TWI488918B - Black polyamide acid composition and black polyimide resin - Google Patents
Black polyamide acid composition and black polyimide resin Download PDFInfo
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本發明是有關一種聚醯胺酸組成物及聚醯亞胺樹脂,且特別是有關於一種黑色聚醯胺酸組成物以及黑色聚醯亞胺樹脂。The present invention relates to a polylysine composition and a polyimine resin, and more particularly to a black polyaminic acid composition and a black polyimine resin.
可撓性積層板主要係由絕緣性塑料層疊合金屬板或金屬箔所構成,在多種絕緣性塑料中,聚醯亞胺樹脂具有良好的耐熱性、可加工性等材料性質,因此適於做為可撓性積層板之絕緣層材料。隨著可撓性積層板廣泛地應用於薄型化、多能化的攝影裝置、顯示裝置等各種電子產品,亦開始要求應用於不同的電子產品中的可撓性積層板需要具備不同的光學性質,例如在顯示裝置中,光源會通過配置於顯示器周邊之可撓性印刷配線板,造成顯示器之框體接合部位對外部產生漏光之問題,目前已有藉由摻合含有碳黑成分的黑色顏料而將可撓性積層板之聚醯亞胺絕緣層黑色化的方法,使可撓性積層板具有遮光性。然而,含有碳黑成分的黑色顏料具有導電性,從而使聚醯亞胺絕緣層之絕緣性降低且材料性質劣化的缺點。因此,如何解決上述種種問題,即是發展本發明之目的。The flexible laminate is mainly composed of an insulating plastic laminated metal plate or a metal foil. Among various insulating plastics, the polyimide resin has good heat resistance and processability, and is therefore suitable for doing. It is the insulating layer material of the flexible laminate. As flexible laminates are widely used in various electronic products such as thinner and more versatile photographic devices and display devices, flexible laminates that are required to be applied to different electronic products are required to have different optical properties. For example, in a display device, a light source passes through a flexible printed wiring board disposed on the periphery of the display, causing a problem of light leakage to the outside of the frame joint portion of the display. Currently, a black pigment containing a carbon black component has been blended. Further, the flexible laminate sheet is made to have a light-shielding property by blackening the polyimide layer of the flexible laminate. However, the black pigment containing a carbon black component has electrical conductivity, thereby lowering the insulating property of the polyimide polyimide insulating layer and deteriorating the material properties. Therefore, how to solve the above problems is to develop the object of the present invention.
本發明的目的就是在提供一種黑色聚醯胺酸組成物,應用於製造黑色聚醯亞胺樹脂,其包含一聚醯胺酸以及一黑色顏料。黑色顏料包 含一苯胺以及一苯胺金屬錯化物。苯胺具有如化學式1所示之結構,其中R1及R2可獨立或同時地選自氫原子、碳數為1~6的烴基、被取代之烷基、被取代之環烷基或被取代之苯基。苯胺金屬錯化物具有如化學式2所示之結構,其中R3及R4可獨立或同時地選自氫原子、碳數為1~6的烴基、被取代之烷基、被取代之環烷基或被取代之苯基,以及M係選自鉻(Cr)、錳(Mn)、鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)或鋅(Zn)。It is an object of the present invention to provide a black polyaminic acid composition for use in the manufacture of a black polyimine resin comprising a poly-proline and a black pigment. Black pigment pack Containing monoaniline and monoaniline metal complex. Aniline has a structure as shown in Chemical Formula 1, wherein R1 and R2 may be independently or simultaneously selected from a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a substituted alkyl group, a substituted cycloalkyl group or a substituted benzene group. base. The aniline metal complex has a structure represented by Chemical Formula 2, wherein R3 and R4 may be independently or simultaneously selected from a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a substituted alkyl group, a substituted cycloalkyl group or a The substituted phenyl group and the M system are selected from the group consisting of chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn).
在本發明之一實施例中,上述黑色聚醯胺酸組成物還可包含一無機陶瓷填料。無機陶瓷填料係選自氮化硼(BN)、三氧化二鋁(Al2O3)、氮化鋁(AlN)、二氧化鈦(TiO2)、二氧化矽(SiO2)其中一種或多種材料混合而成。In an embodiment of the invention, the black polylysine composition may further comprise an inorganic ceramic filler. The inorganic ceramic filler is selected from the group consisting of boron nitride (BN), aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), titanium dioxide (TiO 2 ), and cerium oxide (SiO 2 ).
