TW202027985A - Polyimide Film - Google Patents
Polyimide Film Download PDFInfo
- Publication number
- TW202027985A TW202027985A TW108136695A TW108136695A TW202027985A TW 202027985 A TW202027985 A TW 202027985A TW 108136695 A TW108136695 A TW 108136695A TW 108136695 A TW108136695 A TW 108136695A TW 202027985 A TW202027985 A TW 202027985A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- layer
- mol
- paa
- polyimide film
- Prior art date
Links
Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Wrappers (AREA)
Abstract
Description
本發明係關於一種介電特性(電容率及損耗正切)、耐熱性、尺寸穩定性、電氣特性等優異之用於高頻基板等之聚醯亞胺(PI)薄膜者。高頻基板用於高頻段用之印刷電路或天線基板等。 The present invention relates to a polyimide (PI) film used for high-frequency substrates and the like with excellent dielectric properties (permittivity and loss tangent), heat resistance, dimensional stability, and electrical properties. High frequency substrates are used for printed circuits or antenna substrates for high frequency bands.
用於高頻段用之印刷電路或天線基板等之高頻基板用之軟性銅箔積層板(FCCL),對提昇形成於銅箔上之絕緣層之介電特性(電容率及損耗正切)有效。作為此種高頻基板用FCCL,專利文獻1中揭示有使用1~15莫耳%二聚二胺(以下有時簡稱為「DDA」)作為二胺成分之共聚合PI薄膜形成於銅箔上之FCCL。然而,此處揭示之共聚合PI薄膜於用作高頻基板用FCCL之絕緣層時,存在不易確保良好的介電特性之問題。 The flexible copper foil laminate (FCCL) used for high frequency substrates such as printed circuits or antenna substrates for high frequency bands is effective for improving the dielectric properties (permittivity and loss tangent) of the insulating layer formed on the copper foil. As such FCCL for high frequency substrates, Patent Document 1 discloses that a copolymerized PI film using 1 to 15 mol% dimer diamine (hereinafter sometimes referred to as "DDA") as the diamine component is formed on copper foil The FCCL. However, when the copolymerized PI film disclosed here is used as an insulating layer of FCCL for high-frequency substrates, there is a problem that it is difficult to ensure good dielectric properties.
另一方面,專利文獻2~7中揭示有使用較多量之DDA作為二胺成分之共聚合PI薄膜。然而,此處揭示之共聚合PI薄膜雖然介電特性優異,但為可溶於溶劑之PI,故於用作高頻基板用FCCL之絕緣層時存在耐溶劑性不足之問題。又,於使用較大量之DDA之共聚合PI薄膜中,存在線膨脹係數(CTE)增加之情況,於用作高頻基板用FCCL之絕緣層時,存在不易確保良好的尺寸穩定性之問題。 On the other hand, Patent Documents 2 to 7 disclose copolymerized PI films that use a larger amount of DDA as a diamine component. However, although the copolymerized PI film disclosed here has excellent dielectric properties, it is solvent-soluble PI. Therefore, it has a problem of insufficient solvent resistance when used as an insulating layer of FCCL for high-frequency substrates. In addition, in a copolymerized PI film using a relatively large amount of DDA, the coefficient of linear expansion (CTE) may increase. When used as an insulating layer of FCCL for high frequency substrates, there is a problem that it is difficult to ensure good dimensional stability.
[先前技術文獻] [Prior Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利第6422437號公報 [Patent Document 1] Japanese Patent No. 6422437
[專利文獻2]日本專利特開2018-140544號公報 [Patent Document 2] Japanese Patent Application Publication No. 2018-140544
[專利文獻3]日本專利特表2015-526561號公報 [Patent Document 3] Japanese Patent Publication No. 2015-526561
[專利文獻4]日本專利特開2018-168369號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2018-168369
[專利文獻5]日本專利特開2018-168370號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2018-168370
[專利文獻6]日本專利特開2018-168371號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2018-168371
[專利文獻7]日本專利特開2018-170417號公報 [Patent Document 7] Japanese Patent Laid-Open No. 2018-170417
本發明係解決上述課題者,目的在於提供一種介電特性良好且耐溶劑性、尺寸穩定性優異之可用於高頻基板用FCCL之PI薄膜。 The present invention solves the above-mentioned problems and aims to provide a PI film that has good dielectric properties, excellent solvent resistance, and dimensional stability, which can be used in FCCL for high-frequency substrates.
為解決上述課題而進行銳意研究之結果發現,藉由製成使用DDA作為二胺成分之特定之PI薄膜,而可解決上述課題,以致完成本發明。 As a result of intensive research to solve the above-mentioned problems, it was found that the above-mentioned problems can be solved by forming a specific PI film using DDA as a diamine component, and the present invention has been completed.
本發明將以下內容作為主旨。 The present invention has the following contents as the gist.
<1>一種溶劑不溶性PI薄膜,其相對於總二胺成分,使用了超過15莫耳%且未滿50莫耳%之二聚二胺。 <1> A solvent-insoluble PI film using dimer diamine exceeding 15 mol% and less than 50 mol% relative to the total diamine component.
<2>一種積層薄膜,其包含上述溶劑不溶性PI薄膜及非熱塑性PI薄膜。 <2> A laminated film comprising the aforementioned solvent-insoluble PI film and a non-thermoplastic PI film.
<3>一種FCCL,其包含上述積層PI薄膜及銅箔。 <3> An FCCL including the above-mentioned laminated PI film and copper foil.
本發明之PI薄膜係介電特性、耐溶劑性優異。因此,可較佳地用作構成用於印刷電路或天線基板等之高頻基板用FCCL之絕緣層之PI薄膜。 The PI film of the present invention has excellent dielectric properties and solvent resistance. Therefore, it can be preferably used as a PI film constituting an insulating layer of FCCL for high-frequency substrates used in printed circuits, antenna substrates, and the like.
以下,詳細地說明本發明。 Hereinafter, the present invention will be explained in detail.
