TWI565740B - 藉由電磁波之直接輻射以形成導電圖案之方法，及具有導電圖案於其上之樹脂結構 - Google Patents
藉由電磁波之直接輻射以形成導電圖案之方法，及具有導電圖案於其上之樹脂結構 Download PDFInfo
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- TWI565740B TWI565740B TW103127268A TW103127268A TWI565740B TW I565740 B TWI565740 B TW I565740B TW 103127268 A TW103127268 A TW 103127268A TW 103127268 A TW103127268 A TW 103127268A TW I565740 B TWI565740 B TW I565740B
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- polymer resin
- resin substrate
- metal layer
- metal
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
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Classifications
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- H01—ELECTRIC ELEMENTS
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C23C18/31—Coating with metals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
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Description
本發明係關於一種藉由相對低功率之電磁波的直接輻射以形成導電圖案的方法，其能藉由簡化製程將微細導電圖案形成在不同種類之聚合物樹脂產品或樹脂層上，即使該聚合物樹脂本身不含有特定無機添加劑，以及關於一種具有導電圖案形成於其上的樹脂結構。
近年來，隨著微細電子技術的發展，已更加要求一種結構，其中微細導電圖案係形成在不同種類之樹脂產品或樹脂層之聚合物樹脂基材(或產品)之表面上。在該聚合物樹脂基材和該結構之表面上的導電圖案可被施加以形成不同標的諸如整合於手機殼、不同種類之感應器、MEMS結構、RFID標籤、及類似者之中的天線。
特別地，最近之可攜式裝置諸如智慧型手機、及類似
者，與現有之手機不同的，需要同時具有經安裝之局部地區的網絡功能諸如通訊、藍芽、Wi-Fi、電子支付、及類似者，且由於此理由，需要在一個智慧型手機中同時安裝不同的天線。然而，因為除了以上之外還強調該可攜式裝置(諸如該智慧型手機)之美觀設計方面、及類似者，故已持續地提議且研究一種在該聚合物樹脂基材(諸如該可攜式裝置之匣、及類似者)的表面上形成能作為不同天線之導電圖案的方法，以同時符合這些要求。
隨著對於將導電圖案形成在該聚合物樹脂基材上之技術更加感興趣，提議數項與此相關之技術。例如，建議一種藉由以下方式在聚合物樹脂基材上形成導電圖案的方法：摻混且模製含有過渡金屬諸如銅、鉻、或類似者之特定無機添加劑(例如尖晶石結構之CuCr2O4、及類似者)於聚合物樹脂小片中，以形成聚合物樹脂基材，將電磁波諸如雷射、及類似者直接輻射在預定區上，且電鍍該經雷射輻射之區以形成金屬層。在此方法中，在該經雷射輻射之區中由無機添加劑衍生之成份被暴露且作為用於一種電鍍之晶種，以致可以形成該金屬層和導電圖案。