本發明的再一目的就是在提供一種黑色聚醯亞胺樹脂,其係由上述黑色聚醯胺酸組成物所形成之一黑色聚醯亞胺樹脂。黑色聚醯亞胺樹脂具有玻璃轉移溫度(Tg)為280℃~400℃,以及線性熱膨脹係數CTE 5ppm~50ppm(100℃~200℃)。A further object of the present invention is to provide a black polyimine resin which is a black polyimine resin formed from the above black polyaminic acid composition. The black polyimine resin has a glass transition temperature (Tg) of 280 ° C to 400 ° C and a linear thermal expansion coefficient of CTE 5 ppm to 50 ppm (100 ° C to 200 ° C).
在本發明之黑色聚醯胺酸組成物中所使用之黑色顏料不會影響聚醯亞胺樹脂的材料性質,本發明之黑色聚醯胺酸組成物還更可添加無機陶瓷填料,使用添加有無機陶瓷填料之黑色聚醯胺酸組成物所製成之黑色聚醯亞胺樹脂層,應用於製造背膠膜或可撓性積層結構等用途中,均能達到極佳的光學以及材料性質,進而可供製造出各種薄型化、多能化的電子產品。The black pigment used in the black polyaminic acid composition of the present invention does not affect the material properties of the polyimine resin, and the black polyphthalic acid composition of the present invention can further be added with an inorganic ceramic filler. The black polyimine resin layer made of the black polyamic acid composition of the inorganic ceramic filler can be used for the manufacture of a backing film or a flexible laminated structure, and can achieve excellent optical and material properties. Furthermore, it is possible to manufacture various thin and versatile electronic products.
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說明如下。The above and other objects, features and advantages of the present invention will become more <RTIgt;
100、100 I、100 II、200 I、200 II、300‧‧‧可撓性積層結構100, 100 I, 100 II, 200 I, 200 II, 300‧‧‧Flexible laminated structure
110、120‧‧‧黑色聚醯亞胺樹脂層110, 120‧‧‧ black polyimine resin layer
110 I‧‧‧第一黑色聚醯亞胺樹脂層110 I‧‧‧First black polyimide resin layer
110 II‧‧‧第二黑色聚醯亞胺樹脂層110 II‧‧‧Second black polyimide resin layer
111、121‧‧‧第一表面111, 121‧‧‧ first surface
112、122‧‧‧第二表面112, 122‧‧‧ second surface
113‧‧‧第三表面113‧‧‧ third surface
114‧‧‧第四表面114‧‧‧Fourth surface
210、210 I‧‧‧第一金屬層210, 210 I‧‧‧ first metal layer
210 II、220‧‧‧第二金屬層210 II, 220‧‧‧ second metal layer
230‧‧‧無縫連續式鋼帶230‧‧‧Seamless continuous steel strip
310‧‧‧接著層310‧‧‧Next layer
圖1繪示為本發明之第一較佳實施例剖面示意圖。1 is a cross-sectional view showing a first preferred embodiment of the present invention.
圖1A及1B繪示為應用本發明之第一較佳實施例所製成可撓性積層 結構之剖面示意圖。1A and 1B illustrate a flexible laminate formed by applying the first preferred embodiment of the present invention. Schematic diagram of the structure.
圖2繪示為本發明之第二較佳實施例剖面示意圖。2 is a cross-sectional view showing a second preferred embodiment of the present invention.
圖2A繪示為應用本發明之第二較佳實施例所製成可撓性積層結構之剖面示意圖。2A is a schematic cross-sectional view showing a flexible laminate structure formed by applying the second preferred embodiment of the present invention.