本發明之PI薄膜(以下有時簡稱為「PI-1層」)需要包含相對於總二胺成分,使用了超過15莫耳%且未滿50莫耳%之DDA之PI,較佳為設為16莫耳%以上、40莫耳%以下。 The PI film of the present invention (hereinafter sometimes referred to as "PI-1 layer") needs to contain PI that uses more than 15 mol% and less than 50 mol% of DDA relative to the total diamine components. It is 16 mol% or more and 40 mol% or less.
並且,該PI-1層需為溶劑不溶性。此處,溶劑不溶性係指20℃下對N-甲基-2-吡咯啶酮(NMP)之溶解度未滿5質量%。該PI可為熱塑性,亦可為非熱塑性。 In addition, the PI-1 layer needs to be solvent-insoluble. Here, the solvent insolubility means that the solubility to N-methyl-2-pyrrolidone (NMP) at 20°C is less than 5 mass%. The PI may be thermoplastic or non-thermoplastic.
PI-1層可藉由將相對於總二胺成分使用了超過15莫耳%且未滿50莫耳%之DDA之聚醯胺酸(PAA-1)溶液塗佈於基材上並進行乾燥、熱硬化(醯亞胺化)而獲得。此處,DDA係自碳數24~48之二聚酸衍生之脂肪族二胺,可使用「Priamine 1074、Priamine 1075」(Croda Japan公司製造之商品名)、「Versamine 551、Versamine 552」(Cognis Japan公司製造之商品名)等市售品。 The PI-1 layer can be dried by coating a polyamide acid (PAA-1) solution containing more than 15 mol% and less than 50 mol% of DDA relative to the total diamine component on the substrate , Thermal curing (imidization) to obtain. Here, DDA is an aliphatic diamine derived from a dimer acid with a carbon number of 24 to 48. "Priamine 1074, Priamine 1075" (trade names manufactured by Croda Japan), "Versamine 551, Versamine 552" (Cognis Commercial products such as trade names manufactured by Japan.
PAA-1溶液例如可於含氮極性溶劑中,以大致等莫耳之四羧酸二酐與二胺(包含超過15莫耳%且未滿50莫耳%之DDA及超過50莫耳%且未滿85莫耳%之「其他二胺」之混合物)成為大致等莫耳之方式調配,並於10~70℃下使其聚合反應,而作為光學方面均勻之溶液獲得。 For example, the PAA-1 solution can be used in a nitrogen-containing polar solvent with approximately equal moles of tetracarboxylic dianhydride and diamine (including more than 15 mole% and less than 50 mole% DDA and more than 50 mole% and The mixture of "other diamines" (less than 85 mol%) is prepared in a roughly equal molar manner, and polymerized at 10~70°C to obtain an optically uniform solution.
作為含氮極性溶劑,較佳為醯胺系溶劑、脲系溶劑。作為醯胺系溶劑,例如可列舉:N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺(DMAc)。作為脲系溶劑,例如可列舉:四甲基脲、二甲基伸乙脲。含氮極性溶劑可單獨使用該等,亦可組合使用2種以上。該等之中,較佳為DMAc及NMP。 As the nitrogen-containing polar solvent, an amide-based solvent and a urea-based solvent are preferred. Examples of amide-based solvents include N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, and N,N-dimethylacetamide (DMAc). Examples of urea-based solvents include tetramethylurea and dimethylethylene urea. The nitrogen-containing polar solvent may be used alone or in combination of two or more kinds. Among them, DMAc and NMP are preferred.
作為四羧酸二酐之具體例,可列舉:均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、2,3,3',4'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)、4,4'-氧雙鄰苯二甲酸二酐(ODPA)、3,3',4,4'-二苯基碸四羧酸二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)、2,2-雙〔4-(3,4-二羧基苯氧基)苯基〕丙二酐(BPADA)等四羧酸二酐。該等可單獨使用,亦可組合使用2種以上。為了製成溶劑不溶性之PI,該等之中,較佳為BPDA、PMDA、6FDA。 Specific examples of tetracarboxylic dianhydride include: pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3' ,4'-Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA ), 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2- Tetracarboxylic dianhydride such as bis[4-(3,4-dicarboxyphenoxy)phenyl]malonic anhydride (BPADA). These can be used individually or in combination of 2 or more types. In order to make PI that is solvent-insoluble, among these, BPDA, PMDA, and 6FDA are preferred.
作為上述「其他二胺」之具體例,可列舉:對伸苯基二胺(PDA)、4,4'-二胺基二苯醚(ODA)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)、間伸苯基二胺、2,4-二胺基甲苯、4,4'-二胺基聯苯、4,4'-二胺基-2,2'-雙(三氟甲基)聯苯(PFMB)、2,2'-二甲基-4,4'-二胺基聯苯(DMDB)、3,3'-二胺基二苯碸、4,4,-二胺基二苯碸、4,4'-二胺基二苯硫、4,4'-二胺基二苯甲烷、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷等二胺。該等可單獨使用,亦可組合使用2種以上。為了製成溶劑不溶性之PI,該等之中,較佳為PDA、DMDB、ODA。 Specific examples of the above-mentioned "other diamines" include: p-phenylenediamine (PDA), 4,4'-diaminodiphenyl ether (ODA), 2,2-bis[4-(4- Aminophenoxy) phenyl) propane (BAPP), m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino- 2,2'-bis(trifluoromethyl)biphenyl (PFMB), 2,2'-dimethyl-4,4'-diaminobiphenyl (DMDB), 3,3'-diaminodiphenyl Benzene, 4,4,-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether , 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis (3-Aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfonate, bis[4 -(3-Aminophenoxy)phenyl]sulfur, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and other diamines. These can be used individually or in combination of 2 or more types. In order to make PI that is solvent-insoluble, among these, PDA, DMDB, and ODA are preferred.
為了進一步提昇PI-1層之尺寸穩定性,可於PAA-1溶液中調配填料。 In order to further improve the dimensional stability of the PI-1 layer, fillers can be formulated in the PAA-1 solution.