然而，因為在形成該導電圖案之方法中應使用大量高價且特定之無機添加劑，故所有之缺點是總製造成本增加。此外，因為需將該無機添加劑摻混於該聚合物樹脂碎片本身中，該無機添加劑可使該聚合物樹脂基材或由彼所形成之樹脂產品的物理性質諸如機械性、介電常數、及類似者惡化，或可引起介電損失。另外，該特定無機添加劑
諸如具有該尖晶石結構之CuCr2O4、及類似者本身具有獨特顏色，且這些顏色並非完全黑色或白色，以致該特定無機添加劑在製造該具有黑色、白色或其他消費者所要之不同顏色而含有該特定無機添加劑的聚合物樹脂基材或該樹脂產品時可能是惡化的因素。
由於該缺點，已要求能藉由簡化製程將微細導電圖案形成在不同種類之聚合物樹脂產品或樹脂層上卻在該聚合物樹脂本身中不含有該特定無機添加劑的技術。然而，在簡單省略該特定無機添加劑之添加的情況中，因為該電磁波需要藉由相對強的功率所輻射，該製造成本可頗有增加，該聚合物樹脂產品本身之物理性質可惡化，且有技術困難性，因為難以令人滿意地形成微細導電圖案。
本發明已經進行以致力於提供一種藉由相對低功率電磁波之直接輻射形成導電圖案的方法，其能藉由簡化製程將微細導電圖案形成在不同種類之聚合物樹脂產品或樹脂層上，即使在該聚合物樹脂本身中不含有特定無機添加劑。
此外，本發明已經進行以致力於提供一種樹脂結構，其具有藉由該形成導電圖案之方法所得之導電圖案。
本發明之例示具體例提供一種藉由電磁波之直接輻射形成導電圖案的方法，該方法包括：藉由使該電磁波選擇性地輻射在含有以碳為底質之黑色顏料的聚合物樹脂基材上以形成具有預定表面粗糙度之第一區；在該聚合物樹脂基材上形成導電性晶種；藉由電鍍具有導電性晶種形成於其上的該聚合物樹脂基材以形成金屬層；及由該聚合物樹脂基材之第二區移除該導電性晶種和該金屬層，其中該第二區所具有之表面粗糙度小於該第一區之表面粗糙度。
該聚合物樹脂基材之第一區可具有約1微米或更大之藉由中心線算術平均粗糙度之絕對值(Ra)所定義之表面粗糙度，且該第二區所具有之中心線算術平均粗糙度之絕對值(Ra)可比第一區者小。
本發明之另一例示具體例提供一種具有導電圖案之樹脂結構，其包含：聚合物樹脂基材，其係經區分成第一區(其經形成以具有1微米或更大之藉由中心線算術平均粗糙度之絕對值(Ra)所定義之表面粗糙度)和第二區(其具有比該第一區之表面粗糙度小之表面粗糙度)，且含有以碳為底質之黑色顏料；及導電性晶種和金屬層，其選擇性地形成在該聚合物樹脂基材之第一區上。
依照本發明，即使不將高價且特定之無機添加劑諸如具有尖晶石結構之CuCr2O4、及類似者包含在聚合物樹脂基材本身中，藉由輻射電磁波諸如雷射或類似者形成導電
性圖案之區的表面粗糙度和與金屬層之黏合性可被調節，以致該導電圖案可藉由簡化製程形成在該聚合物樹脂基材上。
特別地，因為該製程係在添加以碳為底質之黑色顏料(其顯出優越之電磁波諸如雷射或類似者之吸收率，例如為低價之一般顏料的碳黑)的狀態中進行，故即使在相對低功率之電磁波的輻射條件下可令人滿意地將微細導電圖案形成在該聚合物樹脂基材上。
因此，可使該導電圖案之形成方法的製造成本降低，且可將由該特定無機添加劑、高功率電磁波輻射、或類似者所造成之該聚合物樹脂基材或產物的物性(諸如機械性、及類似者)的惡化最小化。此外，因為該以碳為底質之黑色顏料本身顯出消費者所要之黑色，故容易獲得著以黑色之樹脂產品、及類似者。
結果，藉由使用該導電圖案之形成方法，可明顯有效地將用於天線、RFID標籤、不同種類之感應器、MEMS結構、及類似者之導電圖案形成在不同種類之樹脂產品諸如智慧型手機殼及類似者之上。