本發明提供一種可應用於製造黑色聚醯亞胺樹脂的黑色聚醯胺酸組成物。在本實施例中,黑色聚醯胺酸組成物主要由聚醯胺酸以及黑色顏料所組成。在本發明中,聚醯胺酸係由二酐化合物、二胺化合物所形成,其中二酐化合物係選自:2,2-雙(3,4-二羧酸)六氟丙烷二酐雙酐(6FDA)、4-(2,5-二氧代四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二甲酸雙酐(TDA)、均苯四甲酸二酐(1,2,4,5-均苯四甲酸二酐,PMDA)、二苯酮四甲酸二酐(benzophenone tetracarboxylic dianhydride,BTDA)、聯苯四羧酸二酐(Biphenyltetracarboxylic dianhydride,BPDA)、4,4,-氧苯二甲酸酐(4,4,-Oxydiphthalic dianhydride,4,4,-ODPA)、3,4,-氧苯二甲酸酐(3,4,-Oxydiphthalic dianhydride,3,4,-ODPA)、雙-二羧基苯基二甲基矽烷二酐(bis dicarboxyphenyl dimethylsilane dianhydride,SiDA)、雙二(羧基苯氧基)二苯硫醚二酐(Bis(dicarboxyphenoxy)diphenyl sulfide dianhydride,BDSDA)、1,4,5,8-亞萘四甲酸二酐(1,4,5,8-Naphthalenetetracarboxylicdianhydride、NTCDA)、對苯二酚二酞酸酐(hydroquinnone diphtalicanhydride、HQDA)、雙酚A二酐(4,4'-bisphenol A dianhydride、BPADA)、1,3-二氫-1,3-二氧-5-異苯并呋喃羧酸亞苯酯3,3',4,4'-二苯基碸四酸酐(3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride、DSDA)、(1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid phenylene ester、TAHQ)、二苯基碸四羧酸二酸酐(sulfonyldiphthalic anhydride,SO 2 DPA)、環丁烷四甲酸二酐(Cyclobutane-1,2,3,4-tetracarboxylic dianhydride, CBDA)、(異丙基二苯氧基)雙(鄰苯二甲酸酐)(isopropylidene di-phenoxy)bis(phthalic anhydride),6HBDA)等其中的一種或多種,但並不限於此; 二胺化合物係選自:4,4-二胺基二苯醚(4,4'-oxydianiline、4,4'-ODA)、3,4-二胺基二苯醯(3,4'-Oxydianiline、3,4'-ODA)、3,3’-二羥基-4,4'-二胺基聯苯(3,3’-dihydroxy-4,4'-diamino-biphenyl、HAB)對苯二胺(p-PDA)、間苯二胺(m-PDA)、對亞甲基二胺(pMDA)、間亞甲基二胺(mMDA)、雙胺基苯氧基苯(Bis aminophenoxy benzene,133APB,134APB)、雙胺基苯氧基苯基六氟丙烷(bis aminophenoxy phenyl hexafluoropropane,4BDAF)、雙胺苯六氟丙烷(bis aminophenyl hexafluoropropane,33-6F,44-6F)、二胺基二苯碸(bis aminophenyl sulfone,4DDS,3DDS)、2,2-雙(4-[4-胺基苯氧基]苯基)丙烷(2,2-Bis(4-[4-aminophenoxy]phenyl)propane、BAPP)、2,2-雙(4-[3-胺基苯氧基]苯基)碸(2,2-Bis(4-[3-aminophenoxy]phenyl)sulfone、m-BAPS)、1,4-雙(4-胺基苯氧基)苯(1,4-Bis(4-aminophenoxy)benzene、TPE-Q)、1,3-雙(4-胺基苯氧基)苯(1,3-Bis(4-aminophenoxy)benzene、TPE-R)、1,3-雙(3-胺基苯氧基)苯(1,3-Bis(3-aminophenoxy)benzene、APB)、4,4-雙(4-胺基苯氧基)聯苯(4,4'-Bis(4-aminophenoxy)biphenyl、BAPB)、1,4-雙(4-胺基苯氧基)-2,5-第三丁基苯(1,4-Bis(4-aminophenoxy)-2,5-di-t-butylbenzene、DTBAB)、4,4'-雙(4-胺基苯氧基)二苯甲酮(4,4'-Bis(4-aminophenoxy)benzophenone、BAPK)二(三氟甲基)二胺基聯苯(Bis(trifluoromethyl)benzidine,TFDB)環己烷二胺(Cyclohexanediamine,13CHD,14CHD)、雙胺基苯氧基苯基丙烷bis aminophenoxy phenyl propane,6HMDA)、雙胺基羥基苯基六氟丙烷(Bis aminohydroxyphenyl hexafluoropropane,DBOH)、雙胺基苯氧基二苯基碸(bis aminophenoxy diphenyl sulfone,DBSDA)等其中的一種或多種,但並不限於此; 黑色顏料包含苯胺以及苯胺金屬錯化物,其中苯胺具有如化學式1所示之結構:,其中R1及R2可獨立或同時地選自氫原子、碳數為1~6的烴基、被取代之烷基、被取代之環烷基或被取代之苯基;以及苯胺金屬錯化物,具有化學式2所示之結構:,其中R3及R4可獨立或同時地選自氫原子、碳數為1~6的烴基、被取代之烷基、被取代之環烷基或被取代之苯基;以及M係選自鉻(Cr)、錳(Mn)、鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)或鋅(Zn)。The present invention provides a black polylysine composition which can be applied to the manufacture of a black polyimine resin. In this embodiment, the black polyaminic acid composition is mainly composed of polyglycine and a black pigment. In the present invention, the poly-proline acid is formed from a dianhydride compound and a diamine compound, wherein the dianhydride compound is selected from the group consisting of: 2,2-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride dianhydride. (6FDA), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (TDA), pyromellitic acid II Anhydride (1,2,4,5-pyromellitic