TWI735477B - 配線基板之製造方法、配線基板及天線 - Google Patents
配線基板之製造方法、配線基板及天線 Download PDFInfo
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- TWI735477B TWI735477B TW105134121A TW105134121A TWI735477B TW I735477 B TWI735477 B TW I735477B TW 105134121 A TW105134121 A TW 105134121A TW 105134121 A TW105134121 A TW 105134121A TW I735477 B TWI735477 B TW I735477B
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- Prior art keywords
- layer
- fluororesin
- group
- electrical insulator
- wiring board
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Abstract
本發明提供一種配線基板之製造方法,所製造之配線基板即便不進行使用金屬鈉之蝕刻處理,亦可抑制形成於電絕緣體層之孔洞中的傳導不良,且即便電絕緣體層中不含由強化纖維構成之織布或不織布,亦可抑制翹曲等無預期之變形。
一種配線基板之製造方法,係於具有第1導體層、電絕緣體層及第2導體層之積層體形成孔洞,並且,對於孔洞之內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後於孔洞之內壁面形成鍍層;其中,前述電絕緣體層含有特定之氟樹脂層(A)及耐熱性樹脂層(B),且不含強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃。
Description
本發明係關於一種配線基板之製造方法。
發明背景
除行動電話等資訊通信終端之外,高速大容量無線通信亦被廣泛利用於汽車等領域。高速大容量無線通信係以進行資訊之傳收信之天線來傳輸高頻信號。作為天線,舉例來說,可使用具有電絕緣體層及設於該電絕緣體層上之導體層的配線基板。配線基板大多是於電絕緣體層之兩面側分別形成有導體層,且該等導體層藉由形成於貫通電絕緣體層之孔洞(通孔)內壁面之鍍層來傳導。此外進行傳收電波之天線,隨著例如電波的頻率變高,愈來愈多是在可形成電子電路且被稱作印刷配線基板等之配線基板上,利用電子電路之配線圖樣來形成。
對於用於傳輸高頻信號之配線基板,所要求的是具有優異之傳輸特性,即傳輸延遲及傳輸損失要小。為提升傳輸特性,需使用相對介電常數及介電正切小的材料作為形成電絕緣體層之絕緣材料。而作為相對介電常數及介電正切小的絕緣材料,為人所知的有氟樹脂。作為絕緣材料,可舉例如使用了聚四氟乙烯(PTFE)等的配線基板(專利文獻1)及使用了具有酸酐殘基之氟樹脂的配線基板
(專利文獻2)。
於使用氟樹脂作為絕緣材料之配線基板而言,要形成孔洞並於該孔洞之內壁面形成鍍層時,一般來說,為了確保孔洞內壁面與鍍層之密著性以抑制傳導不良,會在對孔洞之內壁面進行前處理後進行鍍敷處理。作為前處理,為人所知的有使用了使金屬鈉溶解於四氫呋喃之蝕刻液的蝕刻處理。藉由該蝕刻處理,孔洞內壁面之氟樹脂會部分溶解使得內壁面被粗化,從而藉錨定效應使孔洞內壁面與鍍層之密著性提高。又,因孔洞內壁面之氟原子被羥基等取代以致撥水性降低,故容易於孔洞之內壁面整體形成鍍層。但是,該蝕刻處理所使用之金屬鈉恐有因與水接觸而燃燒(爆炸)之虞,故在處理及保管場所方面須嚴格加以注意。又,因大量使用有機溶劑,故亦有因吸入而危害作業者健康之虞及後處理之類的問題。
於在電絕緣體層兩面積層導體層之配線基板而言,抑制基板發生翹曲等無預期之變形也很重要。抑制翹曲等無預期之變形發生的方法,已知的方法係使電絕緣體層含有由玻璃纖維構成之織布或不織布(專利文獻2)。藉由該織布或不織布,電絕緣體層之線膨脹係數會接近於導體層之線膨脹係數,故可抑制配線基板發生翹曲等無預期之變形。但是,使用了織布或不織布之配線基板的可撓性會降低,故不適於應用作為要求高柔軟性之可撓性基板。
專利文獻1:日本特開2001-7466號公報
專利文獻2:日本特開2007-314720號公報
發明概要
本發明之目的在於提供一種配線基板之製造方法,該方法可製造出下述配線基板:即便不進行使用金屬鈉之蝕刻處理,亦可抑制形成於電絕緣體層之孔洞中的傳導不良,且即便電絕緣體層中未含有由強化纖維構成之織布或不織布亦可抑制翹曲等無預期之變形。
本發明具有以下之結構。
[1]一種配線基板之製造方法,該配線基板具有電絕緣體層、設於前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位於相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層;其中電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種
官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹脂(a)除外);該配線基板之製造方法係於具有前述第1導體層、前述電絕緣體層及前述第2導體層之積層體形成前述孔洞,並且,對於所形成之前述孔洞之內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後,於該孔洞之內壁面形成前述鍍層。
[2]一種配線基板之製造方法,該配線基板具有電絕緣體層、設於前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位於相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層;其中電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹脂(a)除外);該配線基板之製造方法係於具有前述電絕緣體層及前述第2導體層之積層體形成前述孔洞,並且對於所形成之前述孔洞之內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之
後,於該孔洞之內壁面形成前述鍍層,然後於前述電絕緣體層第1面形成前述第1導體層。
[3]如[1]或[2]之配線基板之製造方法,其中前述電絕緣體層具有下述層結構:耐熱性樹脂層(B)/氟樹脂層(A)之層結構、耐熱性樹脂層(B)/氟樹脂層(A)/耐熱性樹脂層(B)之層結構或氟樹脂層(A)/耐熱性樹脂層(B)/氟樹脂層(A)之層結構。
[4]如[1]至[3]中任一項之配線基板之製造方法,其中前述氟樹脂(a)之熔點在260℃以上。
[5]如[1]至[4]中任一項之配線基板之製造方法,其中前述電絕緣體層之相對介電常數為2.0~3.0。
[6]如[1]至[5]中任一項之配線基板之製造方法,其中前述官能基至少含有含羰基之基;且前述含羰基之基選自於由在烴基之碳原子間具有羰基之基、碳酸酯基、羧基、鹵代甲醯基、烷氧羰基及酸酐殘基所構成群組中之至少1種基。
