TWI748769B - Polymer dispersion, method for manufacturing the polymer dispersion, and polymer composite film and its application - Google Patents
Polymer dispersion, method for manufacturing the polymer dispersion, and polymer composite film and its application Download PDFInfo
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本發明涉及高分子材料製備的技術領域，尤其涉及一種高分子分散液的製備方法、高分子複合膜及其應用。 The invention relates to the technical field of polymer material preparation, in particular to a method for preparing a polymer dispersion, a polymer composite membrane and its application.
印刷電路板中的信號傳輸損耗部分源於介電層引起的損失。介電層引起的損失通常與介電層材料的介電常數和介電損失因數有關。此外，介電層材料的極性會影響導線中電子傳輸的穩定性，若絕緣層材料中分子結構極性過大，電路板極化後，導線中的電子將會受到介電層的吸引，嚴重影響電子傳輸的穩定性。因此，如何有效設計介電層的高分子結構，降低介電層高分子材料的介電損失，達到良好的絕緣效果，將成為重要的課題。 The signal transmission loss in the printed circuit board is partly due to the loss caused by the dielectric layer. The loss caused by the dielectric layer is usually related to the dielectric constant and the dielectric loss factor of the dielectric layer material. In addition, the polarity of the dielectric layer material will affect the stability of electron transmission in the wire. If the polarity of the molecular structure in the insulating layer material is too large, after the circuit board is polarized, the electrons in the wire will be attracted by the dielectric layer, which will seriously affect the electrons. Stability of transmission. Therefore, how to effectively design the polymer structure of the dielectric layer, reduce the dielectric loss of the polymer material of the dielectric layer, and achieve a good insulation effect, will become an important issue.
目前，液晶高分子(Liquid-crystalline polymer，LCP)材料因其具有液晶結構，介電損耗較低，被廣泛應用於印刷電路板中。但，LCP材料的固成分和黏度較低，需要在無溶劑且高溫條件下成膜，成膜工藝限制多，而且成膜後與銅板壓合製作成覆銅板的難度也較大。 At present, liquid-crystalline polymer (LCP) materials are widely used in printed circuit boards because of their liquid crystal structure and low dielectric loss. However, the solid content and viscosity of the LCP material are low, and the film needs to be formed under solvent-free and high-temperature conditions. The film-forming process is limited, and it is also difficult to press the copper plate into a copper-clad laminate after the film is formed.
為了解決上述技術問題，本發明提出一種高分子分散液及其製備方法。 In order to solve the above technical problems, the present invention proposes a polymer dispersion and a preparation method thereof.
另外，本發明還提出由上述高分子分散液製得的高分子複合膜及其應用。 In addition, the present invention also proposes a polymer composite membrane prepared from the above polymer dispersion and its application.
本發明提供一種高分子分散液，包括液晶高分子粉體、聚醯胺酸和溶劑，所述高分子分散液的固成分包括所述聚醯胺酸和所述液晶高分子粉體，所述液晶高分子粉體在所述高分子分散液的固成分中的重量百分比為20%~30%，所述聚醯胺酸在所述高分子分散液的固成分中的重量百分比為70%~80%，所述 聚醯胺酸由兩種二胺單體與兩種二酸酐單體聚合而成，兩種所述二胺單體和兩種所述二酸酐單體均分別含有液晶結構和柔性結構。 The present invention provides a polymer dispersion comprising liquid crystal polymer powder, polyamide acid and a solvent. The solid component of the polymer dispersion comprises the polyamide acid and the liquid crystal polymer powder. The weight percentage of the liquid crystal polymer powder in the solid content of the polymer dispersion is 20%-30%, and the weight percentage of the polyamide acid in the solid content of the polymer dispersion is 70%~ 80%, the Polyamide acid is formed by polymerizing two diamine monomers and two dianhydride monomers, and both of the two diamine monomers and the two dianhydride monomers respectively contain a liquid crystal structure and a flexible structure.
本申請實施方式中，所述液晶高分子粉體的粒徑小於或等於3μm。 In the embodiment of the present application, the particle size of the liquid crystal polymer powder is less than or equal to 3 μm.
本申請實施方式中，所述高分子分散液的固含量為25%~35%，黏度為40000cps~50000cps。 In the embodiment of the present application, the solid content of the polymer dispersion is 25% to 35%, and the viscosity is 40,000 cps to 50,000 cps.
本申請實施方式中，所述液晶高分子粉體包括芳香族液晶聚酯。 In the embodiment of the application, the liquid crystal polymer powder includes aromatic liquid crystal polyester.
本發明還提供一種高分子分散液的製備方法，包括以下步驟： 提供聚醯胺酸溶液，所述聚醯胺酸溶液包括聚醯胺酸和溶劑，所述聚醯胺酸由兩種二胺單體與兩種二酸酐單體聚合而成，兩種所述二胺單體和兩種所述二酸酐單體均分別含有液晶結構和柔性結構。 The invention also provides a method for preparing the polymer dispersion, which includes the following steps: A polyamide acid solution is provided. The polyamide acid solution includes polyamide acid and a solvent. The polyamide acid is polymerized by two diamine monomers and two dianhydride monomers, and the two kinds of The diamine monomer and the two diacid anhydride monomers each contain a liquid crystal structure and a flexible structure.
以及，於所述聚醯胺酸溶液中加入液晶高分子粉體，混合得到所述高分子分散液。 And, adding liquid crystal polymer powder to the polyamide acid solution and mixing to obtain the polymer dispersion.
其中，所述高分子分散液的固成分包括所述聚醯胺酸和所述液晶高分子粉體，所述液晶高分子粉體在所述高分子分散液的固成分中的重量百分比為20%~30%，所述聚醯胺酸在所述高分子分散液的固成分中的重量百分比為70%~80%。 Wherein, the solid content of the polymer dispersion includes the polyamide acid and the liquid crystal polymer powder, and the weight percentage of the liquid crystal polymer powder in the solid content of the polymer dispersion is 20. %~30%, the weight percentage of the polyamide acid in the solid content of the polymer dispersion is 70%~80%.
本申請實施方式中，所述液晶高分子粉體的平均粒徑小於或等於3μm。 In the embodiment of the present application, the average particle size of the liquid crystal polymer powder is less than or equal to 3 μm.
本申請實施方式中，所述高分子分散液的固含量為25%~35%，黏度為40000cps~50000cps。 In the embodiment of the present application, the solid content of the polymer dispersion is 25% to 35%, and the viscosity is 40,000 cps to 50,000 cps.
本申請實施方式中，所述液晶高分子粉體包括芳香族液晶聚酯。 In the embodiment of the application, the liquid crystal polymer powder includes aromatic liquid crystal polyester.