dianhydride, PMDA), benzophenone tetracarboxylic dianhydride (BTDA), biphenyltetracarboxylic dianhydride (BPDA), 4 , 4,- oxyphthalic anhydride (4,4,-Oxydiphthalic dianhydride, 4,4,-ODPA), 3,4,- oxyphthalic anhydride (3,4,-Oxydiphthalic dianhydride, 3,4,- ODPA), bis-dicarboxyphenyl dimethylsilane dianhydride (SiDA), bis(carboxyphenoxy)diphenyl sulfide dianhydride (BDSDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), hydroquinnone diphtalicanhydride (HQDA), bisphenol A dianhydride (4, 4'-bisphenol A dianhydride, BPA DA), 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylate, 3,3',4,4'-diphenyltetradecanoic anhydride (3,3', 4,4'-Diphenylsulfone tetracarboxylic dianhydride, DSDA), (1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid phenylene ester, TAHQ), sulfonyldiphthalic anhydride (SO 2 ) DPA), cyclobutane-1, 2,3,4-tetracarboxylic dianhydride ( CBDA), (isopropyl diphenoxy) bis (phthalic anhydride) (isopropylidene di-phenoxy) One or more of bis (phthalic anhydride), 6HBDA), etc., but not limited thereto; the diamine compound is selected from the group consisting of 4,4-diaminodiphenyl ether (4,4'-oxydianiline, 4,4' -ODA), 3,4-diaminodiphenyl hydrazine (3,4'-Oxydianiline, 3,4'-ODA), 3,3'-dihydroxy-4,4'-diaminobiphenyl (3 , 3'-dihydroxy-4,4'-diamino-biphenyl, HAB) p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), p-methylenediamine (pMDA), methylene Bisaminophenoxy benzene (133APB, 134APB), bis aminophenoxy phenyl hexafl Uoropropane, 4BDAF), bis aminophenyl hexafluoropropane (33-6F, 44-6F), bis aminophenyl sulfone (4DDS, 3DDS), 2,2-bis (4-[ 4-aminophenoxy]phenyl)propane (2,2-Bis(4-[4-aminophenoxy]phenyl)propane, BAPP), 2,2-bis(4-[3-aminophenoxy] Phenyl) 2,2-Bis(4-[3-aminophenoxy]phenyl)sulfone, m-BAPS), 1,4-bis(4-aminophenoxy)benzene (1,4-Bis(4) -aminophenoxy)benzene, TPE-Q), 1,3-bis(4-aminophenoxy)benzene, TPE-R, 1,3-double (3 -1,3-Bisphenoxybenzene, APB, 4,4-bis(4-aminophenoxy)biphenyl (4,4'-Bis(4- Aminophenoxy)biphenyl, BAPB), 1,4-bis(4-aminophenoxy)-2,5-t-butylbenzene (1,4-Bis(4-aminophenoxy)-2,5-di-t -butylbenzene, DTBAB), 4,4'-bis(4-aminophenoxy)benzophenone (4,4'-Bis(4-aminophenoxy)benzophenone, BAPK) bis(trifluoromethyl)diamine Bis(trifluoromethyl)benzidine, TFDB) Cyclohexanediamine (13CHD, 14CHD), bisaminophenoxy phenyl bisaminophenoxy phenyl Propane, 6HMDA), Bis aminohydroxyphenyl hexafluoropropane (DBOH), bis aminophenoxy diphenyl sulfone (DBSDA), etc., but not Limited to this; the black pigment comprises aniline and an aniline metal complex, wherein the aniline has a structure as shown in Chemical Formula 1: , wherein R 1 and R 2 may be independently or simultaneously selected from a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a substituted alkyl group, a substituted cycloalkyl group or a substituted phenyl group; and an aniline metal complex compound having The structure shown in Chemical Formula 2: Wherein R 3 and R 4 may be independently or simultaneously selected from a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a substituted alkyl group, a substituted cycloalkyl group or a substituted phenyl group; and the M group is selected from chromium ( Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn).