圖1是以處理序列的方式，概略顯示依照本發明之例示具體例之藉由電磁波之直接輻射形成導電圖案之方法實例的圖。
圖2a是顯示狀態之照片，其中預定區具有藉由實例
1之形成導電圖案的方法中之將雷射輻射至聚合物樹脂基材所形成的表面粗糙度，且圖2b是具有該表面粗糙度之經雷射輻射區的光學顯微照片。
圖3a是顯示狀態之照片，其中該導電圖案係藉由實例1之形成該導電性圖案之方法中之將金屬層及類似者由未受雷射輻射之區選擇性地移除而形成在聚合物樹脂基材上，且圖3b是在該經雷射輻射之區上所形成之金屬層的光學顯微照片。
圖4是顯示藉由形成依照實例1之導電圖案且進行橫切測試所得之結果的照片。
圖5是在依照比較實例1之形成該導電圖案之方法中，於經雷射輻射之區中所形成的金屬層的光學顯微照片。
圖6是顯示藉由在參照實例2中形成該導電圖案且進行橫切測試所得之結果的照片。
圖7是顯示在依照實例1和比較實例2之雷射輻射之前和之後，藉由分析聚合物樹脂基材之XRD圖案所得之結果的視圖。
在下文中將描述一種依照本發明之特定例示具體例之藉由電磁波之直接輻射形成導電圖案的方法及具有所形成之導電圖案的樹脂結構。
依照本發明之例示具體例，該藉由電磁波之直接輻射
以形成導電圖案之方法包括：藉由使該電磁波選擇性地輻射在含有以碳為底質之黑色顏料的聚合物樹脂基材上以形成具有預定表面粗糙度之第一區；在該聚合物樹脂基材上形成導電性晶種；藉由電鍍具有導電性晶種形成於其上的該聚合物樹脂基材以形成金屬層；及由該聚合物樹脂基材之第二區移除該導電性晶種和該金屬層，其中第二區所具有之表面粗糙度小於該第一區之表面粗糙度。
依照本發明之例示具體例，首先，形成具有諸如凹凸形、圖案、不定形狀、或類似者之形狀的表面結構，以致第一區之聚合物樹脂基材藉由將電磁波諸如雷射、或類似者輻射在第一區(其中形成該導電圖案)上而具有預定表面粗糙度。在第一區中，於該聚合物樹脂基材與待藉由電鍍形成在第一區中之金屬層之間的黏合性可因該預定表面粗糙度而得以改良。
同時，在未受該電磁波諸如雷射、或類似者所輻射之第二區中，可因該聚合物樹脂基材本身之原初表面性質而在該聚合物樹脂基材與第二區中之該金屬層之間顯出差的黏合性。
在此，該輻射電磁波之製程係在以下狀態中進行：添加顯出優越之電磁波(諸如雷射、或類似者)吸收率之以碳為底質之黑色顏料(例如為低價一般顏料之碳黑、及類似者)，以致可在第一區中形成所要水平之表面粗糙度且可將在該聚合物樹脂基材表面與該金屬層之間的黏合性改良至所要水平，即使在相對低功率之電磁波的輻射條件下
亦然。
因此，當將用於促進電鍍製程之導電性晶種形成在第一區之聚合物樹脂基材上且進行該電鍍製程時，可在第一區中順利地形成金屬層，其與該聚合物樹脂基材具有優越黏合性；同時，可在第二區中形成金屬層，其由於差的黏合性而容易移除。因此，當將弱的物理力施加至該聚合物樹脂基材上以選擇性地移除第二區之金屬層和導電性晶種時，可容易地將所要之導電圖案形成在該聚合物樹脂基材上。
如上述，依照本發明之例示具體例，例如，即使高價之特定無機添加劑諸如具有尖晶石結構之CuCr2O4、及類似者並未包含在該聚合物樹脂基材本身中，可以調節其中有藉由輻射該電磁波諸如雷射、或類似者所形成之導電圖案的區之表面粗糙度、黏合性及類似者，以致可藉由簡化製程將該導電圖案形成在該聚合物樹脂基材上。此外，藉由使用如上述之以碳為底質之黑色顏料，即使在低功率電磁波輻射條件下，也可令人滿意地將微細導電圖案形成在該聚合物樹脂基材上。
因此，可將形成該導電圖案之方法的製造成本降低，且可將由於該特定無機添加劑所造成之該聚合物樹脂基材或產品之物性(諸如機械性、及類似者)的惡化最小化。此外，因為該以碳為底質之黑色顏料本身顯出消費者所要之黑色，明顯容易獲得著以黑色之樹脂產物、及類似者。