本申請實施方式中，所述含有液晶結構的二胺單體包括對氨基苯甲酸對氨基苯酯、1,4-雙(4-氨基苯氧基)苯以及對苯二甲酸二對氨基苯酯中的一種或幾種。 In the embodiment of the present application, the diamine monomer containing a liquid crystal structure includes p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy)benzene, and di-p-aminophenyl terephthalate One or more of them.
所述含有柔性結構的二胺單體包括4,4'-二氨基二苯醚、2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷、1,3-雙(4'-氨基苯氧基)苯以及1,3-雙(3-氨基苯氧基)苯中的一種或幾種。 The diamine monomer containing a flexible structure includes 4,4'-diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 1,3-bis( One or more of 4'-aminophenoxy)benzene and 1,3-bis(3-aminophenoxy)benzene.
本申請實施方式中，所述含有液晶結構的二酸酐單體包括3,3',4,4'-聯苯四羧酸二酐、對苯基二(偏苯三酸酯)二酸酐以及環己烷-1,4-二基雙(亞甲基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)。 In the embodiment of the present application, the dianhydride monomer containing a liquid crystal structure includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylbis(trimellitic acid ester) dianhydride and cyclic Hexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester).
所述含有柔性結構的二酸酐單體包括4,4'-氧雙鄰苯二甲酸酐及雙酚A型二醚二酐中的一種或幾種。 The dianhydride monomer containing a flexible structure includes one or more of 4,4'-oxydiphthalic anhydride and bisphenol A type diether dianhydride.
本發明還提供一種高分子複合膜，所述高分子複合膜由如上所述的高分子分散液加熱後製得，該高分子複合膜包括液晶高分子晶體和聚醯亞胺晶體，所述液晶高分子晶體和所述聚醯亞胺晶體相互交聯形成網路結構。 The present invention also provides a polymer composite film, which is prepared by heating the polymer dispersion as described above. The polymer composite film includes liquid crystal polymer crystals and polyimide crystals. The liquid crystal The polymer crystal and the polyimide crystal are cross-linked with each other to form a network structure.
本申請實施方式中，所述液晶高分子晶體占所述高分子複合膜的重量百分比為20%~30%。 In the embodiment of the present application, the weight percentage of the liquid crystal polymer crystals in the polymer composite film is 20%-30%.
本申請實施方式中，所述高分子複合膜為各向異性的熱塑性膜。 In the embodiment of the present application, the polymer composite film is an anisotropic thermoplastic film.
本發明還提供一種覆銅板，該覆銅板包括銅箔及層疊於所述銅箔至少一表面的高分子複合膜，所述高分子複合膜包括如上所述的高分子複合膜。 The present invention also provides a copper clad laminate, which includes a copper foil and a polymer composite film laminated on at least one surface of the copper foil, and the polymer composite film includes the polymer composite film as described above.
相較於習知技術，本發明提供的高分子分散液，藉由將液晶高分子粉體與同時含有液晶結構和柔性結構的熱塑性聚醯胺酸混合，形成分散液，可有效提高分散液的固含量和黏度，而且形成的分散液穩定性好，有利於分散液的成膜，形成的覆銅板中高分子複合膜與銅板的接著性良好，同時高分子複合膜中形成的兩種晶相能夠藉由結晶交聯點形成網路結構，有效降低了覆銅板的Df和熱膨脹係數，同時提高了高分子複合膜的機械性能。 Compared with the prior art, the polymer dispersion provided by the present invention, by mixing the liquid crystal polymer powder and the thermoplastic polyamide acid containing both a liquid crystal structure and a flexible structure to form a dispersion, can effectively improve the dispersion The solid content and viscosity, and the stability of the dispersion liquid formed is good, which is conducive to the film formation of the dispersion liquid. By forming a network structure by crystalline cross-linking points, the Df and thermal expansion coefficient of the copper clad laminate are effectively reduced, and the mechanical properties of the polymer composite film are improved at the same time.
100:層覆銅板 100: Layer copper clad laminate
10:銅板 10: Copper plate
20:高分子複合膜 20: Polymer composite membrane
30:高分子分散液膜 30: Polymer dispersion liquid membrane
1:液晶高分子晶體 1: Liquid crystal polymer crystal
2:聚醯胺酸分子 2: Polyamide molecule
3:聚醯亞胺晶體 3: Polyimide crystal
圖1A-1B是本發明一實施方式提供的高分子分散液加熱過程中發生結晶的示意圖。 1A-1B are schematic diagrams of crystallization during heating of a polymer dispersion provided by an embodiment of the present invention.
圖2A-2C是本發明一實施方式提供的覆銅板的製備流程圖。 2A-2C are the preparation flow charts of the copper clad laminate provided by an embodiment of the present invention.
如下具體實施方式將結合上述附圖進一步說明本發明。 The following specific embodiments will further illustrate the present invention in conjunction with the above-mentioned drawings.
下面將結合具體實施例對本發明的技術方案進行清楚、完整地描述。顯然，所描述的實施方式僅是本發明一部分實施方式，而不是全部的實施方式。基於本發明中的實施方式，本領域普通技術人員在沒有做出創造性勞動前提下所獲得的所有其他實施方式，都屬於本發明保護的範圍。 The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
除非另有定義，本文所使用的所有的技術和科學術語與屬於本發明的技術領域的技術人員通常理解的含義相同。在本發明的說明書中所使用的技術手段的名稱只是為了描述具體的實施例的目的，不是旨在於限制本發明。 Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The names of the technical means used in the description of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
在不衝突的情況下，下述的實施例及實施例中的特徵可以相互組合。 In the case of no conflict, the following embodiments and features in the embodiments can be combined with each other.
本發明提供了一種高分子分散液，該高分子分散液包括液晶高分子粉體(LCP粉體)、聚醯胺酸和溶劑，所述高分子分散液的固成分包括所述聚醯胺酸和所述液晶高分子粉體，所述液晶高分子粉體在所述高分子分散液的固成分中的重量百分比為20%~30%，所述聚醯胺酸在所述高分子分散液的固成分中的重量百分比為70%~80%。所述聚醯胺酸由兩種二胺單體與兩種二酸酐單體聚合而成，兩種所述二胺單體和兩種所述二酸酐單體均分別含有液晶結構和柔性結構。 The present invention provides a polymer dispersion, which includes liquid crystal polymer powder (LCP powder), polyamide acid and a solvent, and the solid content of the polymer dispersion includes the polyamide acid And the liquid crystal polymer powder, the weight percentage of the liquid crystal polymer powder in the solid content of the polymer dispersion is 20% to 30%, and the polyamide acid is in the polymer dispersion The weight percentage of the solid content is 70% to 80%. The polyamide acid is formed by polymerizing two diamine monomers and two dianhydride monomers, and both of the two diamine monomers and the two dianhydride monomers respectively contain a liquid crystal structure and a flexible structure.