作為填料,例如可列舉:滑石、煅燒黏土、未煅燒黏土、雲母、玻璃、氧化鈦、鋁、軟水鋁石、氧化矽、碳酸鈣、碳酸鎂、鋁碳酸鎂等碳酸鹽;氫氧化鋁、氫氧化鎂、氫氧化鈣、硫酸鋇、硫酸鈣、亞硫酸鈣、硼酸鋅、偏硼酸鋇、硼酸鋁、硼酸鈣、硼酸鈉、氮化鋁、氮化硼、氮化矽、氮化碳、鈦酸鍶、鈦酸鋇等。該等填料可單獨使用,亦可組合使用2種以上。該等之中,較佳為介電特性優異之氧化矽。 Examples of fillers include carbonates such as talc, calcined clay, uncalcined clay, mica, glass, titanium oxide, aluminum, boehmite, silica, calcium carbonate, magnesium carbonate, and hydromagnesium carbonate; aluminum hydroxide, hydrogen Magnesium oxide, calcium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, carbon nitride, titanium Strontium acid, barium titanate, etc. These fillers may be used alone or in combination of two or more kinds. Among them, silicon oxide with excellent dielectric properties is preferred.
填料之平均粒徑較佳為0.05μm以上且5.0μm以下,更佳為0.1μm以上且2.0μm以下。填料之平均粒徑例如可藉由雷射繞射式粒度分佈測定裝置,以體積基準測定粒子之粒度分佈,並將其中值粒徑(D50)作為平均粒徑。 The average particle diameter of the filler is preferably 0.05 μm or more and 5.0 μm or less, more preferably 0.1 μm or more and 2.0 μm or less. The average particle size of the filler can be measured by a laser diffraction particle size distribution measuring device on a volume basis, and the median particle size (D50) can be used as the average particle size.
相對於調配填料之PI-1質量,PI-1層中包含之填料之含量較佳為30質量%以上、85質量%以下,更佳為40質量%以上、70.0質量%以下。 The content of the filler contained in the PI-1 layer is preferably 30% by mass or more and 85% by mass or less, and more preferably 40% by mass or more and 70.0% by mass or less relative to the mass of PI-1 of the formulated filler.
PI-1層例如可利用以下方法獲得。 The PI-1 layer can be obtained by the following method, for example.
即,可藉由首先於基材上塗佈PAA-1溶液,於100~200℃下乾燥後,將形成之PAA-1被膜於200℃以上之溫度下進行熱硬化(熱醯亞胺化)而獲得。PI-1層之厚度無限制,但較佳為設為1μm以上、150μm以下。 That is, by first coating the PAA-1 solution on the substrate and drying at 100~200℃, the formed PAA-1 film can be thermally cured at a temperature above 200℃ (thermal imidization) And get. The thickness of the PI-1 layer is not limited, but it is preferably 1 μm or more and 150 μm or less.
作為PI-1層之介電特性,較佳為將10GHz下之電容率(Dk)設為3.2以下,更佳為設為3.1以下。並且,較佳為將10GHz下之損耗正切(Df)設為0.004以下,更佳為設為0.003以下。藉此設 置,而可確保作為積層薄膜時之良好的介電特性。 As the dielectric properties of the PI-1 layer, the permittivity (Dk) at 10 GHz is preferably 3.2 or less, and more preferably 3.1 or less. Furthermore, it is preferable to set the loss tangent (Df) at 10 GHz to 0.004 or less, more preferably to 0.003 or less. Set up It can ensure good dielectric properties when used as a laminated film.
包含PI-1層之積層PI薄膜例如為非熱塑性,可藉由將尺寸穩定性優異之PI薄膜(以下有時簡稱為「PI-2層」)與PI-1層積層一體化而獲得。 The laminated PI film including the PI-1 layer is, for example, non-thermoplastic and can be obtained by integrating a PI film with excellent dimensional stability (hereinafter sometimes referred to as "PI-2 layer") and a PI-1 laminated layer.
就確保積層薄膜之剛性之觀點而言,PI-2層之拉伸彈性模數較佳為設為3GPa以上,更佳為設為5GPa以上。此處,拉伸彈性模數使用基於JIS K7161之於拉伸模式下測定彈性模數之值。又,就確保積層薄膜之尺寸穩定性之觀點而言,PI-2層之CTE較佳為設為20ppm/K以下,更佳為設為10ppm/K以下。 From the viewpoint of ensuring the rigidity of the laminated film, the tensile modulus of elasticity of the PI-2 layer is preferably 3 GPa or more, and more preferably 5 GPa or more. Here, the tensile modulus of elasticity uses a value measured in the tensile mode based on JIS K7161. Furthermore, from the viewpoint of ensuring the dimensional stability of the laminated film, the CTE of the PI-2 layer is preferably set to 20 ppm/K or less, more preferably 10 ppm/K or less.
用以形成PI-2層之聚醯胺酸(PAA-2)溶液例如可於含氮極性溶劑中以四羧酸二酐與二胺成為大致等莫耳之方式調配,並於10~70℃下使其聚合反應,作為光學方面均勻之溶液而獲得。 The polyamide acid (PAA-2) solution used to form the PI-2 layer, for example, can be formulated in a nitrogen-containing polar solvent in such a way that tetracarboxylic dianhydride and diamine become roughly equimolar, and the temperature is 10~70℃ Then, it is polymerized and obtained as an optically uniform solution.
此處,作為含氮極性溶劑,可使用上述之含氮極性溶劑,較佳為DMAc及NMP。 Here, as the nitrogen-containing polar solvent, the above-mentioned nitrogen-containing polar solvent can be used, and DMAc and NMP are preferred.
作為四羧酸二酐,可使用上述之四羧酸二酐,較佳為BPDA、PMDA、6FDA。 As the tetracarboxylic dianhydride, the above-mentioned tetracarboxylic dianhydride can be used, and BPDA, PMDA, and 6FDA are preferred.
作為二胺,可使用上述之「其他二胺」,較佳為PDA、DMDB、BAPP、ODA、PFMB。此處使用之二胺為不含DDA之二胺,但只要相對於總二胺成分為5莫耳%以下左右,則可將其組合使用。就確保PI-2層之高剛性、低CTE之觀點而言,以此方式設置較佳。 As the diamine, the aforementioned "other diamines" can be used, and PDA, DMDB, BAPP, ODA, and PFMB are preferred. The diamine used here is a diamine that does not contain DDA, but it can be used in combination as long as it is about 5 mol% or less with respect to the total diamine components. In terms of ensuring the high rigidity and low CTE of the PI-2 layer, this method is better.