同時，在下文中，引用圖式，更明確地針對每一處理
步驟來描述依照本發明之例示具體例之藉由電磁波之直接輻射形成該導電圖案之方法。圖1是以處理序列的方式，概略顯示依照本發明之例示具體例之藉由電磁波之直接輻射形成導電圖案之方法實例的圖。
如圖1中顯示的，在依照例示具體例之形成該導電圖案的方法中，首先藉由將電磁波選擇性地輻射在該聚合物樹脂基材上以形成具有預定表面粗糙度之第一區。
在此，該聚合物樹脂基材在沒有特定限制下可包括能形成不同聚合物樹脂產品或樹脂層的任何熱固性樹脂或任何熱塑性樹脂。能形成該聚合物樹脂基材之聚合物樹脂的特定實例可包括聚對苯二甲酸亞烷基酯樹脂諸如ABS樹脂、聚對苯二甲酸亞丁基酯樹脂、聚對苯二甲酸亞乙基酯樹脂、或類似者、聚碳酸酯樹脂、聚丙烯樹脂及聚鄰苯二甲醯胺樹脂、及類似者，且在此之外，可藉由使用不同聚合物樹脂形成該聚合物樹脂基材。
此外，該聚合物樹脂基材含有該以碳為底質之黑色顏料以增加該電磁波(諸如雷射或類似者)之吸收率，以甚至在低功率電磁波之輻射條件下形成具有預定表面粗糙度之第一區。
可以使用任何包括以碳為底質之成份作為主要成份而具有高的雷射(及類似者)之吸收率且顯出接近黑色之顏色的顏料成份作為該以碳為底質之黑色顏料。其特定實例可以是選自由碳黑、松黑煙灰(pine black soot)、煤灰、燈黑、槽黑、爐黑及乙炔黑所組成之組群中至少一
者。
此外，該以碳為底質之黑色顏料含量以該聚合物樹脂基材重量計可以是約0.01至10重量%，或約0.1至5重量%，或約0.2至1重量%。因此，該聚合物樹脂基材可具有優越之電磁波吸收率，以致即使在低功率電磁波之輻射條件下可形成具有預定表面粗糙度的第一區。此外，可以降低因添加不同添加劑所造成之製造成本的增加，或聚合物樹脂基材之物性惡化。
另外，較佳是：該以碳為底質之黑色顏料所具有之粒子狀態是具有約10奈米至1微米，或約20奈米至200奈米之粒徑，以在該聚合物樹脂基材中具有合適水平之電磁波吸收率，且更加降低該聚合物樹脂基材之物性的惡化。
同時，除了上述之以碳為底質之黑色顏料之外，在該聚合物樹脂基材中視需要還可另外添加或包括一般用以形成該聚合物樹脂產物之添加劑，例如UV穩定劑、熱穩定劑、耐衝擊強化劑、及類似者。該添加劑之合適含量，以整個聚合物樹脂基材重量計，可以是約2重量%或更少或約0.05至2.0重量%。同時，該聚合物樹脂基材不必須包括該特定無機添加劑諸如具有尖晶石結構之CuCr2O4、及類似者，其在先前技藝中係已知用於藉由輻射該電磁波形成該導電圖案。
此外，第一區具有藉由將雷射輻射在上述聚合物樹脂基材上所致之預定表面粗糙度，其中在具有該表面粗糙度之第一區中可以形成相對標準化之圖案諸如孔、網目圖
案、及類似者、或凹凸形狀，或可以形成不定形之表面結構(其中複雜地形成多個不規則孔、圖案或凹凸形狀)，且第一區之聚合物樹脂基材由於不同表面形狀或結構而可具有預定表面粗糙度。同時，為確保在待形成於第一區上之金屬層(導電圖案)與該聚合物樹脂基材表面之間的優越黏合性，第一區之聚合物樹脂基材可藉由輻射電磁波諸如雷射、或類似者而具有預定水平或更高之表面粗糙度。
作為一實例，該聚合物樹脂基材之第一區可具有約1微米或更大、或約1至10微米、或約1至6微米、或約1至3微米之藉由中心線算術平均粗糙度之絕對值(Ra)所定義之表面粗糙度，且未受該電磁波所輻射之第二區可具有之藉由中心線表面粗糙度(Ra)所定義之表面粗糙度小於第一區者，例如約400奈米或更小、或約300奈米或更小、或約0至300奈米、或約50至250奈米。