[7]如[1]至[6]中任一項之配線基板之製造方法,其中相對於前述氟樹脂(a)之主鏈碳數1×106個,該氟樹脂(a)中之前述官能基含量為10~60000個。
[8]如[1]至[7]中任一項之配線基板之製造方法,其中前述氟樹脂(a)係由四氟乙烯、全氟(烷基乙烯基醚)與不飽和二羧酸酐之共聚物構成。
[9]如[1]至[8]中任一項之配線基板之製造方法,其中耐熱性樹脂(b)係由聚醯亞胺構成。
[10]一種配線基板,具有電絕緣體層、設於
前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位在相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層;其特徵在於:電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹脂(a)除外);並且,該配線基板於熱衝擊試驗前後之下述電阻變化率落在±10%之範圍內:電阻變化率:熱衝擊試驗後電絕緣體層兩面介有鍍層之導電體層間的電阻值相對於熱衝擊試驗前之電阻值的變化率,該熱衝擊試驗如下:將配線基板置於-65℃之環境下30分鐘後再置於125℃之環境下30分鐘,以此為一循環並反覆進行100循環。
[11]如[10]之配線基板,其中前述電絕緣體層具有下述層結構:耐熱性樹脂層(B)/氟樹脂層(A)之層結構、耐熱性樹脂層(B)/氟樹脂層(A)/耐熱性樹脂層(B)之層結構或氟樹脂層(A)/耐熱性樹脂層(B)/氟樹脂層(A)之層結構。
[12]一種天線,係由如[10]或[11]之配線基板構成,其中
前述第1導體層與前述第2導體層中之至少任一層為具有天線圖樣之導體層。
依據本發明之配線基板之製造方法可製造出下述配線基板:即便不進行使用金屬鈉之蝕刻處理亦可抑制形成於電絕緣體層之孔洞中的傳導不良,且即便電絕緣體層中未含有由強化纖維構成之織布或不織布亦可抑制翹曲等無預期之變形。
1、2、3:配線基板
1A、2A、3A、1B、2B、3B:積層體
10、10A、10B:電絕緣體層
10a:第1面
10b:第2面
12:第1導體層
14:第2導體層
16:氟樹脂層(A)
18:耐熱性樹脂層(B)
20:孔洞
20a:內壁面
22:鍍層
圖1A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖1B係顯示於圖1A之積層體形成有孔洞之狀態的截面圖。
圖1C係顯示於圖1B之積層體之孔洞內壁面形成有鍍層之狀態的截面圖。
圖2A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖2B係顯示於圖2A之積層體形成有孔洞之狀態的截面圖。
圖2C係顯示於圖2B之積層體之孔洞內壁面形成有鍍層之狀態的截面圖。
圖3A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖3B係顯示於圖3A之積層體形成有孔洞之狀態的截
面圖。
圖3C係顯示於圖3B之積層體之孔洞內壁面形成有鍍層之狀態的截面圖。
圖4A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖4B係顯示於圖4A之積層體形成有孔洞之狀態的截面圖。
圖4C係顯示於圖4B之積層體之孔洞內壁面形成有鍍層之狀態的截面圖。
圖4D係顯示於圖4C之積層體之氟樹脂層之第1面側形成有第1導體層之狀態的截面圖。
圖5A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖5B係顯示於圖5A之積層體形成有孔洞之狀態的截面圖。
圖5C係顯示於圖5B之積層體之孔洞內壁面形成有鍍層之狀態的截面圖。
圖5D係顯示於圖5C之積層體之氟樹脂層之第1面側形成有第1導體層之狀態的截面圖。
圖6A係顯示用於本發明配線基板之製造方法之積層體一例的截面圖。
圖6B係顯示於圖6A之積層體形成有孔洞之狀態的截面圖。
圖6C係顯示於圖6B之積層體之孔洞內壁面形成有鍍
層之狀態的截面圖。
圖6D係顯示於圖6C之積層體之氟樹脂層之第1面側形成有第1導體層之狀態的截面圖。
用以實施發明之形態
於本說明書中下述用語之意思如下。
「耐熱性樹脂」係指熔點在280℃以上之高分子化合物,或是JIS C 4003:2010(IEC 60085:2007)所規定之最高連續使用溫度在121℃以上之高分子化合物。
「熔點」係指與以示差掃描熱量測定(DSC)法測得之熔解波峰之最大值相對應的溫度。
「可熔融成形」係指顯示熔融流動性。
「顯示熔融流動性」係指存在有於負載49N之條件下且在比樹脂熔點高出20℃以上之溫度下熔流速率會成為0.1~1000g/10分的溫度。
「熔流速率」係表示JIS K 7210:1999(ISO 1133:1997)所規定之熔體質量流速(MFR)。
氟樹脂之「相對介電常數」係指利用依據ASTM D 150之變壓器電橋法於溫度23℃±2℃且相對濕度50%±5%RH之環境下以1MHz之頻率作測定之值。
電絕緣體層之「相對介電常數」係指利用分離後介電質共振器法(SPDR法:Split-Post Dielectric Resonator Techniques)於23℃±2℃且50±5%RH之環境下以2.5GHz之頻率作測定之值。
另外,於本說明書中,將源自單體之單元亦記作「單體單元」。例如,將源自含氟單體之單元亦記作「含氟單體單元」。
[配線基板]
以本發明之製造方法製造之配線基板具有電絕緣體層、第1導體層及第2導體層。電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有具後述官能基(Q)之可熔融成形的氟樹脂(a),該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但氟樹脂(a)除外)。第1導體層係設於電絕緣體層之第1面,第2導體層係設於電絕緣體層中與第1面位於相反側之第2面。該配線基板中,具有至少從第1導體層連通至第2導體層之孔洞,該孔洞之內壁面形成有鍍層。
另外,以下,將氟樹脂層(A)亦稱作「層(A)」,將耐熱性樹脂層(B)亦稱作「層(B)」。又,將配線基板及電絕緣體層中從第1導體層往第2導體層之方向的層排列,在層間附上「/」並予以排列來表示。
電絕緣體層中之層(A)可為1層亦可為2層以上。電絕緣體層中之層(B)可為1層亦可為2層以上。電絕緣體層中之層(A)的數目與層(B)的數目之合計宜在5以下。又,層(A)與層(B)雖以交替配置為佳,但必未必得交替配置。
電絕緣體層中之層(A)與層(B)之層順序,就容易抑制翹曲等無預期之變形的觀點來說,以於電絕緣體層之厚度方向成對稱為佳。具體來說,以由2層之層(A)與1層之層(B)構成之電絕緣體層為例,宜具有層(A)/層(B)/層(A)之層結構。又,亦可為層(B)/層(A)/層(B)之層結構的電絕緣體層。
另外,電絕緣體層中之層順序,並不侷限於在厚度方向成對稱之順序。譬如,亦可為具有層(A)/層(B)之層結構的2層結構電絕緣體層。
另外,於配線基板中,於第1導體層之與電絕緣體層相反之側、或是於第2導體層之與電絕緣體層相反之側,可具有樹脂層。作為樹脂層,可舉例如層(A)及層(B)等。又,亦可於第1導體層之與電絕緣體層相反之側、或是於第2導體層之與電絕緣體層相反之側,透過接著層或樹脂層更設有導電層。