本實施方式中，所述液晶高分子粉體的平均粒徑小於或等於3μm。 In this embodiment, the average particle size of the liquid crystal polymer powder is less than or equal to 3 μm.
本實施方式中，所述高分子分散液的固含量為25%~35%，黏度為40000cps~50000cps。藉由添加液晶高分子粉體，液晶高分子粉體不溶但可分散於溶劑中，因此能夠有效提高高分子分散液的黏度，從而提高分散液穩定性，有利於後續成膜。 In this embodiment, the solid content of the polymer dispersion is 25% to 35%, and the viscosity is 40,000 cps to 50,000 cps. By adding the liquid crystal polymer powder, the liquid crystal polymer powder is insoluble but can be dispersed in the solvent, so it can effectively increase the viscosity of the polymer dispersion, thereby improving the stability of the dispersion, and is beneficial to subsequent film formation.
本實施方式中，所述液晶高分子粉體包括但不限於芳香族液晶聚酯。 In this embodiment, the liquid crystal polymer powder includes, but is not limited to, aromatic liquid crystal polyester.
本實施方式中，所述溶劑包括但不限於N-甲基吡咯烷酮(NMP)。 In this embodiment, the solvent includes but is not limited to N-methylpyrrolidone (NMP).
本發明還提供一種高分子分散液的製備方法，包括以下步驟：第一步，合成聚醯胺酸溶液。 The present invention also provides a method for preparing the polymer dispersion, which includes the following steps: the first step is to synthesize a polyamide acid solution.
其中，所述聚醯胺酸由兩種二胺單體與兩種二酸酐單體聚合而成，兩種所述二胺單體和兩種所述二酸酐單體均分別含有液晶結構和柔性結構。 Wherein, the polyamide acid is formed by the polymerization of two diamine monomers and two dianhydride monomers, and the two diamine monomers and the two dianhydride monomers each contain a liquid crystal structure and flexibility. structure.
本實施方式中，含液晶結構的二胺單體包括但不限於對氨基苯甲酸對氨基苯酯(APAB)、1,4-雙(4-氨基苯氧基)苯(ABHQ)以及對苯二甲酸二對氨基苯酯(BPTP)中的一種或幾種。含有柔性結構的二胺單體包括但不限於4,4'-二氨基二苯醚(ODA)、2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷(BAPP)、1,3-雙(4'-氨基苯氧基)苯(TPE-R)以及1,3-雙(3-氨基苯氧基)苯(TPE-M)中的一種或幾種。 In this embodiment, the diamine monomer containing a liquid crystal structure includes, but is not limited to, p-aminophenyl p-aminobenzoate (APAB), 1,4-bis(4-aminophenoxy)benzene (ABHQ), and terephthalic acid. One or more of di-p-aminophenyl formate (BPTP). Diamine monomers containing flexible structures include but are not limited to 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxyphenyl)]propane (BAPP) , One or more of 1,3-bis(4'-aminophenoxy)benzene (TPE-R) and 1,3-bis(3-aminophenoxy)benzene (TPE-M).
本實施方式中，含液晶結構二酸酐單體包括但不限於3,3',4,4'-聯苯四羧酸二酐(BPDA)、對苯基二(偏苯三酸酯)二酸酐(TAHQ)以及環己烷-1,4-二基雙(亞甲基)雙(1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯)(TA-CHDM)中的一種或幾種。含有柔性結構的二酸酐單體包括但不限於4,4'-氧雙鄰苯二甲酸酐(ODPA)及雙酚A型二醚二酐(BPADA)中的一種或幾種。 In this embodiment, the dianhydride monomer containing a liquid crystal structure includes, but is not limited to, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and p-phenylbis(trimellitic acid ester) dianhydride (TAHQ) and cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester) (TA -CHDM) one or more of them. The dianhydride monomer containing a flexible structure includes, but is not limited to, one or more of 4,4'-oxydiphthalic anhydride (ODPA) and bisphenol A diether dianhydride (BPADA).
本實施方式中，四種單體中二胺和二酸酐的結合使隨機的，得到的聚醯胺酸為一系列不同分子結構的聚醯胺酸的混合物。具體地，以下給出了採用二胺為APAB和TPE-R，二酸酐為TAHQ和BPADA得到的具體產物的結構式舉例為：
本實施方式中，所述二胺單體和所述二酸酐單體的添加比例優選1：1。 In this embodiment, the addition ratio of the diamine monomer and the dianhydride monomer is preferably 1:1.
本實施方式中，所述溶劑包括但不限於N-甲基吡咯烷酮(NMP)。 In this embodiment, the solvent includes but is not limited to N-methylpyrrolidone (NMP).
本實施方式中，所述二胺單體與所述二酸酐單體在常溫條件下反應48小時左右生成聚醯胺酸嵌段共聚物。所述聚醯胺酸溶液的固含量為20wt%~30wt%。 In this embodiment, the diamine monomer and the dianhydride monomer react for about 48 hours under normal temperature conditions to form a polyamide acid block copolymer. The solid content of the polyamide acid solution is 20 wt% to 30 wt%.
第二步，於所述聚醯胺酸溶液中加入所述液晶高分子粉體，混合得到所述高分子分散液。所述高分子分散液的固成分包括所述聚醯胺酸和所述液晶高分子粉體，所述液晶高分子粉體在所述高分子分散液的固成分中的重量百分比為20%~30%，所述聚醯胺酸在所述高分子分散液的固成分中的重量百分比為70%~80%。 In the second step, the liquid crystal polymer powder is added to the polyamide acid solution and mixed to obtain the polymer dispersion. The solid content of the polymer dispersion includes the polyamide acid and the liquid crystal polymer powder, and the weight percentage of the liquid crystal polymer powder in the solid content of the polymer dispersion is 20%~ 30%, the weight percentage of the polyamide acid in the solid content of the polymer dispersion is 70% to 80%.