此外，在另一實例中，第一和第二區之表面粗糙度也可以藉由以下方式定義：在依照ISO 2409標準方法之橫切測試中所測得之與該金屬層的黏合程度。例如，當依照ISO 2409標準方法之具有2毫米或更小之間隔的橫切測試係藉由使用具有約4.0至6.0N/10毫米寬之黏合性的帶而進行時，該聚合物樹脂基材之第一區可具有藉由黏合性(例如ISO 0或1級)所限定之表面粗糙度，在該黏合性下，標的金屬層之剝離面積在測試下係對應於該金屬層面積之約5%或更小，且當依照ISO 2409標準方法之具有2毫米或更小之間隔的橫切測試係藉由使用具有約4.0至
6.0N/10毫米寬之黏合性的帶而進行時，該聚合物樹脂基材之第二區可具有藉由黏合性(例如ISO 5級或更大)所限定之表面粗糙度，在該黏合性下，標的金屬層之剝離面積在測試下係對應於該金屬層面積之約65%或更大。
因為第一區之聚合物樹脂基材具有上述之藉由輻射該電磁波諸如雷射、或類似者所致之表面粗糙度，故當將該金屬層在以下之電鍍製程中形成在第一區上時，可用優越之黏合性將該金屬層形成且保留在該聚合物樹脂基材上，以形成優越導電圖案。與第一區相比，因為未受電磁波諸如雷射、或類似者所輻射之第二區的聚合物樹脂基材由於該基材之表面性質而具有上述之表面粗糙度，故當在以下之電鍍製程中形成該金屬層時，該金屬層由於明顯低之黏合性而容易地由第二區移除。結果，第二區之金屬層可容易且選擇性地移除以將該導電圖案形成在第一區之聚合物樹脂基材上。
同時，可在如下述之預定條件下輻射電磁波諸如雷射、或類似者，以使第一區之聚合物樹脂基材具有上述表面粗糙度。
首先，在該電磁波輻射中，可輻射雷射電磁波，例如可輻射具有約248奈米、約308奈米、約355奈米、約532奈米、約585奈米、約755奈米、約1064奈米、約1070奈米、約1550奈米、約2940奈米或約10600奈米之雷射電磁波。在另一實例中，可輻射具有在紅外線(IR)區中之波長的雷射電磁波。
此外，按照該樹脂之種類、該聚合物樹脂基材之物性、厚度、待形成之金屬層的種類或厚度、或在考慮上述因素時之合適水平的黏合性，可以控制或改變輻射該雷射電磁波時的特定條件。同時，可在平均功率約2W或更大、或約2至20W、或約3至10W之條件下輻射該雷射電磁波，以使第一區之聚合物樹脂基材具有如上述之預定表面粗糙度。如上述，既然具有高的電磁波吸收率之該以碳為底質之黑色顏料、及類似者被包含在該聚合物樹脂基材中，甚至可在低功率條件下形成具有合適表面粗糙度之第一區，且欲於稍後形成之金屬層與第一區之聚合物樹脂基材可具有優越黏合性。
此外，該雷射電磁波可藉由相對高之功率被輻射一次，但該雷射電磁波也可藉由相對低之功率被輻射二或更多次。隨著該雷射電磁波之輻射次數增加，該表面粗糙度也增加，在該表面上所形成之結構諸如凹凸形狀、及類似者可由孔形圖案改變成網目圖案、不定形表面結構或類似者。因此，藉由控制輻射雷射電磁波之條件及次數，可在第一區之聚合物樹脂基材上形成合適表面結構，且可提供具有合適水平之表面粗糙度和與該金屬層之優越黏合性。
另外，在輻射雷射電磁波時，按照輻射間隔，可在該聚合物樹脂基材上形成孔形狀或類似形狀之該電磁波的輻射軌跡。然而，為使第一區之聚合物樹脂基材具有上述合適之表面粗糙度，較佳使該雷射電磁波被輻射以致該電磁波之輻射軌跡之中心部份之間的間隔、或該電磁波之輻射
間隔約20微米或更大、或約20至70微米，但不特定限制於此。結果，第一區之聚合物樹脂基材可具有合適之表面粗糙度及合適之與該金屬層的黏合性，且可使該聚合物樹脂基材之物性或類似者之惡化減低。
同時，如上述，在將該電磁波諸如雷射輻射在第一區上之後，可如圖1所示的，將導電性晶種形成在該聚合物樹脂基材上。該導電性晶種係在電鍍時在該聚合物樹脂基材上成長，且促使該金屬層藉由電鍍形成。因此，可將更優越之金屬層和該導電圖案合適地形成在第一區之聚合物樹脂基材上。