形成於配線基板之孔洞,只要是至少從第1導體層連通至第2導體層之孔洞即可,不一定得從配線基板之其中一面貫通至另一面。舉例來說,只要為從第1導體層連通至第2導體層之孔洞,則該孔洞亦可不貫通第1導體層或第2導體層。
以本發明之製造方法所製造之配線基板而言,例如可列舉以下例示之配線基板1~3。
配線基板1係如圖1C所示,具有電絕緣體層10、電絕緣體層10之第1面10a上之第1導體層12、電絕緣體層10之
第2面10b上之第2導體層14。電絕緣體層10具有層(A)16/層(B)18/層(A)16之3層結構。於配線基板1中,形成有從第1導體層12貫通至第2導體層14之孔洞20,且孔洞20之內壁面20a形成有鍍層22。
配線基板2係如圖2C所示,具有電絕緣體層10A、電絕緣體層10A之第1面10a上之第1導體層12、電絕緣體層10A之第2面10b上之第2導體層14。電絕緣體層10A具有層(A)16/層(B)18之2層結構。於配線基板2中,形成有從第1導體層12貫通至第2導體層14之孔洞20,且孔洞20之內壁面20a形成有鍍層22。
配線基板3係如圖3C所示,具有電絕緣體層10B、電絕緣體層10B之第1面10a上之第1導體層12、電絕緣體層10B之第2面10b上之第2導體層14。電絕緣體層10B具有層(B)18/層(A)16/層(B)18之3層結構。於配線基板3中,形成有從第1導體層12貫通至第2導體層14之孔洞20,且孔洞20之內壁面20a形成有鍍層22。
(電絕緣體層)
電絕緣體層係由含有至少1層層(A)與至少1層層(B)之多層結構的層所構成,且不含玻璃布等由織布或不織布構成之強化纖維基材。因電絕緣體層不含強化纖維基材,故會成為具有優異可撓性之配線基板,而可適合作為可撓性基板使用。
電絕緣體層之相對介電常數為2.0~3.5,宜為2.0~3.0。只要電絕緣體層之相對介電常數在前述上限值
以下,就能用於天線等要求低介電常數之用途上。只要電絕緣體層之相對介電常數在前述下限值以上,則電特性以及與鍍層之密著性兩者俱佳。
電絕緣體層之線膨脹係數宜為0~35ppm/℃,較佳為0~30ppm/℃。只要電絕緣體層之線膨脹係數在前述上限值以下,則與導體層之線膨脹係數差會變小,便容易抑制配線基板發生翹曲等無預期之變形。
另外,電絕緣體層之線膨脹係數可以實施例中所載之方法求得。
電絕緣體層之厚度宜為4~1000μm,較佳為6~300μm。只要電絕緣體層之厚度在前述下限值以上,配線基板就難以過度變形,故導體層難以斷線。只要電絕緣體層之厚度在前述上限值以下,則會具有優異之可撓性,又可對應配線基板之小型化及輕量化。
<氟樹脂層(A)>
層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基(以下亦稱「官能基Q」)。
層(A)之厚度宜為2~300μm,較佳為10~150μm。只要層(A)之厚度在前述下限值以上,便容易抑制翹曲等無預期之變形。只要層(A)之厚度在前述上限值以下,則會具有優異之可撓性,又可對應配線基板之小型化及輕量化線膨脹係數。
《氟樹脂(a)》
作為氟樹脂(a),可舉具有下述單元之氟樹脂(a1)為例,該氟樹脂(a1)具有:具有官能基(Q)之單元(1)及源自四氟乙烯(TFE)之單元(2)。氟樹脂(a1)亦可依所需更具有單元(1)及單元(2)以外之其他單元。
作為官能基(Q)中含羰基之基,只要為結構中含有羰基之基即可,可舉例如:在烴基之碳原子間具有羰基之基、碳酸酯基、羧基、鹵代甲醯基、烷氧羰基、酸酐殘基、多氟烷氧羰基及脂肪酸殘基等。其中,從與導體層及鍍層之接著性優異之觀點來看,宜為選自於由在烴基之碳原子間具有羰基之基、碳酸酯基、羧基、鹵代甲醯基、烷氧羰基及酸酐殘基所構成群組中之至少1種基,較佳為羧基及酸酐殘基中之任一者或二者。
在烴基之碳原子間具有羰基之基中的烴基可舉例如碳數2~8之伸烷基等。另外,該伸烷基之碳數係不含羰基之碳數。該伸烷基可為直鏈狀亦可為分枝狀。
鹵代甲醯基中之鹵素原子可列舉氟原子及氯原子等,以氟原子為佳。
烷氧羰基中之烷氧基可為直鏈狀亦可為分枝狀。作為該烷氧基以碳數1~8之烷氧基為佳,且以甲氧基或乙氧基尤佳。
單元(1)所具有之官能基(Q)可為1個亦可為2個以上。單元(1)具有2個以上之官能基(Q)時,其等官能基(Q)可相同亦可相異。
作為含有含羰基之基之單體,可舉例如:為
具有酸酐殘基與聚合性不飽和鍵之化合物的不飽和二羧酸酐、具有羧基之單體(伊康酸及丙烯酸等)、乙烯酯(乙酸乙烯酯等)、甲基丙烯酸酯、丙烯酸酯((多氟烷基)丙烯酸酯等)及CF2=CFORf1CO2X1(但是,Rf1係可含醚性氧原子之碳數1~10之全氟伸烷基,X1係氫原子或碳數1~3之烷基)等。
作為含羥基之單體,可舉例如乙烯酯類、乙烯醚類及烯丙醚類等。
作為含環氧基之單體,可舉例如烯丙基環氧丙基醚、2-甲基烯丙基環氧丙基醚、縮水甘油丙烯酸酯及縮水甘油甲基丙烯酸酯等。
作為含異氰酸酯基之單體,可舉例如:異氰酸2-丙烯醯氧基乙酯、異氰酸2-甲基丙烯醯氧基乙酯、異氰酸2-(2-丙烯醯氧基乙氧基)乙酯及異氰酸2-(2-甲基丙烯醯氧基乙氧基)乙酯等。
從與導體層及鍍層之接著性優異之觀點來看,單元(1)宜至少具有含羰基之基作為官能基(Q)。又,作為單元(1),從熱穩定性及與導體層及鍍層之接著性優異之觀點來看,以選自於由IAH單元、CAH單元及NAH單元所構成群組中之至少1種單元較佳,且以NAH單元尤佳。
單元(1)及單元(2)以外之其他單元,可舉例
如:源自全氟(烷基乙烯基醚)(PAVE)、六氟丙烯(HFP)、氟乙烯、氟化亞乙烯(VdF)、三氟乙烯及三氟氯乙烯(CTFE)等其他單體之單元。
作為PAVE,可舉例如CF2=CFOCF3、CF2=CFOCF2CF3、CF2=CFOCF2CF2CF3(PPVE)、CF2=CFOCF2CF2CF2CF3、CF2=CFO(CF2)8F等,以PPVE為佳。
作為其他單元,以PAVE單元為佳,PPVE單元尤佳。
作為理想之氟樹脂(a1),宜為TFE與PPVE及不飽和二羧酸酐之共聚物,具體來說,可列舉TFE/PPVE/NAH共聚物、TFE/PPVE/IAH共聚物及TFE/PPVE/CAH共聚物等。
另外,氟樹脂(a)亦可具有官能基(Q)作為主鏈末端基。作為主鏈末端基導入之官能基(Q)宜為烷氧羰基、碳酸酯基、羧基、氟甲醯基、酸酐殘基及羥基。該等官能基可藉由適當選定自由基聚合引發劑及鏈轉移劑等來導入。
相對於氟樹脂(a)之主鏈碳數1×106個,氟樹脂(a)中之官能基(Q)含量宜為10~60000個,較佳為100~50000個,更佳為100~10000個,特別理想的是300~5000個。只要官能基(Q)之含量在前述範圍內,則層(A)與導體層或層(B)之界面的接著強度會變得更高。
另外,官能基(Q)之含量可利用核磁共振(NMR)分析及紅外線吸收光譜分析等方法來測定。舉例來說,可如日本特開2007-314720號公報所載,使用紅外線吸收光譜分
析等方法求出構成氟樹脂(a)之全單元中具有官能基(Q)之單元的比率(莫耳%),並從該比率算出官能基(Q)之含量。