再者,為了將PI-2層之PI設為非熱塑性,只要適當選擇上述之四羧酸二酐與二胺之組合即可。此處,非熱塑性PI係指於350℃以下之溫度下即便加熱亦不熔融或軟化之PI。又,非熱塑性PI通常為溶劑不溶性,即表現出良好之耐溶劑性。 Furthermore, in order to make the PI of the PI-2 layer non-thermoplastic, it is only necessary to appropriately select the combination of the above-mentioned tetracarboxylic dianhydride and diamine. Here, non-thermoplastic PI refers to PI that does not melt or soften even if heated at a temperature below 350°C. In addition, non-thermoplastic PI is usually solvent-insoluble, that is, it exhibits good solvent resistance.
積層PI薄膜例如可利用以下方法獲得。 The laminated PI film can be obtained by the following method, for example.
即,首先於基材上塗佈PAA-2溶液並於100~200℃下乾燥後,於形成之PAA-2被膜上塗佈PAA-1溶液,並於100~200℃下乾燥,形成PAA-1被膜,之後,使兩被膜一起於200℃以上之溫度下熱硬化(熱醯亞胺化)。 That is, first coat the PAA-2 solution on the substrate and dry it at 100~200℃, then apply the PAA-1 solution on the formed PAA-2 film and dry it at 100~200℃ to form PAA- 1. After that, the two films are thermally cured (thermal imidization) at a temperature above 200°C.
藉此,可於形成於基材上之PI-2層之表面上形成PI-1層,製成PI-2層與PI-1層之密接性優異之積層薄膜。可於PI-1層上進而形成PI-2層。又,可使塗佈順序相反,於PI-1層之表面形成PI-2層,亦可進而於PI-2層上形成PI-1層。 Thereby, a PI-1 layer can be formed on the surface of the PI-2 layer formed on the substrate, and a laminated film with excellent adhesion between the PI-2 layer and the PI-1 layer can be made. The PI-2 layer can be further formed on the PI-1 layer. In addition, the coating sequence can be reversed, and a PI-2 layer can be formed on the surface of the PI-1 layer, or a PI-1 layer can be further formed on the PI-2 layer.
此處使用之基材並無限制,可使用玻璃板、銅箔等公知之基材。於使用銅箔作為基材之情形時,可製成形成有包含PI-1層與PI-2層之積層PI薄膜層(絕緣層)之FCCL之單面板。又,亦可製成絕緣層之兩表面配置有銅箔之兩面板之FCCL。於該情形時,只要使用PI等接著劑使單面板彼此熱壓接合即可。作為該接著劑,較佳為使用低電容率之熱塑性PI。銅箔之厚度並無限制,較佳為5μm以上且20μm以下者,銅箔可實施化學性或物理性表面處理。作為化學性表面處理,可列舉:鍍鎳、鍍銅-鋅合金等鍍覆處理、利用鋁醇化物、鋁螯合物、矽烷偶合劑等表面處理劑所進行之處理等,其中,較佳為利用矽烷偶合劑所進行之表面處理。作為矽烷偶合劑,較佳地使用具有胺基之矽烷偶合劑。另一方面,作為物理性表面處理,可列舉粗面化處理等。 The substrate used here is not limited, and known substrates such as glass plates and copper foils can be used. In the case of using copper foil as the base material, it can be made into a single panel with FCCL formed with a laminated PI thin film layer (insulating layer) including a PI-1 layer and a PI-2 layer. In addition, it can also be made into FCCL with two panels with copper foil on both surfaces of the insulating layer. In this case, what is necessary is just to use an adhesive agent, such as PI, to thermocompression-bond the single panels. As the adhesive, it is preferable to use thermoplastic PI with low permittivity. The thickness of the copper foil is not limited, and it is preferably 5 μm or more and 20 μm or less, and the copper foil can be subjected to chemical or physical surface treatment. Examples of chemical surface treatments include plating treatments such as nickel plating, copper-zinc alloy plating, and treatments with surface treatment agents such as aluminum alkoxides, aluminum chelate compounds, and silane coupling agents. Among them, preferred are Surface treatment with silane coupling agent. As the silane coupling agent, a silane coupling agent having an amine group is preferably used. On the other hand, as physical surface treatment, roughening treatment and the like can be mentioned.
作為PI-2層,亦可使用「Kapton」(東麗杜邦公司製造之商品名)、「Upilex」(Ube Industries公司製造之商品名)等市售之PI薄膜。 As the PI-2 layer, commercially available PI films such as "Kapton" (trade name manufactured by Toray DuPont) and "Upilex" (trade name manufactured by Ube Industries) can also be used.
該等PI薄膜係包含非熱塑性PI者。 These PI films contain non-thermoplastic PI.
於使用該等PI薄膜作為PI-2層之情形時,只要於PI薄膜上塗佈PAA-1溶液,乾燥後,進行熱硬化,於PI-2層上形成PI-1層即可。 In the case of using these PI films as the PI-2 layer, as long as the PAA-1 solution is coated on the PI film, and after drying, it is thermally cured to form a PI-1 layer on the PI-2 layer.
該等PI薄膜為了提昇與PI-1層之接著性,可實施化學性或物理性表面處理。作為化學性表面處理,可列舉利用矽烷偶合劑、鋁醇化物等所進行之表面處理。另一方面,作為物理性表面處理,可列舉粗面化處理、電漿處理等。 In order to improve the adhesion of the PI films to the PI-1 layer, chemical or physical surface treatments can be implemented. Examples of chemical surface treatments include surface treatments with silane coupling agents, aluminum alcoholates, and the like. On the other hand, as a physical surface treatment, roughening treatment, plasma treatment, etc. are mentioned.
包含PI-1層與PI-2層之積層薄膜之合計厚度並無限制,但較佳可設為5μm以上且200μm以下。 The total thickness of the laminated film including the PI-1 layer and the PI-2 layer is not limited, but it can preferably be 5 μm or more and 200 μm or less.
