kg步驟S1製備之聚醯胺酸溶液及20Kg之PFA粒子加入上述溶液之中,再以均質機5000rpm攪拌2小時,為40重量%之氟素高分子粒子分散液。 After mixing 17.5Kg of dimethylacetamide solvent and 0.4Kg of dispersant, add 25Kg of the polyamide solution prepared in step S1 and 20Kg of PFA particles into the above solution, and then stir with a homogenizer at 5000rpm for 2 hours, as 40% by weight fluorine polymer particle dispersion.
比較例1Comparative example 1
重複實施例1之步驟,惟步驟S3控制烘烤溫度,得膠態聚醯亞胺膜溶劑含量為70%。 Repeat the steps of Example 1, but control the baking temperature in step S3 to obtain a colloidal polyimide film with a solvent content of 70%.
比較例2Comparative example 2
重複實施例1之步驟S1、S2,接續進行步驟C、D與E, Repeat steps S1 and S2 of Example 1, and continue with steps C, D and E.
步驟C.聚醯亞胺膜基材之製備Step C. Preparation of polyimide film substrate
將聚醯胺酸溶液混合脫水劑及催化劑,添加比例為聚醯胺酸:脫水劑:催化劑之莫耳比為1:2:1塗佈於鋼板上,並進入烘箱烘烤後於鋼板上剝離,再進入高溫段烘箱烘烤,即得到反應、烘乾皆完全之聚醯亞胺膜作為基材。 Mix the polyamic acid solution with a dehydrating agent and a catalyst in a molar ratio of polyamic acid:dehydrating agent:catalyst of 1:2:1, apply it on the steel plate, and bake it in an oven before peeling off the steel plate. , and then enter the high-temperature oven for baking, and then a polyimide film with complete reaction and drying is obtained as the base material.
步驟D.氟素高分子粒子分散液塗佈Step D. Fluorine polymer particle dispersion coating
將氟素高分子粒子分散液塗佈於步驟C製備之聚醯亞胺膜之雙面。 The fluorine polymer particle dispersion is coated on both sides of the polyimide film prepared in step C.
步驟E:烘烤形成聚醯亞胺複合膜Step E: Baking to form polyimide composite film
進入烘箱烘烤,高溫烘箱溫度介於150~550℃之間,得到雙面覆氟素高分子層之聚醯亞胺複合膜,厚度為氟素高分子層/聚醯亞胺膜/氟素高分子層=12微米/50微米/12微米,並進行外觀評價。 Enter the oven for baking. The high-temperature oven temperature is between 150 and 550°C to obtain a polyimide composite film covered with a fluorine polymer layer on both sides. The thickness is fluorine polymer layer/polyimide film/fluorine. Polymer layer = 12 microns/50 microns/12 microns, and conduct appearance evaluation.
烘烤其間於200℃以下烘烤段取得氟素高分子粒子層已乾燥但尚未熔融成膜之半成品聚醯亞胺複合膜,進行百格測試、手觸測試。 During the baking process, the semi-finished polyimide composite film whose fluorine polymer particle layer has been dried but has not yet been melted into a film is obtained in the baking section below 200°C, and is subjected to a hundred grid test and a hand touch test.
比較例3Comparative example 3
重複實比較2之步驟,惟步驟S2製作之氟素高分子粒子分散液中添加相對於總固體組成物之20重量%之聚醯胺酸,如步驟B Repeat the steps of comparison 2, except that 20% by weight of polyamide relative to the total solid composition is added to the fluorine polymer particle dispersion produced in step S2, as in step B.
實施例1~3與比較例2進行比較。比較半成品,實施例中氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜,比塗佈於乾膜之上,具有更加的接著性,且直接觸摸不掉粉。完成步驟D後,實施例1~3之外觀明顯優於比較例2。 Examples 1 to 3 are compared with Comparative Example 2. Comparing the semi-finished products, in the example, the fluorine polymer particle dispersion is coated on the colloidal polyimide film, which has better adhesion than coating on the dry film, and does not fall off when touched directly. After completing step D, the appearance of Examples 1 to 3 is obviously better than that of Comparative Example 2.
實施例1~3與比較例1進行比較,實施例中氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜對於氟素塗佈層的接著性有明顯幫助,但比較例1中,當膠態聚醯亞胺膜的溶劑含量高於70%,則出現膜面龜裂的情況。 Comparing Examples 1 to 3 with Comparative Example 1, in the Examples, coating the fluorine polymer particle dispersion on the colloidal polyimide film significantly helps the adhesion of the fluorine coating layer, but in Comparative Example 1 , when the solvent content of the colloidal polyimide film is higher than 70%, cracks on the film surface will occur.
實施例2、實施例4與比較例3進行比較。比較半成品,添加聚醯胺酸溶液作為氟素粒子之間的黏著劑塗佈於膠態膜之上對接著性有明顯提升;比較例3塗佈於乾膜之上雖有提升但百格測試僅提升至B1。 Example 2, Example 4 and Comparative Example 3 are compared. Comparing the semi-finished products, adding a polyamide solution as an adhesive between the fluorine particles and coating it on the colloidal film significantly improved the adhesion; although Comparative Example 3 was coated on the dry film, the adhesion was improved, but the 100-square test Only promoted to B1.
實施例1~4對於與銅箔之接著力有明顯提升,原因為聚醯亞胺基材膜與氟素高分子層之間之接著力提升所致。 Examples 1 to 4 have a significant improvement in the adhesion with the copper foil, which is due to the improvement in the adhesion between the polyimide base film and the fluorine polymer layer.
熟習本領域之技藝者可理解,在不悖離後附申請專利範圍所界定之範疇下針對本發明所進行之各種變化或修改係落入本發明之一部分。 Those skilled in the art will understand that various changes or modifications made to the present invention without departing from the scope defined in the appended patent application are part of the present invention.
S1:提供一聚醯胺酸溶液 S1: Provide a polyamide solution
S2:製備一氟素高分子粒子分散液 S2: Preparation of monofluoropolymer particle dispersion
S3:將聚醯胺酸溶液製成膠態聚醯亞胺膜 S3: Make the polyamide acid solution into a colloidal polyimide membrane
S4:將氟素高分子粒子分散液塗佈於膠態聚醯亞胺膜之雙面上 S4: Coat the fluorine polymer particle dispersion on both sides of the colloidal polyimide film
S5:烘烤形成聚醯亞胺複合膜 S5: Bake to form polyimide composite film
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