氟樹脂(a)之熔點宜在260℃以上,較佳為260~320℃,更佳為295~315℃,295~310℃特別理想。只要氟樹脂(a)之熔點在前述下限值以上,則層(A)之耐熱性優異。只要氟樹脂(a)之熔點在前述上限值以下,則氟樹脂(a)之成形性優異。
氟樹脂(a)之熔點可依構成氟樹脂(a)之單元的種類及比例以及氟樹脂(a)之分子量等來作調整。
氟樹脂(a)於372℃且負載49N之條件下的熔流速率(MFR)宜為0.1~1000g/10分,較佳為0.5~100g/10分,更佳為1~30g/10分。只要熔流速率在前述上限值以下,便有焊料耐熱性提升之傾向。只要熔流速率在前述下限值以上,則氟樹脂(a)之成形性優異。
熔流速率係氟樹脂(a)之分子量之基準,表示熔流速率大的話分子量即小,而熔流速率小的話則分子量大。氟樹脂(a)之熔流速率可依氟樹脂(a)之製造條件來作調整。例如,縮短聚合時之聚合時間的話,會有氟樹脂(a)之熔流速率變大的傾向。又,減少製造時之自由基聚合引發劑使用量的話,則有氟樹脂(a)之熔流速率變小的傾向。
氟樹脂(a)之相對介電常數宜為2.0~3.2,較佳為2.0~3.0。氟樹脂(a)之相對介電常數愈低,則愈容易降低層(A)之相對介電常數。
氟樹脂(a)之相對介電常數例如可依單元(2)之含量來
作調整。有單元(2)之含量愈高氟樹脂(a)之相對介電常數會變得愈低之傾向。
層(A)中所含之氟樹脂(a)可為1種,亦可在2種以上。
《其他成分》
層(A)中在無損本發明效果之範圍內亦可含有未被製成織布或不織布之態樣的玻璃纖維及添加劑等。作為添加劑以介電常數及介電正切低之無機填料為佳。
作為無機填料,可舉例如:氧化矽、黏土、滑石、碳酸鈣、雲母、矽藻土、氧化鋁、氧化鋅、氧化鈦、氧化鈣、氧化鎂、氧化鐵、氧化錫、氧化銻、氫氧化鈣、氫氧化鎂、氫氧化鋁、鹼性碳酸鎂、碳酸鎂、碳酸鋅、碳酸鋇、碳鈉鋁石、水滑石、硫酸鈣、硫酸鋇、矽酸鈣、蒙脫石、膨土、活性白土、海泡石、絲狀鋁英石、絹雲母、玻璃纖維、玻璃珠、氧化矽系中空球體、碳黑、碳奈米管、碳奈米角、石墨、碳纖維、玻璃中空球體、碳燼(carbon burn)、木粉及硼酸鋅等。
無機填料可為多孔質亦可為非多孔質。從介電常數及介電正切更低之觀點來看,無機填料以多孔質為佳。
無機填料可單獨使用1種,亦可併用2種以上。
從電特性優異之觀點來看,層(A)中之氟樹脂(a)之含有比率宜在50質量%以上,較佳在80質量%以上。氟樹脂(a)之含有比率之上限並無特別限定,亦可為100質量%。
<耐熱性樹脂(B)>
層(B)係含有耐熱性樹脂(b)(但氟樹脂(a)除外)的層。因電絕緣體層含有層(B),故與僅有層(A)的情況相比,可將電絕緣體層之線膨脹係數縮小。
層(B)之厚度宜為每1層3~500μm,較佳為5~300μm,更佳為6~200μm。只要層(B)之厚度在前述下限值以上,則電絕緣性優異,又容易抑制翹曲等無預期之變形。只要層(B)之厚度在前述上限值以下,就可將配線基板整體之厚度變薄。
電絕緣體層中層(B)之總厚度相對於層(A)之總厚度的比值B/A宜為10~0.1,較佳為5~0.2。只要比值B/A在前述下限值以上,則容易抑制配線基板之翹曲等無預期之變形。只要比值B/A在前述上限值以下,則可容易製得電特性優異之配線基板。
比值B/A需考慮層(A)及層(B)個別之線膨脹係數來選定,以使電絕緣體層之線膨脹係數成為0~35ppm/℃。
《耐熱性樹脂(b)》
作為耐熱性樹脂(b),可列舉聚醯亞胺(芳香族聚醯亞胺等)、聚芳香酯、聚碸、聚芳碸(聚醚碸等)、芳香族聚醯胺、芳香族聚醚醯胺、聚伸苯硫、聚芳基醚酮、聚醯胺醯亞胺及液晶性聚酯等。
作為耐熱性樹脂(b)以聚醯亞胺及液晶性聚酯為佳,而從耐熱性方面來看則以聚醯亞胺尤佳。
聚醯亞胺可為熱硬化性聚醯亞胺亦可為熱可塑性聚
醯亞胺。但為熱硬化性聚醯亞胺時,層(B)中之聚醯亞胺係由該熱硬化性聚醯亞胺之硬化物構成。
作為聚醯亞胺以芳香族聚醯亞胺為佳。
作為芳香族聚醯亞胺,則以芳香族多元羧酸二酐與芳香族二胺之縮聚合所製造之全芳香族聚醯亞胺為佳。
聚醯亞胺通常係藉由多元羧酸二酐(或其衍生物)與二胺之反應(聚縮合),經由聚醯胺酸(聚醯亞胺前驅物)而獲得。
聚醯亞胺尤其是芳香族聚醯亞胺因其剛硬的主鏈結構而不溶於溶劑等,並且具有不融之性質。因此,首先,藉由多元羧酸二酐與二胺之反應,以合成可溶於有機溶劑的聚醯亞胺前驅物(聚醯胺酸(polyamic acid或polyamide acid)),並在聚醯胺酸之階段以各種方法來進行成形加工。其後將聚醯胺酸加熱或以化學方法使其行脫水反應並且環化(醯亞胺化)而製成聚醯亞胺。
作為芳香族多元羧酸二酐及芳香族二胺之具體例,可舉日本特開2012-145676號公報之段落[0055]及[0057]所載等。該等可單獨使用1種,亦可併用2種以上。
作為耐熱性樹脂(b),從提升電特性之觀點來看則液晶性聚酯亦佳。尤其是,從提升耐熱性之觀點來看,液晶性聚酯其熔點在300℃以上且相對介電常數在3.2以下,介電正切在0.005以下即可。作為液晶性聚酯可使用KURARAY CO.,LTD.製之「Vecstar(註冊商標)」及日本W.L.Gore & Associates,Inc.製之「BIAC」等之液晶性
聚酯製薄膜。
耐熱性樹脂層(B)中所含之耐熱性樹脂(b)可為1種,亦可在2種以上。
《其他成分》
於層(B)中在無損本發明效果之範圍內,亦可含有未被製成織布或不織布之態樣的玻璃纖維及添加劑等。作為添加劑以介電常數及介電正切低之無機填料為佳。無機填料例如可與於層(A)所列舉者相同。
從層(B)之耐熱性優異以及容易抑制翹曲等無預期之變形的觀點來看,層(B)中之耐熱性樹脂(b)之含有比率宜在50質量%以上,較佳在80質量%以上。耐熱性樹脂(b)含量的上限並無特別限定,亦可為100質量%。
(導體層)
作為導體層,以電阻低之金屬箔為佳。金屬箔可列舉由銅、銀、金及鋁等金屬構成的箔。金屬可單獨使用1種,亦可併用2種以上。併用2種以上金屬時,作為金屬箔而言以施有金屬鍍敷之金屬箔為佳,且以施有鍍金之銅箔尤佳。
導體層之厚度,宜為每1層0.1~100μm,較佳為1~50μm,且1~40μm尤其理想。
各導電體層之金屬材料之種類及其厚度亦可不同。
從減低進行高頻帶信號傳輸時之集膚效應之觀點來看,導體層之電絕緣體層側表面可經過粗化。且於導體層之與經粗化表面相反之側的表面,可形成有具有防鏽性之鉻酸鹽等的氧化物皮膜。
導體層可依所需藉由形成圖樣來形成有配線。另外,導體層亦可具有配線以外之形態。
(鍍層)
鍍層只要為通過該鍍層可確保第1導體層與第2導體層之傳導者即可。鍍層可舉例如鍍銅層、鍍金層、鍍鎳層、鍍鉻層、鍍鋅層及鍍錫層等,且以鍍銅層為佳。
以本發明之配線基板的用途來說,宜為由本發明之配線基板構成之天線,該本發明之配線基板係第1導體層及第2導體層中至少任一層為具有天線圖樣的導體層。作為天線,可舉例如國際公開第2016/121397號公報所載者。另外,本發明之配線基板的用途並不侷限於天線,特別是可用作使用於高頻電路之通訊及感測器等之印刷電路板等。
配線基板還可有效用作需要高頻特性之雷達、網路之路由器、底板、無線基礎架構等電子機器用基板或汽車用各種感測器用基板及引擎管理感測器用基板,特別是適於以減低毫米波段之傳輸損耗為目的之用途。
配線基板還可有效用作需要高頻特性之雷達、網路之路由器、底板、無線基礎架構等電子機器用基板或汽車用各種感測器用基板及引擎管理感測器用基板,特別是適於以減低毫米波段之傳輸損耗為目的之用途。