應用上述黑色聚醯胺酸組成物來製造黑色聚醯亞胺樹脂可如下述方式來完成。請參見圖1所示本發明之第一較佳實施例剖面示意圖。首先,添加黑色顏料於上述聚醯胺酸而形成黑色聚醯胺酸組成物,其中添加黑色顏料之固體成分重量為上述聚醯胺酸之固體成分重量之1%~30%,再以溶劑溶解上述黑色聚醯胺酸組成物製成黑色聚醯胺酸溶液。接著,以精密塗佈或預鑄(Casting)黑色聚醯胺酸溶液於第一金屬層210表面,其中第一金屬層210之材料可以為銅、鋁、鐵、銀、鈀、鎳、鉻、鉬、鎢、鋅、不鏽鋼或上述金屬之合金層,第一金屬層210之厚度介於5微米~70微米。之後,以250℃~400℃之高溫,經10分鐘~300分鐘對上述黑色聚醯胺酸溶液予以熟化後,即可於金屬層210上形成黑色聚醯亞胺樹脂層110,黑色聚醯亞胺樹脂層110與金屬層210構成可撓性積層結構100。The use of the above black polyaminic acid composition to produce a black polyimine resin can be accomplished as follows. Please refer to FIG. 1 for a schematic cross-sectional view of a first preferred embodiment of the present invention. First, a black pigment is added to the polylysine to form a black polyaminic acid composition, wherein the weight of the solid component added with the black pigment is 1% to 30% by weight of the solid component of the polylysine, and then dissolved in a solvent. The above black polyaminic acid composition was made into a black polyaminic acid solution. Next, a surface of the first metal layer 210 is coated with a fine coating or a Casting black polyaminic acid solution, wherein the material of the first metal layer 210 may be copper, aluminum, iron, silver, palladium, nickel, chromium, An alloy layer of molybdenum, tungsten, zinc, stainless steel or the above metal, the first metal layer 210 having a thickness of between 5 micrometers and 70 micrometers. Thereafter, after the black polyaminic acid solution is aged at a high temperature of 250 ° C to 400 ° C for 10 minutes to 300 minutes, a black polyimine resin layer 110 can be formed on the metal layer 210, black poly The amine resin layer 110 and the metal layer 210 constitute the flexible laminate structure 100.
詳細來說,製備黑色聚醯胺酸溶液的溶劑可選自:N-甲基-2- 吡咯烷酮(N-methyl-2-pyrrolidone、NMP)、N,N-二甲基乙醯胺(N,N-dimethylacetamide、DMAc)、γ-丁內酯(γ-butyrolactone、GBL)、二甲基甲醯胺(Dimethylformamide、DMF)、2-丁氧基乙醇(2-Butoxyethanol)、2-乙氧基乙醇(2-Ethoxyethanol)等其中一種或多種溶劑混合,但並不限於此。經高溫熟化上述黑色聚醯胺酸溶液所形成的黑色聚醯亞胺樹脂層110,其玻璃轉移溫度Tg(℃)為280℃~400℃,較佳為340℃以上;線性熱膨脹係數CTE 5ppm~50ppm(100℃~200℃)。可撓性積層結構100包含有黑色聚醯亞胺樹脂層110,不僅具有良好的遮光效果,也具有良好的加工性,所以可撓性積層結構100可應用於製造各種薄型化、多能化的電子產品。值得一提的是,在不同的實施方式中,可於第一金屬層210上重複數次上述精密塗佈或預鑄黑色聚醯胺酸溶液與高溫熟化黑色聚醯胺酸溶液形成黑色聚醯亞胺樹脂層110之步驟,用以調整可撓性積層結構100的積層數目或厚度尺寸。In detail, the solvent for preparing the black polyaminic acid solution may be selected from the group consisting of: N-methyl-2- Pyrrolidone (N-methyl-2-pyrrolidone, NMP), N,N-dimethylacetamide (DMAc), γ-butyrolactone (GBL), dimethylformate One or more solvents such as Dimethylformamide (DMF), 2-Butoxyethanol, 2-Ethoxyethanol, and the like are mixed, but are not limited thereto. The black polyimine resin layer 110 formed by curing the black polyaminic acid solution at a high temperature has a glass transition temperature Tg (° C.) of 280° C. to 400° C., preferably 340° C. or more; and a linear thermal expansion coefficient of CTE 5 ppm. 50ppm (100 ° C ~ 200 ° C). The flexible laminate structure 100 includes the black polyimide resin layer 110, which not only has good light shielding effect but also good processability, so the flexible laminate structure 100 can be applied to manufacture various thin and versatile products. electronic product. It is worth mentioning that, in different embodiments, the above precision coating or the ruthenium black polyaminic acid solution and the high temperature aging black polyaminic acid solution may be repeated on the first metal layer 210 to form a black polyfluorene. The step of the imide resin layer 110 is for adjusting the number of layers or the thickness of the flexible laminate structure 100.