本實施方式中，將液晶高分子粉體的顆粒加入聚醯胺酸溶液中，所述液晶高分子粉體不溶但能均勻分散在溶液中，形成所述高分子分散液。所述液晶高分子粉體的平均粒徑小於或等於3μm，這個尺寸的所述液晶高分子粉體能夠更好地與所述聚醯胺酸接觸，提高兩者的接觸面積，同時有利於粉體顆粒在所述高分子分散液中的均勻分散，便於後續塗布成膜。若所述液晶高分子粉體的平均粒徑過大，所述高分子分散液易產生沉降、後續塗布成膜時容易出現厚度不均的現象，而且大顆粒的所述液晶高分子粉體與所述聚醯胺酸不能充分接觸，導致後續無法均相成膜。 In this embodiment, the particles of the liquid crystal polymer powder are added to the polyamide acid solution. The liquid crystal polymer powder is insoluble but can be uniformly dispersed in the solution to form the polymer dispersion. The average particle size of the liquid crystal polymer powder is less than or equal to 3 μm. The liquid crystal polymer powder of this size can better contact the polyamide acid, increase the contact area between the two, and is beneficial to the powder. The uniform dispersion of bulk particles in the polymer dispersion is convenient for subsequent coating and film formation. If the average particle size of the liquid crystal polymer powder is too large, the polymer dispersion is prone to sedimentation, and uneven thickness is likely to occur during subsequent coating and film formation. In addition, the large particles of the liquid crystal polymer powder and the The polyamide acid can not be fully contacted, resulting in the subsequent failure to form a homogeneous film.
本實施方式中，所述高分子分散液的固含量為25%~35%，黏度為40000cps~50000cps。藉由在熱塑性的聚醯胺酸溶液中添加液晶高分子粉體形成混合均勻的分散液，可有效提高分散液的固含量和黏度，有利於後續成膜。 In this embodiment, the solid content of the polymer dispersion is 25% to 35%, and the viscosity is 40,000 cps to 50,000 cps. By adding liquid crystal polymer powder to the thermoplastic polyamide solution to form a uniformly mixed dispersion, the solid content and viscosity of the dispersion can be effectively increased, which is beneficial to subsequent film formation.
本實施方式中，所述液晶高分子粉體包括但不限於芳香族液晶聚酯。 In this embodiment, the liquid crystal polymer powder includes, but is not limited to, aromatic liquid crystal polyester.
本發明還提供一種高分子複合膜，所述高分子複合膜由如上所述的高分子分散液加熱後製得。請參考圖1A-1B，分散液在加熱固化成膜的過程中，液晶高分子粉體對應的液晶高分子晶體1熔融形成能流動的熔體，聚醯胺酸分子2加熱環化形成聚醯亞胺熔體，液晶高分子熔體均勻分佈在聚醯亞胺熔體內，如圖1A所示。並且液晶高分子粉體具有液晶結構(酯基)，聚醯亞胺中也含有液晶結構(酯基)，在冷卻過程中均能發生結晶，液晶高分子熔體重新結晶再次形成液晶高分子晶體1，聚醯亞胺結晶形成聚醯亞胺晶體3，如圖1B所示。由於兩熔體均勻混合在一起，兩種結晶相還會形成大量的物理性結晶交聯點，這些交聯點將所述液晶高分子結晶相和所述聚醯亞胺結晶相連接在一起形成網路結構，如圖1B中放大圖的結構，液晶高分子晶體1和聚醯亞胺晶體3相互穿插形成物理性結晶交聯網路結構。形成的網狀結構有效提高了高分子複合膜的機械性能，同時降低了高分子複合膜的熱膨脹係數(CTE)，從而提升了
高分子複合膜的尺寸穩定性。另外，在形成高分子分散液時，由於液晶高分子粉體均勻分佈在聚醯胺酸溶液中，而且液晶高分子粉體的平均粒徑非常小，在加熱成膜過程中，液晶高分子粉體能充分熔融，與聚醯亞胺熔體形成均勻的混合熔體，兩種熔體結晶後形成兩種晶體，兩種晶體交叉混合形成網路結構，並且兩晶體的排列方向呈現各向異性，從而賦予了所述高分子複合膜各向異性的特點。
The present invention also provides a polymer composite membrane, which is prepared by heating the polymer dispersion as described above. Please refer to Figure 1A-1B, during the process of heating and curing the dispersion into a film, the liquid
本實施方式中，所述液晶高分子粉體的平均粒徑小於或等於3μm，在形成分散液的過程中，這個尺寸的液晶高分子粉體能夠更好地與聚醯胺酸接觸，提高兩者的接觸面積，同時有利於提高所述高分子分散液的黏度，便於所述高分子分散液塗布成膜。當所述液晶高分子粉體的平均粒徑過大時，所述高分子分散液易產生沉降、後續塗布成膜時容易出現厚度不均的現象，而且在高溫熔融時，粒徑大於3μm的所述液晶高分子粉體顆粒無法完全熔融，導致無法均相成膜。 In this embodiment, the average particle size of the liquid crystal polymer powder is less than or equal to 3 μm. In the process of forming a dispersion, the liquid crystal polymer powder of this size can better contact with the polyamide acid to improve the two The contact area of the polymer dispersion liquid is also beneficial to increase the viscosity of the polymer dispersion liquid and facilitate the coating and film formation of the polymer dispersion liquid. When the average particle size of the liquid crystal polymer powder is too large, the polymer dispersion is prone to sedimentation, and uneven thickness is likely to occur during subsequent coating and film formation. Moreover, when the liquid crystal polymer powder is melted at a high temperature, the particle size is greater than 3μm. The liquid crystal polymer powder particles cannot be completely melted, resulting in the inability to form a homogeneous film.
本實施方式中，可以藉由調節所述液晶高分子粉體和所述聚醯胺酸的含量來調整兩種晶體的占比，進而調節複合膜的機械性能和電性能等。另外還可以藉由調節聚醯胺酸合成過程中液晶結構的引入來進一步調整上述複合膜的機械性能和電性能。 In this embodiment, the proportions of the two crystals can be adjusted by adjusting the content of the liquid crystal polymer powder and the polyamide acid, thereby adjusting the mechanical properties and electrical properties of the composite film. In addition, the mechanical and electrical properties of the composite film can be further adjusted by adjusting the introduction of the liquid crystal structure during the synthesis of polyamide acid.
本實施方式中，高分子複合膜中所述液晶高分子晶體1占所述高分子複合膜的重量百分比為20%~30%。
In this embodiment, the liquid
本實施方式中，所述加熱溫度為350℃~370℃，加熱時間為30min~60min。具體的加熱溫度可以根據實際高分子分散液的玻璃化轉變溫度而變化。 In this embodiment, the heating temperature is 350° C. to 370° C., and the heating time is 30 min to 60 min. The specific heating temperature can be changed according to the glass transition temperature of the actual polymer dispersion.