於本發明中,所製造之配線基板之總厚度宜為10~1500μm,較佳為12~200μm。只要配線基板之總厚度在前述下限值以上,便容易抑制翹曲等無預期之變形。
只要配線基板之總厚度在前述上限值以下,則會具有優異之可撓性,而成為可適用作為可撓性基板之配線基板。
熱衝擊試驗後之配線基板之電阻值相對於熱衝擊試驗前之配線基板之電阻值的變化率宜落在±10%之範圍內,該熱衝擊試驗係將配線基板置於-65℃之環境下30分鐘後再置於125℃之環境下30分鐘,以此為一循環並反覆進行100循環。更佳為落在±7%之範圍內,更理想者係落在±5%之範圍內。只要該變化率在範圍內,則會具有優異之耐熱性。藉由使用熔點高之氟樹脂(a)、熔點高之熱可塑性耐熱性樹脂(b)或是為熱硬化性樹脂之硬化物的耐熱性樹脂(b),該變化率之絕對值有變小之傾向。
[配線基板之製造方法]
本發明之配線基板之製造方法依據進行孔加工時積層體中有無第1導體層而大致分成下述方法(i)及方法(ii)。
方法(i):對具有第1導體層之積層體進行孔加工之方法。
方法(ii):對不具第1導體層之積層體進行孔加工之方法。
以下,就方法(i)及方法(ii)個別進行說明。
(方法(i))
方法(i)具有下述步驟。
步驟(i-1):對呈第1導體層/電絕緣體層/第2導體層之層結構的積層體,形成至少從第1導體層連通至第2導體層之孔洞。
步驟(i-2):對形成於積層體之孔洞的內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者。
步驟(i-3):於步驟(i-2)後之孔洞的內壁面形成鍍層。
<步驟(i-1)>
製造積層體之方法並無特別限制,可採用眾所周知之方法。
舉例來說,呈第1導體層/層(A)/層(B)/層(A)/第2導體層之層結構的積層體,可用以下方法製得。依序積層金屬箔、由氟樹脂(a)構成之樹脂膜、由耐熱性樹脂(b)構成之樹脂膜、由氟樹脂(a)構成之樹脂膜、金屬箔,並予以熱壓。
孔洞係以至少從第1導體層連通至第2導體層之方式形成。即,是以至少貫通位在第1導體層與第2導體層間之電絕緣體層的方式來形成孔洞。從較電絕緣體層更靠第1導體層側起形成孔洞時,只要第1導體層與第2導體層因該孔洞而連通,則該孔洞可達到第2導體層內亦可不達到。從較電絕緣體層更靠第2導體層側起形成孔洞時,只要第1導體層與第2導體層因該孔洞而連通,則該孔洞可達到第1導體層內亦可不達到。
於積層體開孔之方法並無特別限定,可採用眾所周知之方法,例如使用鑽孔器或雷射來開孔之方法等。
於積層體形成之孔洞的直徑無特別限定,可適當作設定。
<步驟(i-2)>
在積層體形成孔洞後,於在該孔洞之內壁面形成鍍層之前,對該孔洞之內壁面施行過錳酸溶液處理及電漿處理中之任一者或二者以作為前處理。於步驟(i-2)中,不進行使用金屬鈉之蝕刻處理作為前處理。
進行過錳酸溶液處理及電漿處理二者作為前處理時,基於下述觀點,宜先進行過錳酸溶液處理,該等觀點係:開孔加工時發生之污跡(樹脂殘渣)除去性;以及容易充分確保孔洞內壁面與鍍層之密著性,且容易於孔洞之內壁面整體形成鍍層。另外,亦可於電漿處理後實施過錳酸溶液處理。
<步驟(i-3)>
於前處理後之孔洞內壁面形成鍍層之方法,並無特別限定,可舉例如無電電鍍法等。
本發明因電絕緣體層具備了含有具官能基(Q)且與鍍層之接著性優異之氟樹脂(a)的層(A),且不含由織布或不織布構成之強化纖維基材,故即便不進行使用金屬鈉之蝕刻處理,亦可於孔洞之內壁面整體形成鍍層。因此,第1導體層與第2導體層之傳導會穩定並受到確保。
又,本發明因電絕緣體層除了層(A)還具有層(B),且線膨脹係數被控制在0~35ppm/℃,故亦可抑制所得配線基板發生翹曲等無預期之變形。
以下,就方法(i)之一例進行說明。
<第1實施態樣>
以方法(i)製造配線基板1時,係使用圖1A所示具有第
1導體層12/電絕緣體層10/第2導體層14之層結構的積層體1A。電絕緣體層10具有層(A)16/層(B)18/層(A)16之層結構。如圖1B所示,利用鑽孔器或雷射等,於積層體1A形成從第1導體層12貫通至第2導體層14之孔洞20。其次,對於所形成之孔洞20之內壁面20a,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後如圖1C所示,對孔洞20之內壁面20a進行無電電鍍等而形成鍍層22。
<第2實施態樣>
以方法(i)製造配線基板2時,係使用圖2A所示具有第1導體層12/電絕緣體層10A/第2導體層14之層結構的積層體2A。電絕緣體層10A具有層(A)16/層(B)18之層結構。與配線基板1的情況相同,如圖2B所示,於積層體2A形成從第1導體層12貫通至第2導體層14之孔洞20。然後,對於所形成之孔洞20之內壁面20a,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後如圖2C所示,於孔洞20之內壁面20a形成鍍層22。
<第3實施態樣>
以方法(i)製造配線基板3時,係使用圖3A所示具有第1導體層12/電絕緣體層10B/第2導體層14之層結構的積層體3A。電絕緣體層10B具有層(B)18/層(A)16/層(B)18之層結構。與配線基板1的情況相同,如圖3B所示,於積層體3A形成從第1導體層12貫通至第2導體層14之孔洞20。其次,對於所形成之孔洞20之內壁面20a,不進行使用金
屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後如圖3C所示,於孔洞20之內壁面20a進行無電電鍍等而形成鍍層22。
(方法(ii))
方法(ii)具有以下之步驟。
步驟(ii-1):於具有電絕緣體層/第2導體層之層結構的積層體,形成至少從電絕緣體層之第1面連通至第2導體層的孔洞。
步驟(ii-2):對形成於積層體之孔洞的內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者。
步驟(ii-3):於步驟(ii-2)後之孔洞的內壁面形成鍍層。
步驟(ii-4):於電絕緣體層之第1面形成第1導體層。
<步驟(ii-1)>
步驟(ii-1)係使用除不具第1導體層外其他皆與方法(i)相同之積層體,形成至少從電絕緣體層之第1面連通至第2導層之孔洞,除此以外可按照與步驟(i-1)同樣之方式進行。
<步驟(ii-2)、步驟(ii-3)>
步驟(ii-2)及步驟(ii-3)除使用經步驟(ii-1)形成有孔洞之積層體以外,可按照與步驟(i-2)及步驟(i-3)依同樣之方式進行。
<步驟(ii-4)>
於電絕緣體層之第1面形成第1導體層之方法並無特
別定,可舉例如無電電鍍法等。又,可依所需利用蝕刻於第1導體層形成圖樣。
步驟(ii-4)可於步驟(ii-3)之前進行,亦可於步驟(ii-3)之後進行,或可與步驟(ii-3)同時進行。
以下,就方法(ii)之一例進行說明。
<第4實施態樣>
以方法(ii)製造配線基板1時,可舉以下方法為例。