又,PI-1層與PI-2層之厚度比率並無限制,但較佳可將PI-1層之厚度設為積層薄膜整體之10~80%,更佳設為30~70%。 In addition, the thickness ratio of the PI-1 layer to the PI-2 layer is not limited, but the thickness of the PI-1 layer can preferably be set to 10 to 80% of the entire laminated film, more preferably 30 to 70%.
作為本發明之積層薄膜之介電特性,較佳可將10GHz下之電容率(Dk)設為3.3以下,更佳設為3.2以下。並且較佳將10GHz下之損耗正切(Df)設為0.005以下,更佳設為0.004以下。藉此,可確保將積層薄膜作為高頻基板用FCCL之絕緣層時之良好的介電特性。 As the dielectric properties of the laminated film of the present invention, the permittivity (Dk) at 10 GHz can be preferably set to 3.3 or less, more preferably 3.2 or less. And it is preferable to set the loss tangent (Df) at 10 GHz to 0.005 or less, more preferably 0.004 or less. This can ensure good dielectric properties when the laminated film is used as the insulating layer of the FCCL for high-frequency substrates.
又,本發明之積層薄膜之CTE較佳設為40ppm/K以下,更佳設為30ppm/K以下。 In addition, the CTE of the laminated film of the present invention is preferably set to 40 ppm/K or less, more preferably set to 30 ppm/K or less.
藉此,可確保將積層薄膜作為高頻基板用FCCL之絕緣層時之良好的尺寸穩定性。 This can ensure good dimensional stability when the laminated film is used as the insulating layer of the FCCL for high-frequency substrates.
[實施例] [Example]
以下基於實施例具體地說明本發明,但本發明並不僅限於該等實施例。再者,於以下實施例及比較例中,特性值之測定 方法如下。 The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. Furthermore, in the following examples and comparative examples, the measurement of characteristic values Methods as below.
<介電特性> <Dielectric Properties>
將充分乾燥之薄膜作為試樣,單面製作圓盤共振器,使用網路分析儀(安捷倫科技公司製造),以10GHz測定電容率(Dk)、損耗正切(Df)。測定對相同之試樣進行3次,將其平均值作為測定值。 Using the fully dried film as a sample, a disc resonator was fabricated on one side, and a network analyzer (manufactured by Agilent Technologies) was used to measure the permittivity (Dk) and loss tangent (Df) at 10 GHz. The measurement was performed 3 times on the same sample, and the average value was used as the measurement value.
<CTE> <CTE>
將充分乾燥之薄膜作為試樣,使用熱機械特性分析裝置(TMA,TA Instrument公司製造TMA2940),以5℃/min之定速升溫、30mN之拉伸模式測定於氮氣中使其自20℃升溫且在100℃~250℃之間之尺寸變化量,並藉此算出。 A fully dried film was used as a sample, and a thermomechanical characteristic analyzer (TMA, TMA2940 manufactured by TA Instrument) was used to measure the temperature at a constant rate of 5°C/min and a tensile mode of 30mN in nitrogen to increase the temperature from 20°C And calculate the dimensional change between 100℃ and 250℃.
<實施例1> <Example 1>
於氮氣環境下向玻璃製之反應容器添加作為二胺成分之PDA:0.42莫耳、DDA(Croda Japan股份有限公司製造「Priamine 1075」,分子量:549):0.18莫耳、作為四羧酸二酐成分之BPDA:0.6莫耳、作為溶劑之NMP,並於60℃攪拌下使其反應3小時,藉此,獲得固形份濃度為18質量%之均勻之PAA-1溶液。 Add PDA as a diamine component to a glass reaction vessel under nitrogen atmosphere: 0.42 mol, DDA ("Priamine 1075" manufactured by Croda Japan Co., Ltd., molecular weight: 549): 0.18 mol, as tetracarboxylic dianhydride Composition BPDA: 0.6 mol, NMP as a solvent, and reacted at 60°C for 3 hours with stirring, thereby obtaining a uniform PAA-1 solution with a solid concentration of 18% by mass.
於玻璃板上以硬化後之PI-1層之厚度成為20μm之方式塗佈PAA-1溶液,之後,於氮氣環境下於130℃下乾燥20分鐘,藉此,於銅箔上形成PAA-1之被膜。 The PAA-1 solution was coated on the glass plate so that the thickness of the cured PI-1 layer became 20μm, and then dried at 130°C for 20 minutes in a nitrogen atmosphere, thereby forming PAA-1 on the copper foil The envelope.
將以此方式獲得之被膜於氮氣環境下慢慢升溫後,並於350℃下處理60分鐘,進行熱硬化,藉此將PAA-1被膜轉換為PI薄膜。 之後,藉由將PI薄膜自玻璃板剝離而獲得PI薄膜(A-1)。 The film obtained in this way was slowly heated in a nitrogen atmosphere, and then treated at 350° C. for 60 minutes for thermal curing, thereby converting the PAA-1 film into a PI film. After that, the PI film (A-1) was obtained by peeling the PI film from the glass plate.
依照上述之方法測定所獲得之PI薄膜之諸特性,將其結果示於表1。再者,將所獲得之PI薄膜為溶劑不溶性之情形表記為「○」,將可溶性之情形表記為「×」。 The properties of the obtained PI film were measured according to the above-mentioned method, and the results are shown in Table 1. In addition, the case where the obtained PI film is solvent-insoluble is marked as "○", and the case where the obtained PI film is soluble is marked as "×".