請參見圖1A所示剖面示意圖,可撓性積層結構100 I以及100 II同樣為一種單面金屬可撓性積層結構,可撓性積層結構100 I包含第一黑色聚醯亞胺樹脂層110 I以及第一金屬層210 I。第一黑色聚醯亞胺樹脂層110 I具有第一表面111以及第二表面112,第一金屬層210 I接合於第二表面112。可撓性積層結構100 II包含第二黑色聚醯亞胺樹脂層110 II以及第二金屬層210 II。第二黑色聚醯亞胺樹脂層110 II具有第三表面113以及第四表面114,第二金屬層210 II接合於第四表面。接著,於第一表面111上形成接著層310,其中接著層之材料係選自環氧樹脂、苯氧基樹脂、丙烯酸樹脂、胺基甲酸乙酯樹脂其中一種或多種材料混合而成。之後,熱壓著可撓性積層結構100 I以及100 II,而形成一種具有雙層黑色聚醯亞胺樹脂層以及雙面金屬層之可撓性積層結構200 I。Referring to the cross-sectional view of FIG. 1A, the flexible laminated structures 100 I and 100 II are also a single-sided metal flexible laminated structure, and the flexible laminated structure 100 I includes a first black polyimide resin layer 110 I. And a first metal layer 210 I. The first black polyimide resin layer 110 I has a first surface 111 and a second surface 112, and the first metal layer 210I is bonded to the second surface 112. The flexible laminate structure 100 II includes a second black polyimide resin layer 110 II and a second metal layer 210 II. The second black polyimide resin layer 110 II has a third surface 113 and a fourth surface 114, and the second metal layer 210 II is bonded to the fourth surface. Next, an adhesive layer 310 is formed on the first surface 111, wherein the material of the adhesive layer is selected from the group consisting of epoxy resin, phenoxy resin, acrylic resin, and urethane resin. Thereafter, the flexible laminate structures 100 I and 100 II are heat-pressed to form a flexible laminate structure 200 1 having a double-layered black polyimide resin layer and a double-sided metal layer.
再請參見圖1B所示剖面示意圖,完成如圖1所示之可撓性積層結構100後,於第一表面111上形成接著層310。接著,對位第二金屬層220與接著層310,其中第二金屬層220之材料可以為銅、鋁、鐵、銀、鈀、鎳、鉻、鉬、鎢、鋅、不鏽鋼或上述金屬之合金層,第二金屬層220之厚度介於5微米~70微米,而形成另一種具有雙面金屬層之可撓性積層結構200 II。Referring to the cross-sectional view of FIG. 1B, after the flexible laminate structure 100 shown in FIG. 1 is completed, the adhesive layer 310 is formed on the first surface 111. Next, the second metal layer 220 and the subsequent layer 310 are aligned, wherein the material of the second metal layer 220 may be copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zinc, stainless steel or an alloy of the above metals. The layer, the second metal layer 220 has a thickness of between 5 micrometers and 70 micrometers, and forms another flexible laminate structure 200 II having a double-sided metal layer.
為了能提高可撓性積層結構之遮光性,本發明還提供一種可應用於製造黑色聚醯亞胺樹脂的黑色聚醯胺酸組成物。在本實施例中,黑色聚醯胺酸組成物除包含如第一實施例中所述之聚醯胺酸以及黑色顏料,更包含一無機陶瓷填料。該無機陶瓷填料係選自氮化硼(BN)、三氧化二鋁(Al2O3)、氮化鋁(AlN)、二氧化鈦(TiO2)、二氧化矽(SiO2)其中一種或多種材料混合而成。使用本實施例中所述包含有無機陶瓷填料之黑色聚醯胺酸組成物來製成黑色聚醯亞胺樹脂,可以是如第一實施例中所說明的方法,或是以下述方法來完成。In order to improve the light blocking property of the flexible laminate structure, the present invention also provides a black polyaminic acid composition which can be applied to the manufacture of a black polyimide resin. In the present embodiment, the black polyaminic acid composition further comprises an inorganic ceramic filler in addition to the polyamic acid as described in the first embodiment and the black pigment. The inorganic ceramic filler is selected from the group consisting of boron nitride (BN), aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), titanium dioxide (TiO 2 ), and cerium oxide (SiO 2 ). The black polyimine resin composition containing the inorganic polyamic acid filler described in the present embodiment is used to form a black polyimine resin, which may be the method as described in the first embodiment, or may be carried out in the following manner. .