使用圖4A所示的積層體1B,其於電絕緣體層10之第2面10b具有第2導體層14,為電絕緣體層10/第2導體層14之層結構。電絕緣體層10具有層(A)16/層(B)18/層(A)16之層結構。如圖4B所示,利用鑽孔器或雷射等對積層體1B形成從電絕緣體層10貫通至第2導體層14之孔洞20。其次,對於所形成之孔洞20之內壁面20a,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者。繼而,如圖4C所示,於孔洞20之內壁面20a進行無電電鍍等而形成鍍層22。接著,如圖4D所示,於電絕緣體層10之第1面10a進行無電電鍍等而形成第1導體層12。
<第5實施態樣>
以方法(ii)製造配線基板2時,係使用圖5A所示的積層體2B,其於電絕緣體層10A之第2面10b具有第2導體層14,為電絕緣體層10A/第2導體層14之層結構。電絕緣體層10A具有層(A)16/層(B)18之層結構。與配線基板1的情況相同,如圖5B所示,於積層體2B形成從電絕緣體層10A
貫通至第2導體層14之孔洞20。然後,對於所形成之孔洞20之內壁面20a,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者。繼而,如圖5C所示,於孔洞20之內壁面20a形成鍍層22,並如圖5D所示,於電絕緣體層10之第1面10a形成第1導體層12。
<第6實施態樣>
以方法(ii)製造配線基板3時,係使用圖6A所示的積層體3B,其於電絕緣體層10B之第2面10b具有第2導體層14,為電絕緣體層10B/第2導體層14之層結構。電絕緣體層10B具有層(B)18/層(A)16/層(B)18之層結構。與配線基板1的情況相同,如圖6B所示,於積層體3B形成從電絕緣體層10B貫通至第2導體層14之孔洞20。然後,對於所形成之孔洞20之內壁面20a,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者。繼而,如圖6C所示,於孔洞20之內壁面20a形成鍍層22,並如圖6D所示,於電絕緣體層10之第1面10a側形成第1導體層12。
如以上所作說明,於本發明之配線基板之製造方法中,電絕緣體層含有含氟樹脂(a)之層(A),且不含由織布或不織布構成之強化纖維基材,該氟樹脂(a)具有官能基(Q)且接著性優異。藉此,即便對形成於電絕緣體層之孔洞不進行使用金屬鈉之蝕刻處理,孔洞之內壁面與鍍層之密著性亦會充分受到確保。因此,可於孔洞之內壁面整體形成鍍層,而可抑制孔洞中之傳導不良。「可不進行
使用金屬鈉之蝕刻處理」,在可挪用將不含氟原子之樹脂作為絕緣材料使用以製造配基板的現存設備之觀點上來說亦是有利。
又,於本發明之配線基板之製造方法中,電絕緣體層除了層(A)之外還含有層(B),且電絕緣體層之線膨脹係數被控制在0~35ppm/℃。因此,於所得之配線基板中,第1導體層及第2導體層之線膨脹係數與電絕緣體層之線膨脹係數會接近,從而可抑制翹曲等無預期之變形。
以下,藉由實施例詳細說明本發明,但本發明並不為以下之記載所限定。
[共聚組成]
氟樹脂之共聚組成中,NAH單元之比率(莫耳%)係利用以下之紅外線吸收光譜分析求得。其他單元之比率則是利用熔融NMR分析及氟含量分析求得。(NAH單元之比率的測定)
將氟樹脂加壓成形而獲得200μm之薄膜,並針對前述薄膜進行紅外線吸收光譜分析。於所得之紅外線吸收光譜中,測定出NAH單元之吸收峰即1778cm-1之吸收峰的吸光度。將該吸光度除以NAH之莫耳吸光係數20810mol-1.l.cm-1,而求得氟樹脂中之NAH單元的比率。
[熔點]
使用Seiko Instruments Inc.製之示差掃描熱量計(DSC裝置),記錄已將氟樹脂於10℃/分之速度下升溫時之
熔解波峰,並以與該熔解波峰之極大值相對應的溫度(℃)為熔點(Tm)。
[MFR]
使用Technol Seven Co.,Ltd.製之熔融指數量測儀(Melt Indexer),測定於372℃且49N負載下從直徑2mm且長度8mm之噴嘴流出10分鐘(單位時間)之氟樹脂的質量(g),並將其作為MFR(g/10分)。
[氟樹脂之相對介電常數之測定]
使用絕緣破壞試驗裝置(YSY-243-100RHO(YAMAYOSHIKENKI.COM製)),以依據ASTM D 150之變壓器電橋法,於溫度23℃±2℃且相對濕度50%±5%RH之試驗環境下,在頻率1MHz下測定氟樹脂之相對介電常數。
[電絕緣體層之相對介電常數之測定]
以蝕刻去除積層體之銅箔,並就已露出之電絕緣體層利用分離後介電質共振器法(SPDR法),於23℃±2℃且50±5%RH之環境下求出頻率2.5GHz之相對介電常數。
以測定介電常數之機器種類而言,係使用QWED公司製之標稱基本頻率2.5GHz型分離後介電質共振器、KEYSIGHT TECHNOLOGIES製之向量網路分析器(vector network analyzer)E8361C及KEYSIGHT TECHNOLOGIES製之介電常數算出用軟體「85071E option 300」。
[線膨脹係數之測定]
以蝕刻去除積層體之銅箔,並作成將露出之電絕緣體層截斷成4mm×55mm之短條狀的試樣。使該試樣於烘箱中以250℃乾燥2小時,進行試樣之狀態調整。其次,使用SII公司製熱機械分析裝置(TMA/SS6100),於空氣環境下且夾頭間距離20mm下,施加2.5g之外加負載,同時以5℃/分之速度將試樣從30℃升溫至250℃,並測定隨試樣之線膨脹產生之位移量。測定結束後,從50~100℃之試樣位移量求出於50~100℃下之線膨脹係數(ppm/℃)。
[鍍層之評價]
針對於各例中所得之配線基板,以外觀觀察來確認形成於孔洞內壁面之鍍層,並以以下基準予以評價。
○(優良):孔洞之內壁面整體形成有鍍層。
×(不良):孔洞之內壁面部分形成有鍍層,且孔洞之內壁面有一部分露出。
[耐熱性之評價]
針對配線基板,於下述熱衝擊試驗前後,測定以形成於孔洞內壁面之鍍層為中介的電絕緣體層兩面之銅箔間之電阻值。電阻值之測定係使用微歐姆計(mΩ HiTESTER)(型號:3540,HIOKI E.E.Corporation製)。
熱衝擊試驗係將配線基板置於-65℃之環境下30分鐘後再置於125℃之環境下30分鐘,以此為一循環並反覆進行100循環。
以熱衝擊試驗前後之電阻值變化落在±10%之範圍內時為合格。
[使用原料]
AK225cb:1,3-二氯-1,1,2,2,3-五氟丙烷(AK225cb,旭硝子公司製)。
PPVE:CF2=CFO(CF2)3F(旭硝子公司製)。
[製造例1]
將369kg之AK225cb及30kg之PPVE裝入已預先脫氣之內容積430L(公升)之附攪拌機的聚合槽中。接著,將聚合槽內加熱升溫至50℃並進一步裝入50kg之TFE,之後,將該聚合槽內之壓力升壓至0.89MPa/G。另外,「/G」係表示其壓力為表壓。
將(全氟丁醯基)過氧化物與PPVE溶解於AK225cb中使前者成為0.36質量%之濃度且後者成為2質量%之濃度,而調製出聚合引發劑溶液。一邊在1分鐘6.25mL之速度下將該聚合引發劑溶液3L連續添加於前述聚合槽中,一邊進行聚合。於聚合反應中連續放入TFE以使聚合槽內之壓力保持在0.89MPa/G。又,連續地放入將NAH溶解於AK225cb中使濃度成為0.3質量%所作成的溶液,以使其相對於聚合反應中放入的TFE之莫耳數為0.1莫耳%之比率。