本實施方式中，所述高分子複合膜的熱膨脹係數小於或等於45ppm/℃，抗張強度大於或等於130MPa，延伸率大於或等於18%。 In this embodiment, the thermal expansion coefficient of the polymer composite film is less than or equal to 45 ppm/°C, the tensile strength is greater than or equal to 130 MPa, and the elongation is greater than or equal to 18%.
具體地，所述高分子複合膜的成膜過程為：在一離型基材上塗布厚度大於或等於50μm的上述高分子分散液，再將塗布有高分子分散液膜層的離型基材過烘箱進行烘烤加熱，通常在350℃~370℃範圍內加熱30min~60min，得到所述高分子複合膜。在上述溫度下所述液晶高分子粉體顆粒會熔融，變成熔體，可以更好地均相成膜。 Specifically, the film forming process of the polymer composite film is: coating the above polymer dispersion with a thickness greater than or equal to 50 μm on a release substrate, and then applying the release substrate coated with the polymer dispersion film layer Bake and heat in an oven, usually in the range of 350° C. to 370° C., for 30 min to 60 min, to obtain the polymer composite film. At the above temperature, the liquid crystal polymer powder particles will melt and become a melt, which can better form a homogeneous film.
請參閱圖2A-2C，本發明還提供一種覆銅板100的製備流程，具體包括如下步驟：請參閱圖2A，提供一銅箔10，所述銅箔10的厚度可以根據實際使用需求來選擇，具體地，本實施方式中，所述銅箔10的厚度為12μm。
2A-2C, the present invention also provides a preparation process of copper clad
請參閱圖2B，於所述銅箔10的一表面塗布上述高分子分散液，形成高分子分散液膜30，得到一中間體，具體地，本實施方式中，高分子分散液膜30的厚度為50μm。
2B, the above-mentioned polymer dispersion is coated on a surface of the
請參閱圖2C，將所述中間體置於烤箱內加熱，使所述高分子分散液膜30固化形成一高分子複合膜20，得到所述覆銅板100。在本實施方式中，所述高分子分散液膜30在350℃~370℃範圍內加熱30min~60min，得到所述高分子複合膜20。
Referring to FIG. 2C, the intermediate is placed in an oven and heated to solidify the polymer
所述覆銅板100包括銅箔10及層疊於所述銅箔10表面的高分子複合膜20，所述高分子複合膜20為如上所述的高分子複合膜。
The copper clad
本實施方式中，所述覆銅板100具有優良的電性能，10GHz的頻率下進行電性能測試，可知覆銅板具有優異的介電損耗因數(Df)和介電常數(Dk)，其中Dk優選為3.3~3.2，Df優選為0.002~0.001。
In this embodiment, the copper clad
本實施方式中，所述高分子複合膜20在所述銅箔10表面的剝離強度優選大於或等於0.7kgf/cm。耐熱性測試中，在288℃/10sec條件下上述高分子複合膜耐熱性良好。
In this embodiment, the peel strength of the
另外，還可以藉由上述方法製備雙面覆銅板。 In addition, the double-sided copper clad laminate can also be prepared by the above-mentioned method.
本發明還提供另一種覆銅板的製備方法，先製備出高分子複合膜，然後將高分子複合膜貼合在銅箔的至少一面進行熱壓形成所述覆銅板。具體熱壓貼合的具體條件為：熱壓溫度為350℃~370℃，單位面積的壓力為30~80kgf/mm2，熱壓試劑在10~30min內。具體地，可藉由此方法製備單面或雙面覆銅板。以下藉由具體實施例來對本申請的方案進行進一步說明。 The present invention also provides another method for preparing a copper clad laminate. The polymer composite film is first prepared, and then the polymer composite film is attached to at least one side of the copper foil and hot pressed to form the copper clad laminate. The specific conditions for hot pressing are as follows: the hot pressing temperature is 350°C to 370°C, the pressure per unit area is 30 to 80 kgf/mm 2 , and the hot pressing reagent is within 10 to 30 minutes. Specifically, single-sided or double-sided copper clad laminates can be prepared by this method. The following specific examples are used to further illustrate the solution of the present application.
以下合成例1-5均為聚醯胺酸溶液的具體合成方式，合成的聚醯胺酸溶液的固含量為20wt%~30wt%。合成聚醯胺酸溶液後，於12μm銅板上塗布50μm厚度的聚醯胺酸溶液，並在350℃~370℃條件下烘烤30min~60min，除去溶劑並使聚醯胺酸環化形成聚醯亞胺並熔融，再冷卻形成聚醯亞胺膜，從而得到覆銅板，並對上述覆銅板進行機械性能及電性能等的測試。 The following synthesis examples 1-5 are specific synthesis methods of the polyamide acid solution, and the solid content of the synthesized polyamide acid solution is 20 wt% to 30 wt%. After synthesizing the polyamic acid solution, coat a 50μm thick polyamic acid solution on a 12μm copper plate, and bake at 350℃~370℃ for 30min~60min, remove the solvent and cyclize the polyamide acid to form polyamide The imine is melted, and then cooled to form a polyimide film, thereby obtaining a copper clad laminate, and testing the mechanical and electrical properties of the copper clad laminate.
合成例1 Synthesis example 1
於500mL反應瓶中分別加入NMP(243.8g)、TPE-M(0.1mol,29.23g)，待攪拌至溶解後，再加入BPADA(0.1mol,52.05g)攪拌反應48小時，即配置完成聚醯胺酸溶液。 Add NMP (243.8g) and TPE-M (0.1mol, 29.23g) into a 500mL reaction flask respectively, and after stirring to dissolve, add BPADA (0.1mol, 52.05g) and stir for 48 hours to complete the configuration. Amino acid solution.
合成例2 Synthesis Example 2
於500mL反應瓶中分別加入NMP(205.97g)、APAB(0.1mol,22.83g)，待攪拌至溶解後，再加入TAHQ(0.1mol,45.83g)攪拌反應48小時，即配置完成聚醯胺酸溶液。 Add NMP (205.97g) and APAB (0.1mol, 22.83g) into a 500mL reaction flask respectively, and after stirring to dissolve, add TAHQ (0.1mol, 45.83g) and stir for 48 hours to complete the configuration. Solution.
合成例3 Synthesis Example 3
於500mL反應瓶中分別加入NMP(225.20g)、TPE-M(0.1mol,29.2g)，待攪拌至溶解後，再加入TAHQ(0.1mol,45.83g)攪拌反應48小時，即配置完成聚醯胺酸溶液。 Add NMP (225.20g) and TPE-M (0.1mol, 29.2g) into a 500mL reaction flask respectively, and after stirring to dissolve, add TAHQ (0.1mol, 45.83g) and stir for 48 hours to complete the configuration. Amino acid solution.