請參見圖2所示本發明之第二較佳實施例剖面示意圖。首先,以溶劑溶解上述聚醯胺酸、黑色顏料以及無機陶瓷填料,而製備成包含有無機陶瓷填料之黑色聚醯胺酸溶液。接著,塗佈包含有無機陶瓷填料之黑色聚醯胺酸溶液於無縫連續式鋼帶230上。接著,以250℃~400℃之高溫,經10分鐘~300分鐘對包含有無機陶瓷填料之黑色聚醯胺酸溶液予以熟化後,即可於無縫連續式鋼帶230上形成包含有無機陶瓷填料之黑色聚醯亞胺樹脂層120。之後,可將包含有無機陶瓷填料之黑色聚醯亞胺樹脂層120自無縫連續式鋼帶上脫附,而形成包含有無機陶瓷填料之黑色聚醯亞胺樹脂膜,黑色聚醯亞胺樹脂層120的厚度值介於5微米~100微米。Please refer to FIG. 2 for a schematic cross-sectional view of a second preferred embodiment of the present invention. First, a solution of the above polyamic acid, a black pigment, and an inorganic ceramic filler is dissolved in a solvent to prepare a black polyaminic acid solution containing an inorganic ceramic filler. Next, a black polyaminic acid solution containing an inorganic ceramic filler is applied to the seamless continuous steel strip 230. Then, the black polyaminic acid solution containing the inorganic ceramic filler is aged at a high temperature of 250 ° C to 400 ° C for 10 minutes to 300 minutes to form an inorganic ceramic on the seamless continuous steel strip 230. A black polyimine resin layer 120 of filler. Thereafter, the black polyimine resin layer 120 containing the inorganic ceramic filler may be desorbed from the seamless continuous steel strip to form a black polyimine resin film containing the inorganic ceramic filler, black polyimine. The resin layer 120 has a thickness ranging from 5 micrometers to 100 micrometers.
本發明所選用之無機陶瓷填料,除可增加黑色聚醯亞胺樹脂的遮光性,更可修飾黑色聚醯亞胺樹脂的材料性質。簡要來說,該無機陶瓷填料為顆粒狀固態無機化合物,選擇該無機陶瓷填料的平均粒徑大小,較佳為形成黑色聚醯亞胺樹脂層的膜層厚度的10%~50%,但不以此為限。於製備包含有無機陶瓷填料之黑色聚醯胺酸溶液時,添加該無機陶瓷填料的固體成分重量較佳為聚醯胺酸的固體成分重量的1%~30%。此外,還可依據黑色聚醯亞胺樹脂應用於不同的用途,而相對應地添加該有無機陶瓷填料之固體成分重量,用以調整黑色聚醯亞胺樹脂層120之材料性質。The inorganic ceramic filler selected for use in the invention can not only increase the light-shielding property of the black polyimine resin, but also modify the material properties of the black polyimide resin. Briefly, the inorganic ceramic filler is a granular solid inorganic compound, and the average particle size of the inorganic ceramic filler is selected, preferably 10% to 50% of the thickness of the black polyimine resin layer, but not This is limited to this. When the black polyamic acid solution containing the inorganic ceramic filler is prepared, the weight of the solid component added to the inorganic ceramic filler is preferably from 1% to 30% by weight based on the solid component of the polyamic acid. In addition, the black polyimide resin can be applied to different applications, and the weight of the solid component of the inorganic ceramic filler is correspondingly added to adjust the material properties of the black polyimide resin layer 120.