聚合開始8小時後,於已放入32kg之TFE之時間點,將聚合槽內之溫度降溫至室溫且同時將壓力排氣至常壓。將所得漿料與AK225cb固液分離之後,於150℃下乾燥15
小時,藉此獲得33kg之粒狀的氟樹脂(a1-1)。
氟樹脂(a1-1)之共聚組成係NAH單元/TFE單元/PPVE單元=0.1/97.9/2.0(莫耳%)。氟樹脂(a1-1)之熔點為300℃,相對介電常數為2.1,MFR則為17.6g/10分。又,相對於氟樹脂(a1-1)之主鏈碳數1×106個,氟樹脂(a1-1)之官能基(Q)(酸酐基)之含量為1000個。
[製造例2]
使用具有750mm寬之衣架型模具(coat hanger die)的30mmφ單軸擠出機,在模具溫度340℃下將氟樹脂(a1-1)擠製成形而獲得厚度12.5μm之氟樹脂薄膜(以下稱「薄膜(1)」)。將厚度12μm之電解銅箔(福田金屬箔粉公司製,CF-T4X-SVR-12,表面粗度(Rz)1.2μm)、薄膜(1)及為耐熱性樹脂(b)薄膜之厚度25μm之聚醯亞胺薄膜(DU PONT-TORAY CO.,LTD.製,製品名「Kapton(註冊商標)」),以銅箔/薄膜(1)/聚醯亞胺薄膜/薄膜(1)/銅箔之順序進行積層,並於溫度360℃且壓力3.7MPa下真空壓製10分鐘而製得積層體(α-1)。對積層體(α-1)中薄膜(1)/聚醯亞胺薄膜/薄膜(1)之部分進行壓製而形成了由氟樹脂層(A-1)/耐熱性樹脂層(B-1)/氟樹脂層(A-1)構成之3層結構電絕緣體層。
以蝕刻去除在積層體(α-1)兩面的銅箔,並測定電絕緣體層之相對介電常數及線膨脹係數,得到其相對介電常數為2.86,線膨脹係數為19ppm/℃。
[製造例3]
使用具有750mm寬之衣架型模具的30mmφ單軸擠出機,在模具溫度340℃下將氟樹脂(a1-1)擠製成形而獲得厚度50μm之氟樹脂薄膜(以下稱「薄膜(2)」)。將厚度12μm之電解銅箔(福田金屬箔粉公司製,CF-T4X-SVR-12,表面粗度(Rz)1.2μm)及薄膜(2),以銅箔/薄膜(2)/銅箔之順序進行積層,並於溫度360℃且壓力3.7MPa下真空壓製10分鐘而製得積層體(α-2)。對積層體(α-2)中薄膜(2)之部分進行壓製而形成了由氟樹脂層(A-2)構成之單層結構的電絕緣體層。
以蝕刻去除在積層體(α-2)兩面的銅箔,並測定電絕緣體層之相對介電常數及線膨脹係數,得到其相對介電常數為2.07,線膨脹係數為198ppm/℃。
[製造例4]
以蝕刻去除下述兩面覆銅積層體(新日鐵化學公司製,ESPANEX M series(MB12-50-12REQ))之單面的銅箔而製成單面覆銅積層體,該兩面覆銅積層體具有厚度50μm之聚醯亞胺樹脂層作為絕緣層,且於其兩面分別設有厚度12μm之銅箔。將單面覆銅積層體中業經蝕刻去除銅箔的面與薄膜(2)合在一起,以單面覆銅積層體/薄膜(2)/薄膜(2)/單面覆銅積層體之順序進行積層,並於溫度360℃且壓力3.7MPa下真空壓製10分鐘而製得積層體(α-3)。對積層體(α-3)中聚醯亞胺樹脂層/薄膜(2)/薄膜(2)/聚醯亞胺樹脂層之部分進行壓製而形成有由耐熱性樹脂層(B-2)/氟樹脂層(A-3)/耐熱性樹脂層(B-2)構成之3層結構的電絕緣體
層。
以蝕刻去除在積層體(α-3)兩面的銅箔,並測定電絕緣體層之相對介電常數及線膨脹係數,得到其相對介電常數為2.88,線膨脹係數為28ppm/℃。
[實施例1]
對於積層體(α-1),利用鑽孔器進行0.3mmφ之孔加工,形成從積層體(α-1)之其中一面貫通至另一面的孔洞(通孔)。其次,對於所形成之孔洞之內壁面,施行去膠渣處理(過錳酸溶液處理)。就已形成通孔之積層體(α-1),使用膨潤液(羅門哈斯(ROHM and HAAS)公司製之MLB211及CupZ之混合比為2:1質量比之混合液)於液溫:80℃且處理時間:5分鐘下進行處理,且使用氧化液(羅門哈斯公司製之MLB213A-1及MLB213B-1之混合比為1:1.5質量比之混合液)於液溫:80℃且處理時間:6分鐘下進行處理,並且使用中和液(羅門哈斯公司製之MLB216-2)於液溫:45℃且處理時間:5分鐘下進行處理。
為於去膠渣處理後之積層體(α-1)之通孔內壁面形成鍍層,而對積層體(α-1)之通孔內壁面施行鍍敷處理。關於鍍敷處理,由羅門哈斯公司販售有系統液體,使用系統液體並按照所發表之程序進行無電電鍍。針對去膠渣處理後之積層體(α-1),使用洗淨液(ACL-009)於液溫:55℃且處理時間:5分鐘下進行處理。經水洗後,針對積層體(α-1),使用過硫酸鈉-硫酸系軟蝕刻處理劑,於液溫:室溫且處理時間:2分鐘下進行軟蝕刻處理。於水洗後,針對積層體
(α-1)使用處理液(MAT-2-A及MAT-2-B各使成為5:1體積比之混合液)於液溫:60℃且處理時間:5分鐘下進行活化處理。且就積層體(α-1),使用處理液(MAB-4-A及MAB-4-B各使成為1:10體積比之混合液)於液溫:30℃且處理時間:3分鐘下進行還原處理,並以無電電鍍令用以使銅析出之Pd觸媒附著於通孔之內壁面。於水洗後,針對積層體(α-1),使用處理液(PEA-6)於液溫:34℃且處理時間:30分鐘下進行鍍敷處理,使通孔之內壁面析出銅而形成鍍層,從而製得配線基板。
[實施例2]
對於積層體(α-1),利用鑽孔器進行0.3mmφ之孔加工,形成從積層體(α-1)之其中一面貫通至另一面之孔洞(通孔)。其次,對於所形成之孔洞之內壁面,以與實施例1相同之操作使用含過錳酸鈉鹽之去膠渣液施行過錳酸溶液處理,之後,進一步於氬氣氣體環境下實施電漿處理。接著,於該孔洞之內壁面利用無電電鍍形成由銅構成之鍍層,而製得配線基板。
[實施例3]
對於積層體(α-1)使用CO2雷射加工機(Hitachi,Ltd.製,LC-2K212)替代利用鑽孔器進行之孔加工,並於設定加工直徑:0.15mm、輸出:24.0W、頻率:2,000Hz之條件下,進行通孔加工。藉此形成0.15mmφ之通孔。除了形成0.15mmφ之通孔以外係依與實施例1同樣方式製得配線基板。
[實施例4]
對於積層體(α-1)使用CO2雷射加工機(Hitachi,Ltd.製,LC-2K212)替代利用鑽孔器進行之孔加工,並於設定加工直徑:0.1mm、輸出:24.0W、頻率:2,000Hz之條件下,進行通孔加工。藉此形成0.15mmφ之通孔。除了形成0.15mmφ之通孔以外係依與實施例2同樣方式製得配線基板。
[實施例5]
對於積層體(α-3),利用鑽孔器進行0.3mmφ之孔加工,形成從積層體(α-3)之其中一面貫通至另一面之孔洞(通孔)。其次,對於所形成之孔洞之內壁面,使用含過錳酸鈉鹽之去膠渣液施行過錳酸溶液處理後,進一步於氬氣氣體環境下實施電漿處理。接著,於該孔洞之內壁面利用無電電鍍形成由銅構成之鍍層,而製得配線基板。
[實施例6]
對於積層體(α-1),利用鑽孔器進行0.3mmφ之孔加工,形成從積層體(α-1)之其中一面貫通至另一面之孔洞(通孔)。其次,對於所形成之孔洞之內壁面,除了於實施例1之操作中在使用各種液體之處理步驟中施行28千赫之超音波處理以外,係以同樣之操作施行過錳酸溶液處理,之後利用無電電鍍於該孔洞之內壁面形成由銅構成之鍍層,而製得配線基板。
[比較例1]
除了使用積層體(α-2)替代積層體(α-1)以外,係依與