合成例4 Synthesis Example 4
於500mL反應瓶中分別加入NMP(224.62g)、APAB(0.1mol,22.83g)，待攪拌至溶解後，再加入BPADA(0.1mol,52.05g)攪拌反應48小時，即配置完成聚醯胺酸溶液。 Add NMP (224.62g) and APAB (0.1mol, 22.83g) into a 500mL reaction flask respectively, and after stirring to dissolve, add BPADA (0.1mol, 52.05g) and stir for 48 hours to complete the configuration. Solution.
合成例5 Synthesis Example 5
於500mL反應瓶中分別加入NMP(224.91g)、TPE-M(0.05mol,14.61g)，待攪拌至溶解後，再加入TAHQ(0.05mol,22.93g)攪拌反應1小時後，再加入APAB(0.05mol,11.41g)，待攪拌至溶解後，再加入BPADA(0.05mol,26.02g)攪拌反應48小時，即配置完成聚醯胺酸溶液。 Add NMP (224.91g) and TPE-M (0.05mol, 14.61g) into a 500mL reaction flask respectively, and after stirring to dissolve, add TAHQ (0.05mol, 22.93g) and stir and react for 1 hour, then add APAB( 0.05mol, 11.41g), after stirring to dissolve, add BPADA (0.05mol, 26.02g) and stir for 48 hours to complete the configuration of the polyamide acid solution.
製備聚醯胺酸各原料的具體配比及相應覆銅板的測試結果如表1所示。 The specific proportions of the raw materials for the preparation of polyamide acid and the test results of the corresponding copper clad laminates are shown in Table 1.
注：Ts為聚醯亞胺的熱加工溫度，其中Ts介於玻璃化轉變溫度Tg和熔融溫度Tm之間。 Note: Ts is the thermal processing temperature of polyimide, where Ts is between the glass transition temperature Tg and the melting temperature Tm.
以下實施例1-3均為高分子分散液的具體合成方式，合成的高分子分散液的固含量為25wt%~35wt%。合成高分子分散液後，於12μm銅板上塗布50μm厚度的高分子分散液，並在350℃~370℃條件下烘烤30min~60min，除去溶劑並使聚醯亞胺和液晶高分子粉體熔融，再冷卻形成高分子複合膜，從而得到覆銅板，並對上述覆銅板進行機械性能及電性能等的測試。 The following Examples 1-3 are specific synthesis methods of polymer dispersions, and the solid content of the synthesized polymer dispersions is 25 wt% to 35 wt%. After synthesizing the polymer dispersion, coat the polymer dispersion with a thickness of 50μm on a 12μm copper plate, and bake at 350℃~370℃ for 30min~60min, remove the solvent and melt the polyimide and liquid crystal polymer powder , And then cooled to form a polymer composite film, thereby obtaining a copper clad laminate, and testing the mechanical and electrical properties of the copper clad laminate.
實施例1 Example 1
於100ml反應瓶中依次加入合成例5合成的聚醯胺酸溶液10g、LF31-P粉體0.625g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10 g of the polyamide acid solution synthesized in Synthesis Example 5 and 0.625 g of LF31-P powder into a 100 ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
實施例2 Example 2
於100ml反應瓶中依次加入合成例5合成的聚醯胺酸溶液10g、LF31-P粉體0.833g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10 g of the polyamide acid solution synthesized in Synthesis Example 5 and 0.833 g of LF31-P powder into a 100 ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
實施例3 Example 3
於100ml反應瓶中依次加入合成例5合成的聚醯胺酸溶液10g、LF31-P粉體1.07g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10g of the polyamide acid solution synthesized in Synthesis Example 5 and 1.07g of LF31-P powder into a 100ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
製備高分子分散液各原料的具體配比及具有高分子複合膜的覆銅板的測試結果如表2所示。 The specific ratios of the raw materials for preparing the polymer dispersion and the test results of the copper clad laminate with polymer composite film are shown in Table 2.
以下對比例1-8分別合成了液晶高分子分散液和高分子分散液，合成分散液後於12μm銅板上塗布50μm厚度的相應溶液，並在350℃~370℃條件下烘烤30min~60min，除去溶劑並加熱，再冷卻形成相應膜材，從而得到相應覆銅板，並對上述覆銅板進行機械性能及電性能等的測試。 In the following comparative examples 1-8, the liquid crystal polymer dispersion and the polymer dispersion were synthesized. After the synthesis of the dispersion, the corresponding solution with a thickness of 50 μm was coated on a 12 μm copper plate and baked at 350 ℃ ~ 370 ℃ for 30 min to 60 min. The solvent is removed, heated, and then cooled to form the corresponding film material, thereby obtaining the corresponding copper clad laminate, and testing the mechanical and electrical properties of the above copper clad laminate.
對比例1 Comparative example 1
於100ml反應瓶中依次加入LF31-P粉體3.5g、NMP 31.5g，攪拌6小時，使粉體完全分散於溶劑中，可得到LF31-P分散液。 Add 3.5g of LF31-P powder and 31.5g of NMP into a 100ml reaction flask, and stir for 6 hours to completely disperse the powder in the solvent to obtain LF31-P dispersion.
對比例2 Comparative example 2
於100ml反應瓶中依次加入合成例1合成的聚醯胺酸溶液10g、LF31-P粉體0.625g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10g of the polyamide acid solution synthesized in Synthesis Example 1 and 0.625g of LF31-P powder into a 100ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
對比例3於100ml反應瓶中依次加入合成例2合成的聚醯胺酸溶液10g、LF31-P粉體0.625g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Comparative Example 3 In a 100ml reaction flask, 10g of the polyamide acid solution synthesized in Synthesis Example 2 and 0.625g of LF31-P powder were added in sequence, and stirred for 6 hours to completely disperse the powder in the polyamide acid solution. Molecular dispersion.
對比例4於100ml反應瓶中依次加入合成例3合成的聚醯胺酸溶液10g、LF31-P粉體0.625g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Comparative Example 4 In a 100ml reaction flask, 10g of the polyamide acid solution synthesized in Synthesis Example 3 and 0.625g of LF31-P powder were added in sequence, and stirred for 6 hours to completely disperse the powder in the polyamide acid solution. Molecular dispersion.