<實施例2> <Example 2>
將PAA-1溶液中之二胺組成設為PDA:0.45莫耳、DDA:0.15莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-2)。將所獲得之PI薄膜之諸特性示於表1。 Except that the diamine composition in the PAA-1 solution was set to PDA: 0.45 mol and DDA: 0.15 mol, the PI film (A-2) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例3> <Example 3>
將PAA-1溶液中之二胺組成設為PDA:0.36莫耳、DDA:0.24莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-3)。將所獲得之PI薄膜之諸特性示於表1。 Except for setting the diamine composition in the PAA-1 solution to PDA: 0.36 mol and DDA: 0.24 mol, the PI film (A-3) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例4> <Example 4>
將PAA-1溶液中之二胺組成設為PDA:0.50莫耳、DDA:0.10莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-4)。將所獲得之PI薄膜之諸特性示於表1。 Except for setting the diamine composition in the PAA-1 solution to PDA: 0.50 mol and DDA: 0.10 mol, the PI film (A-4) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例5> <Example 5>
將PAA-1溶液中之四羧酸二酐組成設為BPDA:0.48莫耳、PMDA:0.12莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-5)。將所獲得之PI薄膜之諸特性示於表1。 The composition of the tetracarboxylic dianhydride in the PAA-1 solution was set to BPDA: 0.48 mol and PMDA: 0.12 mol, except that the PI film (A-5) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例6> <Example 6>
將PAA-1溶液中之二胺組成設為PDA:0.45莫耳、DDA:0.15莫耳,將四羧酸二酐組成設為BPDA:0.48莫耳、6FDA:0.12莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-6)。將所獲得之PI薄膜之諸特性示於表1。 The diamine composition in the PAA-1 solution is set to PDA: 0.45 mol, DDA: 0.15 mol, the tetracarboxylic dianhydride composition is set to BPDA: 0.48 mol, 6FDA: 0.12 mol, in addition to The PI film (A-6) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例7> <Example 7>
將PAA-1溶液中之二胺組成設為PDA:0.48莫耳、DDA:0.12莫耳,將四羧酸二酐組成設為BPDA:0.48莫耳、PMDA:0.12莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-7)。將所獲得之PI薄膜之諸特性示於表1。 The diamine composition in the PAA-1 solution is set to PDA: 0.48 mol, DDA: 0.12 mol, and the tetracarboxylic dianhydride composition is set to BPDA: 0.48 mol, PMDA: 0.12 mol, in addition to The PI film (A-7) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<實施例8> <Example 8>
將PAA-1溶液中之二胺組成設為DMDB:0.42莫耳、DDA:0.18莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(A-8)。將所獲得之PI薄膜之諸特性示於表1。 Except for setting the diamine composition in the PAA-1 solution to DMDB: 0.42 mol and DDA: 0.18 mol, the PI film (A-8) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<比較例1> <Comparative Example 1>
將PAA-1溶液中之二胺設為PDA:0.60莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(B-1)。將所獲得之PI薄膜之諸特性示於表1。 Except that the diamine in the PAA-1 solution was set to PDA: 0.60 mol, a PI film (B-1) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<比較例2> <Comparative Example 2>
將PAA-1溶液中之二胺組成設為PDA:0.54莫耳、DDA:0.06莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(B-2)。將所獲得之PI薄膜之諸特性示於表1。 Except that the diamine composition in the PAA-1 solution was set to PDA: 0.54 mol and DDA: 0.06 mol, the PI film (B-2) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<比較例3> <Comparative Example 3>
將PAA-1溶液中之二胺組成設為DMDB:0.54莫耳、DDA:0.06莫耳,除此以外,以與實施例1相同之方式獲得PI薄膜(B-3)。將所獲得之PI薄膜之諸特性示於表1。 Except for setting the diamine composition in the PAA-1 solution to DMDB: 0.54 mol and DDA: 0.06 mol, the PI film (B-3) was obtained in the same manner as in Example 1. The properties of the obtained PI film are shown in Table 1.
<比較例4> <Comparative Example 4>
將PAA-1溶液中之二胺組成設為ODA:0.3莫耳、DDA:0.3莫耳,將四羧酸二酐設為BPADA,除此以外,以與實施例1相同之方式獲得PI薄膜(B-4)。將所獲得之PI薄膜之諸特性示於表1。 The diamine composition in the PAA-1 solution was set to ODA: 0.3 mol, DDA: 0.3 mol, and tetracarboxylic dianhydride was set to BPADA, except that the PI film was obtained in the same manner as in Example 1 ( B-4). The properties of the obtained PI film are shown in Table 1.
<比較例5> <Comparative Example 5>
將PAA-1溶液中之二胺組成設為ODA:0.3莫耳、DDA:0.3莫耳,將四羧酸二酐設為ODPA,除此以外,以與實施例1相同之方式獲得PI薄膜(B-5)。將所獲得之PI薄膜之諸特性示於表1。 The diamine composition in the PAA-1 solution was set to ODA: 0.3 mol, DDA: 0.3 mol, and tetracarboxylic dianhydride was set to ODPA, except that the PI film was obtained in the same manner as in Example 1 ( B-5). The properties of the obtained PI film are shown in Table 1.
[表1]
如表1所示,可知實施例中所獲得之利用本發明所得之PI薄膜A-1~A-8確保良好的介電特性且為溶劑不溶性。與此相對,可知比較例1~3中所獲得之PI薄膜為溶劑不溶性,但介電特性不良。又,可知比較例4、5中所獲得之PI薄膜雖然介電特性良好,但為溶劑可溶性,耐溶劑性不足。 As shown in Table 1, it can be seen that the PI films A-1 to A-8 obtained by the present invention obtained in the examples ensure good dielectric properties and are solvent-insoluble. In contrast, it can be seen that the PI films obtained in Comparative Examples 1 to 3 are solvent-insoluble, but have poor dielectric properties. In addition, it can be seen that the PI films obtained in Comparative Examples 4 and 5 have good dielectric properties, but are solvent-soluble and have insufficient solvent resistance.
<實施例9> <Example 9>
於氮氣環境下向玻璃製之反應容器添加作為二胺成分之PDA:0.48莫耳、ODA:0.12莫耳、作為四羧酸二酐成分之BPDA:0.6莫耳、作為溶劑之NMP,並於攪拌下於60℃下使其反應3小時,藉此,獲得固形份濃度為18質量%之均勻的PPA-2溶液。 Add PDA as a diamine component: 0.48 mol, ODA: 0.12 mol, BPDA as a tetracarboxylic dianhydride component: 0.6 mol, and NMP as a solvent to a glass reaction vessel under a nitrogen atmosphere, and stir The reaction was carried out at 60° C. for 3 hours, thereby obtaining a uniform PPA-2 solution with a solid concentration of 18% by mass.