實施例1同樣方式製得配線基板。
將各例之電絕緣體層之層結構、相對介電常數及線膨脹係數、孔洞之直徑、前處理之種類以及評價結果示於表1。
如表1所示,以本發明之製造方法製得之實施例1~5之配線基板,即便不進行使用金屬鈉之蝕刻處理,亦於孔洞之內壁面整面形成有鍍層。又,實施例1~5之配線基板,因電絕緣體層之線膨脹係數為0~35ppm/℃,故無發生翹曲之虞。又,實施例3及4之配基板於熱衝擊試驗前後之電阻值之變化落在±10%之範圍內,故於耐熱性方面亦優異。
另一方面,比較例1之配線基板雖然孔洞之內壁面整面形成有鍍層,但電絕緣體層之線膨脹係數大到198ppm/℃,故容易發生翹曲而有實用上的問題。
另外,在此引用已於2015年10月22日提出申請之日本專利申請案2015-208154號之說明書、申請專利範圍、摘要及圖式之全部內容,並將其納入作為本發明之說明書之揭示。
1:配線基板
1A、2A:積層體
10:電絕緣體層
10a:第1面
10b:第2面
12:第1導體層
14:第2導體層
16:氟樹脂層(A)
18:耐熱性樹脂層(B)
20:孔洞
20a:內壁面
22:鍍層
Claims (12)
- 一種配線基板之製造方法,該配線基板具有電絕緣體層、設於前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位於相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層;其中電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹脂(a)除外);該配線基板之製造方法係於具有前述第1導體層、前述電絕緣體層及前述第2導體層之積層體形成前述孔洞,並且,對於所形成之前述孔洞之內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後,於該孔洞之內壁面形成前述鍍層。
- 一種配線基板之製造方法,該配線基板具有電絕緣體層、設於前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位於相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層; 其中電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹脂(a)除外);該配線基板之製造方法係於具有前述電絕緣體層及前述第2導體層之積層體形成前述孔洞,並且對於所形成之前述孔洞之內壁面,不進行使用金屬鈉之蝕刻處理而是施行過錳酸溶液處理及電漿處理中之任一者或二者,之後,於該孔洞之內壁面形成前述鍍層,然後於前述電絕緣體層第1面形成前述第1導體層。
- 如請求項1或2之配線基板之製造方法,其中前述電絕緣體層具有下述層結構:耐熱性樹脂層(B)/氟樹脂層(A)之層結構、耐熱性樹脂層(B)/氟樹脂層(A)/耐熱性樹脂層(B)之層結構或氟樹脂層(A)/耐熱性樹脂層(B)/氟樹脂層(A)之層結構。
- 如請求項1或2之配線基板之製造方法,其中前述氟樹脂(a)之熔點在260℃以上。
- 如請求項1或2之配線基板之製造方法,其中前述電絕緣體層之相對介電常數為2.0~3.0。
- 如請求項1或2之配線基板之製造方法,其 中前述官能基至少含有含羰基之基;且前述含羰基之基選自於由在烴基之碳原子間具有羰基之基、碳酸酯基、羧基、鹵代甲醯基、烷氧羰基及酸酐殘基所構成群組中之至少1種基。
- 如請求項1或2之配線基板之製造方法,其中相對於前述氟樹脂(a)之主鏈碳數1×106個,該氟樹脂(a)中之前述官能基含量為10~60000個。
- 如請求項1或2之配線基板之製造方法,其中前述氟樹脂(a)係由四氟乙烯、全氟(烷基乙烯基醚)與不飽和二羧酸酐之共聚物構成。
- 如請求項1或2之配線基板之製造方法,其中前述耐熱性樹脂(b)係由聚醯亞胺構成。
- 一種配線基板,具有電絕緣體層、設於前述電絕緣體層第1面之第1導體層以及設於前述電絕緣體層中與前述第1面位在相反側之第2面的第2導體層,並且具有至少從前述第1導體層連通至前述第2導體層之孔洞,前述孔洞之內壁面形成有鍍層;其特徵在於:電絕緣體層係一含有至少1層氟樹脂層(A)與至少1層耐熱性樹脂層(B)之多層結構層,且不含由織布或不織布構成之強化纖維基材,相對介電常數為2.0~3.5,線膨脹係數為0~35ppm/℃;其中,該氟樹脂層(A)含有可熔融成形之氟樹脂(a),該氟樹脂(a)具有選自於由含羰基之基、羥基、環氧基及異氰酸酯基所構成群組中之至少1種官能基,該耐熱性樹脂層(B)則含有耐熱性樹脂(b)(但前述氟樹 脂(a)除外);並且,該配線基板於熱衝擊試驗前後之下述電阻變化率落在±10%之範圍內:電阻變化率:熱衝擊試驗後電絕緣體層兩面介有鍍層之導電體層間的電阻值相對於熱衝擊試驗前之電阻值的變化率,該熱衝擊試驗如下:將配線基板置於-65℃之環境下30分鐘後再置於125℃之環境下30分鐘,以此為一循環並反覆進行100循環。
- 如請求項10之配線基板,其中前述電絕緣體層具有下述層結構:耐熱性樹脂層(B)/氟樹脂層(A)之層結構、耐熱性樹脂層(B)/氟樹脂層(A)/耐熱性樹脂層(B)之層結構或氟樹脂層(A)/耐熱性樹脂層(B)/氟樹脂層(A)之層結構。
- 一種天線,係由如請求項10或11之配線基板構成,其中前述第1導體層與前述第2導體層中之至少任一層為具有天線圖樣之導體層。
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KR102628572B1 (ko) * | 2017-05-18 | 2024-01-23 | 에이지씨 가부시키가이샤 | 불소 수지 필름 및 적층체, 그리고, 열 프레스 적층체의 제조 방법 |
WO2020122156A1 (ja) | 2018-12-13 | 2020-06-18 | 株式会社村田製作所 | 樹脂多層基板、および樹脂多層基板の製造方法 |
WO2020145133A1 (ja) | 2019-01-11 | 2020-07-16 | ダイキン工業株式会社 | フッ素樹脂組成物、フッ素樹脂シート、積層体及び回路用基板 |
KR20200120349A (ko) * | 2019-04-12 | 2020-10-21 | 동우 화인켐 주식회사 | 연성 인쇄회로 기판 |
CN112440532A (zh) * | 2019-08-27 | 2021-03-05 | 康宁股份有限公司 | 用于高频印刷电路板应用的有机/无机层叠体 |
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JP7514157B2 (ja) | 2020-10-12 | 2024-07-10 | 日本メクトロン株式会社 | スルーホール形成方法およびフレキシブルプリント配線板用基板 |
KR102258790B1 (ko) * | 2021-01-14 | 2021-05-28 | 동우 화인켐 주식회사 | 안테나 소자 및 이를 포함하는 화상 표시 장치 |
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