對比例5 Comparative example 5
於100ml反應瓶中依次加入合成例4合成的聚醯胺酸溶液10g、LF31-P粉體0.625g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10 g of the polyamide acid solution synthesized in Synthesis Example 4 and 0.625 g of LF31-P powder into a 100 ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
對比例6 Comparative example 6
於100ml反應瓶中依次加入合成例4合成的聚醯胺酸溶液10g、LF31-P粉體1.07g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10g of the polyamide acid solution synthesized in Synthesis Example 4 and 1.07g of LF31-P powder into a 100ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
對比例7 Comparative example 7
於100ml反應瓶中依次加入合成例5合成的聚醯胺酸溶液10g、LF31-P粉體0.441g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10 g of the polyamide acid solution synthesized in Synthesis Example 5 and 0.441 g of LF31-P powder into a 100 ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
對比例8 Comparative example 8
於100ml反應瓶中依次加入合成例5合成的聚醯胺酸溶液10g、LF31-P粉體1.35g，攪拌6小時，使粉體完全分散於聚醯胺酸溶液中，可得到高分子分散液。 Add 10 g of the polyamide acid solution synthesized in Synthesis Example 5 and 1.35 g of LF31-P powder into a 100 ml reaction flask, and stir for 6 hours to completely disperse the powder in the polyamide acid solution to obtain a polymer dispersion. .
製備液晶高分子分散液和高分子分散液各原料的具體配比及相應覆銅板的測試結果如表3所示。 Table 3 shows the specific ratios of the raw materials for the preparation of the liquid crystal polymer dispersion and the polymer dispersion and the test results of the corresponding copper clad laminates.
注：表1-3中相應的測試標準為：剝離強度的測試標準為IPC-TM650 2.4.9，漂錫測試的測試標準為IPC-TM650 2.4.13，抗張強度和延伸率的測試標準為ASTM D638。 Note: The corresponding test standards in Table 1-3 are: the test standard for peel strength is IPC-TM650 2.4.9, the test standard for bleaching tin test is IPC-TM650 2.4.13, and the test standard for tensile strength and elongation is IPC-TM650 2.4.13 ASTM D638.
表2-3中的LF31-P粉體購自新日本石油株式會社(Nippon Oil & Energy Corporation，JXTG)，平均粒徑<3μm，為全酯基結晶高分子。 The LF31-P powder in Table 2-3 was purchased from Nippon Oil & Energy Corporation (JXTG), with an average particle size of <3 μm, and is a fully ester-based crystalline polymer.
測試結果表明：由對比例1可知將LF31-P粉體(粒徑<3μm，全酯基結晶高分子)分散於NMP中，但經高溫燒結後，無法自行成膜。 The test results show that from Comparative Example 1, LF31-P powder (particle size <3μm, full ester-based crystalline polymer) is dispersed in NMP, but after high-temperature sintering, it cannot form a film by itself.
由合成例1~5可知，聚醯胺酸的合成過程中，加入含有液晶結構的單體(具體為酯基)，可使聚醯胺酸形成的覆銅板具有優異的介電損耗因數Df，並且聚醯胺酸分子鏈中液晶結構比例越多，Df值越優異，其中合成例2中二胺單體為APAB，二酸酐單體為TAHQ，兩單體中都含有液晶結構，使得聚醯胺酸的分子鏈中的液晶結構含量最多，Df相較合成例3~5的Df值低，但相應的Dk值卻升高。同時覆銅板上複合膜的剝離強度降低，液晶結構增加會使複合膜與銅箔的接著力降低，從而使剝離強度降低。而合成例3~5，有摻混相同比例的柔性結構(具體為-O-)，Df值較高，Dk值下降，同時柔性結構的添加提高了複合膜與銅箔的接著性，從而剝離強度得到提升。其中合成例5中添加的含有液晶結構的二胺單體及二酸酐單體採用分段添加聚合的方式，增加了液晶結構的分散性，進而得到具有優異Dk值和Df值，同時保有優異的剝離強度。 It can be seen from Synthesis Examples 1 to 5 that the addition of monomers containing liquid crystal structure (specifically ester groups) during the synthesis of polyamide acid can make the copper clad laminate formed by polyamide acid have an excellent dielectric loss factor Df. And the more the ratio of the liquid crystal structure in the polyamide acid molecular chain, the better the Df value. The diamine monomer in Synthesis Example 2 is APAB, and the dianhydride monomer is TAHQ. Both monomers contain liquid crystal structure, making polyamide The content of the liquid crystal structure in the molecular chain of the amino acid is the most, and the Df value is lower than that of Synthesis Examples 3 to 5, but the corresponding Dk value is higher. At the same time, the peel strength of the composite film on the copper clad laminate is reduced, and the increase in the liquid crystal structure will reduce the adhesive force of the composite film and the copper foil, thereby reducing the peel strength. In the synthesis examples 3~5, there are flexible structures (specifically -O-) blended in the same proportion, the Df value is higher, and the Dk value decreases. At the same time, the addition of the flexible structure improves the adhesion between the composite film and the copper foil, thereby peeling off Strength is improved. Among them, the diamine monomer and dianhydride monomer containing the liquid crystal structure added in Synthesis Example 5 adopt the method of stepwise addition polymerization, which increases the dispersibility of the liquid crystal structure, thereby obtaining excellent Dk and Df values, while maintaining excellent Peel strength.
實施例1~3採用了合成例5合成的聚醯胺酸，與合成例5相比，實施例1~3由於添加了添加了20wt%~30wt%全酯基並且不溶於溶劑的LF31-P粉體(粒徑<3μm)。液晶高分子粉體的添加能夠提高結晶結構數量，產生大量物理性結晶交聯結構，進而提升了高分子複合膜的機械性能，而且製備的覆銅板均具有優異的Df和Dk，介電損耗因數(Df)和熱膨脹係數(CTE)隨著LF31-P粉體添加量的增加有下降的趨勢，另外，高分子複合膜的剝離強度達到目標值(剝離強度大於或等於0.7kgf/cm)。 Examples 1 to 3 used the polyamide acid synthesized in Synthesis Example 5. Compared with Synthesis Example 5, Examples 1 to 3 added LF31-P which was insoluble in solvents and added 20wt% to 30wt% of full ester groups. Powder (particle size <3μm). The addition of liquid crystal polymer powder can increase the number of crystalline structures and produce a large number of physical crystalline cross-linked structures, thereby improving the mechanical properties of the polymer composite film, and the prepared copper clad laminates have excellent Df, Dk, and dielectric loss factor. (Df) and coefficient of thermal expansion (CTE) have a downward trend with the increase of LF31-P powder addition. In addition, the peel strength of the polymer composite film reaches the target value (the peel strength is greater than or equal to 0.7kgf/cm).