於厚度18μm之銅箔上以硬化後之PI-2層之厚度成為5μm之方式塗佈PAA-2溶液,之後,於氮氣環境下130℃下乾燥20分鐘,藉此,於銅箔上形成PAA-2之被膜。其次,於該PAA-2被膜上以硬化後之PI-1層之厚度成為15μm之方式塗佈實施例1中獲得之 PAA-1溶液,之後,於氮氣環境下130℃下乾燥20分鐘,藉此,於PAA-2被膜上形成PAA-1被膜。進而,於該PAA-1被膜上以硬化後之PI-2層之厚度成為5μm之方式塗佈PAA-2溶液,之後,於氮氣環境下130℃下乾燥20分鐘,藉此,於PAA-1被膜上形成PAA-2被膜。 Coat the PAA-2 solution on a copper foil with a thickness of 18μm so that the thickness of the hardened PI-2 layer becomes 5μm, and then dry it at 130°C for 20 minutes in a nitrogen atmosphere, thereby forming PAA on the copper foil -2 of the film. Next, the PAA-2 film was coated with the layer obtained in Example 1 so that the thickness of the cured PI-1 layer became 15 μm The PAA-1 solution was then dried under a nitrogen atmosphere at 130° C. for 20 minutes, thereby forming a PAA-1 film on the PAA-2 film. Furthermore, the PAA-2 solution was coated on the PAA-1 film so that the thickness of the cured PI-2 layer became 5μm, and then dried under a nitrogen atmosphere at 130°C for 20 minutes, thereby, the PAA-1 A PAA-2 film is formed on the film.
使以此方式獲得之3層之積層被膜於氮氣環境下慢慢升溫之後,於350℃下處理60分鐘進行熱硬化,藉此,將PAA-1及PAA-2轉換為PI,獲得於銅箔上依序形成PI-2層、PI-1層、PI-2層之積層體。藉由自該積層體蝕刻去除銅箔,藉此,獲得包含3層PI之積層薄膜(L-1)。將所獲得之積層PI薄膜之諸特性示於表1。 The 3-layer laminate film obtained in this way is slowly heated in a nitrogen atmosphere, and then treated at 350°C for 60 minutes for thermal curing, thereby converting PAA-1 and PAA-2 into PI, and obtaining it on copper foil A laminate of PI-2 layer, PI-1 layer, and PI-2 layer is sequentially formed on the top. The copper foil was removed by etching from the laminate, thereby obtaining a laminate film (L-1) containing three layers of PI. Table 1 shows the characteristics of the obtained laminated PI film.
另一方面,將PAA-2溶液以硬化後之PI-2層之厚度成為10μm之方式塗佈於玻璃板,於與上述之條件相同條件下進行乾燥、熱硬化,藉此獲得PI-2被膜,將該PI-2被膜自玻璃板剝離,獲得PI-2薄膜。該薄膜為非熱塑性,其CTE為16.5ppm/K。 On the other hand, the PAA-2 solution is applied to the glass plate so that the thickness of the cured PI-2 layer becomes 10μm, and it is dried and thermally cured under the same conditions as the above conditions to obtain a PI-2 film , The PI-2 film was peeled from the glass plate to obtain a PI-2 film. The film is non-thermoplastic and its CTE is 16.5 ppm/K.
<實施例10> <Example 10>
於氮氣環境下向玻璃製之反應容器添加作為二胺成分之DMDB:0.6莫耳、作為四羧酸二酐成分之BPDA:0.6莫耳、作為溶劑之NMP,並於60℃攪拌下使其反應3小時,藉此獲得固形份濃度為18質量%之均勻的PAA-2溶液。 Add DMDB as a diamine component: 0.6 mol, BPDA as a tetracarboxylic dianhydride component: 0.6 mol, and NMP as a solvent to a glass reaction vessel under a nitrogen atmosphere, and react with stirring at 60°C For 3 hours, a uniform PAA-2 solution with a solid content concentration of 18% by mass was obtained.
於厚度18μm之銅箔上以硬化後之PI-2層之厚度成為4μm之方式塗佈PAA-2溶液,之後,於130℃氮氣環境下乾燥20分鐘,藉此,於銅箔上形成PAA-2之被膜。其次,於該PAA-2被膜上以硬化後之PI-1層之厚度成為18μm之方式塗佈實施例1中獲得之 PAA-1溶液,之後,於氮氣環境下130℃下乾燥20分鐘,藉此,於PAA-2被膜上形成PAA-1被膜。進而,於該PAA-1被膜上以硬化後之PI-2層之厚度成為4μm之方式塗佈PAA-2溶液,之後,於130℃氮氣環境下乾燥20分鐘,藉此,於PAA-1被膜上形成PAA-2被膜。 The PAA-2 solution was coated on a copper foil with a thickness of 18μm so that the thickness of the hardened PI-2 layer became 4μm, and then dried at 130°C in a nitrogen atmosphere for 20 minutes, thereby forming PAA- on the copper foil 2 of the film. Next, the PAA-2 film was coated with the layer obtained in Example 1 so that the thickness of the cured PI-1 layer became 18 μm The PAA-1 solution was then dried under a nitrogen atmosphere at 130° C. for 20 minutes, thereby forming a PAA-1 film on the PAA-2 film. Furthermore, the PAA-2 solution was coated on the PAA-1 film so that the thickness of the cured PI-2 layer became 4μm, and then dried at 130°C in a nitrogen atmosphere for 20 minutes, thereby, the PAA-1 film A PAA-2 film is formed on it.
使以此方式獲得之3層之積層被膜於氮氣環境下慢慢升溫之後,於350℃下處理60分鐘,進行熱硬化,藉此,將PAA-1及PAA-2轉換為PI,獲得於銅箔上依序形成PI-2層、PI-1層、PI-2層之積層體。自該積層體蝕刻去除銅箔,獲得包含3層PI之積層薄膜(L-2)。將所獲得之積層PI薄膜之諸特性示於表1。 The three-layer laminated film obtained in this way is slowly heated in a nitrogen atmosphere, and then treated at 350°C for 60 minutes for thermal curing, thereby converting PAA-1 and PAA-2 into PI, and obtaining copper A laminate of PI-2 layer, PI-1 layer, and PI-2 layer is sequentially formed on the foil. The copper foil was etched and removed from the laminate to obtain a laminate film (L-2) containing three layers of PI. Table 1 shows the characteristics of the obtained laminated PI film.