請參見圖2A所示剖面示意圖,如上述方法將黑色聚醯亞胺樹脂層120自無縫連續式鋼帶上脫附,而形成包含有無機陶瓷填料之黑色聚醯亞胺樹脂膜。黑色聚醯亞胺樹脂層120具有第一表面121以及第二表面122。接著,於第一表面121上形成接著層310,其中接著層310之材料 同樣係可選自環氧樹脂、苯氧基樹脂、丙烯酸樹脂、胺基甲酸乙酯樹脂其中一種或多種材料混合而成,從而黑色聚醯亞胺層120與接著層310構成可撓性機層結構300。可撓性積層結構300可做為電子電路基板之背膠膜,貼附覆蓋於電子電路基板之圖案化金屬配線層上,例如:銅導線層,用以防止金屬配線層氧化或電子元件受潮而導致影響電子裝置的效能。黑色聚醯亞胺層120若係應用於製造背膠膜,其線性熱膨脹係數CTE較佳為9ppm~35ppm(100℃~200℃),更佳為12ppm~25ppm(100℃~200℃)。本實施例中包含有無機陶瓷填料之黑色聚醯亞胺樹脂層120,其同樣可依據上述第一實施例中所揭示之方法,應用於製造單面金屬可撓性積層結構或雙面金屬可撓性積層結構,其製造方法之步驟於此不再贅述。黑色聚醯亞胺樹脂層120若係應用於單面金屬可撓性積層結構或雙面金屬可撓性積層結構,其線性熱膨脹係數CTE較佳為14ppm~22ppm(100℃~200℃)。Referring to the cross-sectional view shown in FIG. 2A, the black polyimine resin layer 120 is desorbed from the seamless continuous steel strip as described above to form a black polyimide film comprising an inorganic ceramic filler. The black polyimide resin layer 120 has a first surface 121 and a second surface 122. Next, an adhesive layer 310 is formed on the first surface 121, wherein the material of the subsequent layer 310 Similarly, the epoxy resin, the phenoxy resin, the acrylic resin, the urethane resin may be mixed one or more materials, so that the black polyimide layer 120 and the adhesive layer 310 form a flexible machine layer. Structure 300. The flexible laminated structure 300 can be used as a backing film of an electronic circuit substrate, and is attached to a patterned metal wiring layer covering the electronic circuit substrate, for example, a copper wire layer for preventing oxidation of the metal wiring layer or moisture of the electronic component. Lead to affect the performance of electronic devices. The black polyimine layer 120 is preferably used in the manufacture of a backing film, and has a linear thermal expansion coefficient CTE of 9 ppm to 35 ppm (100 ° C to 200 ° C), more preferably 12 ppm to 25 ppm (100 ° C to 200 ° C). The black polyimine resin layer 120 containing the inorganic ceramic filler in the embodiment can also be applied to the manufacture of the single-sided metal flexible laminated structure or the double-sided metal according to the method disclosed in the above first embodiment. The flexible laminated structure, the steps of the manufacturing method thereof will not be described herein. The black polyimine resin layer 120 is preferably used in a single-sided metal flexible laminate structure or a double-sided metal flexible laminate structure, and has a linear thermal expansion coefficient CTE of 14 ppm to 22 ppm (100 ° C to 200 ° C).
綜上所述,在本發明之黑色聚醯胺酸組成物中所使用之黑色顏料不會影響聚醯亞胺樹脂的材料性質,本發明之黑色聚醯胺酸組成物還更可添加無機陶瓷填料,使用添加有無機陶瓷填料之黑色聚醯胺酸組成物所製成之黑色聚醯亞胺樹脂層,應用於製造背膠膜或可撓性積層結構等用途中,均能達到極佳的光學以及材料性質,進而可供製造出各種薄型化、多能化的電子產品。In summary, the black pigment used in the black polyaminic acid composition of the present invention does not affect the material properties of the polyimide resin, and the black polyphthalic acid composition of the present invention can further contain inorganic ceramics. The filler, a black polyimide resin layer made of a black polyamic acid composition added with an inorganic ceramic filler, is excellent for use in the manufacture of a backing film or a flexible laminate structure. Optical and material properties make it possible to manufacture a variety of thin, versatile electronic products.
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視本案所附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached to this case.
100 I、100 II、200 I‧‧‧可撓性積層結構100 I, 100 II, 200 I‧‧‧Flexible laminate structure
110 I‧‧‧第一黑色聚醯亞胺層110 I‧‧‧First black polyimine layer
110 II‧‧‧第二黑色聚醯亞胺層110 II‧‧‧Second black polyimine layer
111‧‧‧第一表面111‧‧‧ first surface
112‧‧‧第二表面112‧‧‧ second surface
113‧‧‧第三表面113‧‧‧ third surface
114‧‧‧第四表面114‧‧‧Fourth surface
210 I‧‧‧第一金屬層210 I‧‧‧First metal layer
210 II‧‧‧第二金屬層210 II‧‧‧Second metal layer
310‧‧‧接著層310‧‧‧Next layer
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