相較於實施例1，對比例3~5對應的高分子分散液雖然添加了相同含量的液晶高分子粉體，液晶高分子粉體的添加能夠提高結晶結構數量及產生物理性結晶交聯結構，進而提升了高分子複合膜的機械性能，覆銅板的Df也有所降低，但高分子複合膜的剝離強度和熱膨脹係數均降低，同時覆銅板的Dk升高，這是因為對比例3中用於製備聚醯胺酸的二胺單體與二酸酐單體都是含液晶結構的單體，沒有搭配柔性結構，導致聚醯胺酸分子的自由度降低，分子鏈的柔韌性降低，使聚醯胺酸分子與液晶高分子粉體的相容性變差，導致高分子複合膜的熱膨脹係數和剝離強度降低，同時覆銅板的Dk有所升高。對比例4~5用於製備聚醯胺酸的二胺單體或二酸酐單體單獨引入液晶結構，結晶相在網路結構中的分佈相對於實施例1而言均勻性下降，從而降低了液晶高分子結晶相與聚醯亞胺結晶相的物理性結晶交聯點的數量，導致高分子複合膜的Df、剝離強度和熱膨脹係數均降低，同時覆銅板的Dk升高且超過了目標值(Dk優選在3.2~3.3之間)。 Compared with Example 1, although the polymer dispersions corresponding to Comparative Examples 3 to 5 are added with the same content of liquid crystal polymer powder, the addition of liquid crystal polymer powder can increase the number of crystalline structures and produce physical crystalline cross-linked structures. , Thus improving the mechanical properties of the polymer composite film, the Df of the copper clad laminate has also been reduced, but the peel strength and thermal expansion coefficient of the polymer composite film are reduced, and the Dk of the copper clad laminate is increased. The diamine monomers and dianhydride monomers used in the preparation of polyamide acid are monomers containing liquid crystal structure, and there is no flexible structure. The compatibility between the amide acid molecules and the liquid crystal polymer powder becomes poor, resulting in a decrease in the thermal expansion coefficient and peel strength of the polymer composite film, and an increase in the Dk of the copper clad laminate. In Comparative Examples 4~5, the diamine monomer or dianhydride monomer used to prepare polyamide acid is introduced into the liquid crystal structure alone, and the distribution of the crystalline phase in the network structure is less uniform than in Example 1, thereby reducing The number of physical crystalline cross-linking points between the liquid crystal polymer crystal phase and the polyimide crystal phase leads to a decrease in the Df, peel strength and thermal expansion coefficient of the polymer composite film, while the Dk of the copper clad laminate increases and exceeds the target value (Dk is preferably between 3.2 and 3.3).
與實施例3相比，對比例6雖然添加了相同含量的液晶高分子粉體，能夠提高結晶結構數量及物理性結晶交聯結構，使得高分子複合膜的機械性能提升，覆銅板的Df值下降，但同時高分子複合膜的剝離強度下降，覆銅板的Dk值上升，並超過了目標值。 Compared with Example 3, in Comparative Example 6, although the same content of liquid crystal polymer powder is added, it can increase the number of crystal structures and the physical crystal cross-linking structure, so that the mechanical properties of the polymer composite film are improved, and the Df value of the copper clad laminate Decrease, but at the same time the peel strength of the polymer composite film decreased, and the Dk value of the copper clad laminate increased and exceeded the target value.
而對比例2中採用的合成例1的聚醯胺酸，其中合成例1的聚醯胺酸中無液晶結構，表明無液晶結構的聚醯胺酸與LF31-P粉體相容性差，從而造成高分子複合膜膜機械性能下降，剝離強度大幅下降。 However, the polyamide acid of Synthesis Example 1 used in Comparative Example 2 has no liquid crystal structure in the polyamide acid of Synthesis Example 1, which indicates that the polyamide acid without a liquid crystal structure has poor compatibility with LF31-P powder, thus As a result, the mechanical properties of the polymer composite membrane are reduced, and the peel strength is greatly reduced.
由實施例1~3和對比例7~8可知，LF31-P粉體添加量提升，有利於覆銅板Df值的下降，但覆銅板的Dk值會上升同時高分子複合膜的剝離強度會下降。對比例7中LF31-P粉體添加量太少，Df值未到達目標值(Df優選在0.001~0.002之間)。而對比例8中LF31-P粉體添加量太多，Dk值及剝離強度均超過目標值(Dk優選在3.2~3.3之間)。 From Examples 1 to 3 and Comparative Examples 7 to 8, it can be seen that the increase in the amount of LF31-P powder added is beneficial to the decrease of the Df value of the copper clad laminate, but the Dk value of the copper clad laminate will increase and the peel strength of the polymer composite film will decrease. . In Comparative Example 7, the amount of LF31-P powder added was too small, and the Df value did not reach the target value (Df is preferably between 0.001 and 0.002). In Comparative Example 8, the LF31-P powder was added too much, and the Dk value and the peel strength both exceeded the target value (Dk is preferably between 3.2 and 3.3).
綜上所述，本發明提供的高分子分散液，藉由將液晶高分子粉體與同時含有液晶結構和柔性結構的熱塑性聚醯胺酸混合，形成分散液，可有效提高分散液的固含量和黏度，而且形成的分散液穩定性好，有利於分散液的成膜，形成的覆銅板中高分子複合膜與銅板的接著性良好，同時高分子複合膜中 形成的兩種晶相能夠藉由結晶交聯點形成網路結構，有效降低了覆銅板的Df和熱膨脹係數，同時提高了高分子複合膜的機械性能。 In summary, the polymer dispersion provided by the present invention can effectively increase the solid content of the dispersion by mixing the liquid crystal polymer powder with the thermoplastic polyamide containing both a liquid crystal structure and a flexible structure to form a dispersion. And viscosity, and the stability of the dispersion formed is good, which is conducive to the film formation of the dispersion. The adhesion of the polymer composite film to the copper plate in the formed copper clad laminate is good. The two crystal phases formed can form a network structure through the crystal cross-linking points, which effectively reduces the Df and thermal expansion coefficient of the copper clad laminate, and at the same time improves the mechanical properties of the polymer composite film.
以上實施例和對比例的說明只是用於幫助理解本發明的方法及其核心思想；另外，對於本領域的普通技術人員來說，可以根據本發明的技術構思做出其它各種相應的改變與變形，而所有這些改變與變形都應屬於本發明請求項的保護範圍。 The descriptions of the above embodiments and comparative examples are only used to help understand the method and core idea of the present invention; in addition, for those of ordinary skill in the art, various other corresponding changes and modifications can be made according to the technical idea of the present invention. , And all these changes and modifications shall belong to the protection scope of the claims of the present invention.
1:液晶高分子晶體 1: Liquid crystal polymer crystal
3:聚醯亞胺晶體 3: Polyimide crystal
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