另一方面,將PAA-2溶液以硬化後之PI-2層之厚度成為10μm之方式塗佈於玻璃板,於與上述之條件相同條件下進行乾燥、熱硬化,藉此獲得PI-2被膜,將該PI-2被膜自玻璃板剝離,獲得PI-2薄膜。該薄膜為非熱塑性,其CTE為8.3ppm/K。 On the other hand, the PAA-2 solution is applied to the glass plate so that the thickness of the cured PI-2 layer becomes 10μm, and it is dried and thermally cured under the same conditions as the above conditions to obtain a PI-2 film , The PI-2 film was peeled from the glass plate to obtain a PI-2 film. The film is non-thermoplastic and its CTE is 8.3 ppm/K.
[表2]
如表2所示,可知利用本發明所得之積層PI薄膜表現出良好的介電特性。 As shown in Table 2, it can be seen that the laminated PI film obtained by the present invention exhibits good dielectric properties.
又,可知由於CTE低至30ppm以下,故尺寸穩定性良好。 In addition, it can be seen that since the CTE is as low as 30 ppm or less, dimensional stability is good.
(產業上之可利用性) (Industrial availability)
本發明之PI薄膜其介電特性、耐溶劑性、尺寸穩定性優異。因此,可較佳地用作構成用於印刷電路或天線基板等之高頻基板用FCCL之絕緣層之PI薄膜。 The PI film of the present invention has excellent dielectric properties, solvent resistance and dimensional stability. Therefore, it can be preferably used as a PI film constituting an insulating layer of FCCL for high-frequency substrates used in printed circuits, antenna substrates, and the like.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-193012 | 2018-10-12 | ||
JP2018193012 | 2018-10-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202027985A true TW202027985A (en) | 2020-08-01 |
TWI788596B TWI788596B (en) | 2023-01-01 |
Family
ID=70724914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108136695A TWI788596B (en) | 2018-10-12 | 2019-10-09 | Polyimide film and the flexible cupper-clad laminate comprising the same |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP7095880B2 (en) |
TW (1) | TWI788596B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI775295B (en) * | 2020-12-31 | 2022-08-21 | 財團法人工業技術研究院 | Polymer and resin composition thereof |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7156055B2 (en) * | 2019-01-24 | 2022-10-19 | 荒川化学工業株式会社 | Polyimide, adhesive, film-like adhesive, adhesive layer, adhesive sheet, resin-coated copper foil, copper-clad laminate, printed wiring board, multilayer wiring board, and manufacturing method thereof |
JP2022165323A (en) * | 2021-04-19 | 2022-10-31 | 日東電工株式会社 | Film for metal layer laminate and metal layer laminate |
WO2023218512A1 (en) * | 2022-05-09 | 2023-11-16 | 株式会社レゾナック | Poly(amic acid)-containing liquid and method for producing poly(amic acid)-containing liquid |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6403503B2 (en) | 2013-09-30 | 2018-10-10 | 新日鉄住金化学株式会社 | Copper-clad laminate, printed wiring board and method of using the same |
KR20150077317A (en) * | 2013-12-27 | 2015-07-07 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Polyamic acid composition, polymide, resin film and metal-clad laminate |
-
2019
- 2019-10-09 TW TW108136695A patent/TWI788596B/en active
- 2019-10-09 JP JP2019185674A patent/JP7095880B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI775295B (en) * | 2020-12-31 | 2022-08-21 | 財團法人工業技術研究院 | Polymer and resin composition thereof |
Also Published As
Publication number | Publication date |
---|---|
JP7095880B2 (en) | 2022-07-05 |
TWI788596B (en) | 2023-01-01 |
JP2020076072A (en) | 2020-05-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI788596B (en) | Polyimide film and the flexible cupper-clad laminate comprising the same | |
JP4734837B2 (en) | Polyimide film with improved adhesiveness, method for producing the same, and laminate | |
TWI768525B (en) | Polyimide film, method of producing the same, and multilayer film, flexible metal foil laminate and electronic component containing the same | |
US7811660B2 (en) | Polyimide film having high adhesiveness and method for producing same | |
TWI765392B (en) | Polyimide film, method of producing the same, and multilayer film, flexible metal foil laminate and electronic component containing the same | |
KR20070053799A (en) | Novel polyimide film improved in adhesion | |
KR101757023B1 (en) | Cross-linked polyimide resin and method for producing same, adhesive resin composition and cured product thereof, cover lay film, circuit board, heat-conductive substrate, and heat-conductive polyimide film | |
JP6488170B2 (en) | Circuit board | |
TWI556970B (en) | Manufacturing method of multilayer polyimide flexible metal-clad laminate | |
JP2006183040A (en) | Polyimide, polyimide film and laminated body | |
CN114651036A (en) | Polyimide film having improved dimensional stability and method for preparing the same | |
EP1606108B1 (en) | Double-sided metallic laminate and method for manufacturing the same | |
KR102647086B1 (en) | Metal-clad laminate and circuit board | |
TW202124555A (en) | Resin composition, resin film and metal-clad laminate capable of improving dielectric properties without impairing mechanical properties such as bendability due to addition of inorganic fillers | |
JP7461622B2 (en) | Polyimide Film | |
JP2019014062A (en) | Laminate, flexible metal-clad laminated sheet, and flexible printed circuit board | |
JP7503289B2 (en) | Polyimide | |
JP7378122B2 (en) | polyimide film | |
JP2010267691A (en) | Polyimide film for metallizing, and metal laminate polyimide film | |
TWI846159B (en) | Polyimide precursor composition, polyimide film, multilayer film, flexible metal clad laminate and electronic parts including the same | |
TWI846160B (en) | Polyamic acid, polyimide film, multilayer film, flexible metal clad laminate and electronic parts using the same | |
JP2004315601A (en) | Polyimide film with improved adhesiveness, its preparation method, and its laminate | |
JP7520338B2 (en) | Laminated Film | |
JP7429411B2 (en) | Laminated body for high frequency board | |
JP7231932B2 (en) | polyimide film |