導電性晶種可含有金屬奈米粒子、金屬離子、或金屬錯合離子。此外，該金屬離子或該金屬錯合離子可被使用以作為離子本身或作為偶合該金屬離子之含有金屬的化合物或作為含有金屬錯合離子之金屬錯合物，或甚至作為該含有金屬之化合物或該金屬錯合物的粒子。
可被包括在該導電性晶種中的金屬原子的種類並不特別限制，只要該金屬原子具有導電性。例如，該導電性晶種可含有至少一種選自由銅(Cu)、鉑(Pt)、鈀(Pd)、銀(Ag)、金(Au)、鎳(Ni)、鎢(W)、鈦(Ti)、鉻(Cr)、鋁(Al)、鋅(Zn)、錫(Sn)、鉛(Pb)、鎂(Mg)、錳(Mn)及鐵(Fe)、彼等之離子或錯合離子組成之群組之金屬。
此外，為要在該聚合物樹脂基材上形成該導電性晶種，可將含有上述導電性晶種諸如該金屬奈米粒子、該金
屬離子、或該金屬錯合離子的分散液或溶液施加在該聚合物樹脂基材上，接著進行沉澱方法、乾燥方法、及/或還原方法，藉此形成所要形式(例如粒子形式)之導電性晶種。更特別地，當該分散液或類似者含有該金屬奈米粒子，該金屬奈米粒子藉由溶解度差異而沉澱且乾燥以合適地形成粒子形式之導電性晶種，且當該分散液或類似者含有該金屬離子、或該金屬錯合離子(或含這些離子之金屬化合物或錯合物)時，將該金屬離子、或該金屬錯合離子還原且乾燥以合適地形成粒子形式之導電性晶種。
在此，該金屬離子或該金屬錯合離子之還原可藉由使用一般還原劑以進行，例如至少一種選自由下列所組成之群組之還原劑：以醇為底質之還原劑、以醛為底質之還原劑、以次磷酸鹽為底質之還原劑、以聯胺為底質之還原劑、硼氫化鈉及氫化鋰鋁。
此外，該分散液或該溶液可合適地包括能改良在該聚合物樹脂基材與該導電性晶種之間的封閉黏合性的以水為底質之聚合物溶液、或能使該金屬離子或該金屬錯合離子穩定之以水為底質之錯合劑以作為液相介質。
另外，該導電性晶種之分散液或溶液可藉由用於將液相組成物施加至該聚合物樹脂基材的一般製程，例如浸漬、旋轉塗覆、噴灑、或類似者之方法來施加。
如上述所形成之導電性晶種可形成在該聚合物樹脂基材之整個表面上(其包括在該第一區上所形成之表面凹凸形、圖案、或表面結構之間的空間)，且可在該電鍍製程
中用以使該金屬層順利形成且控制該金屬層之電鍍速率、物理性質或類似者。
同時，在如上述輻射該電磁波之後，就立即可以進行用於形成該導電性晶種的方法；然而，在以具有比該分散液或溶液之表面張力低之表面張力之表面活性劑選擇性地表面處理該聚合物樹脂基材之後，可以進行該形成導電性晶種的製程。此外，該聚合物樹脂基材可在下述狀態中被表面處理：將表面活性劑添加至用於形成該導電性晶種之該分散液或該溶液本身。
表面活性劑可允許該導電性晶種更均勻地形成且維持在該聚合物樹脂基材表面上，尤其是在該表面凹凸形、圖案、或表面結構之間。該理由是因為該表面活性劑將在該表面結構之間的空氣移除以幫助該導電性晶種更容易地滲透在該等表面結構之間。因此，當附加以該表面活性劑之處理時，將該導電性晶種順利地整個吸附該第一區上，且可藉由該電鍍製程使該金屬層更均勻且順利地形成。此外，由於以該表面活性劑處理及該導電性晶種之形成，可更改良在該第一區上金屬層與該聚合物樹脂基材的黏合性以順利地形成具有優越導電性之導電性圖案。
該表面活性劑之種類可視如上述之導電性晶種的分散液或溶液的種類而改變，且可包括任何具有比該分散液或溶液之表面張力低之表面張力的液相介質。例如，可以使用具有相對低表面張力之有機溶劑諸如乙醇、及類似者作為該界面活性劑。
此外，該表面活性劑可藉由浸漬該聚合物樹脂基材數秒至數分鐘之方法、及類似者來處理。
同時，引用圖1，在將該導電性晶種形成在該聚合物樹脂基材上之後，可藉由電鍍聚合物樹脂基材(其上形成導電性晶種)以形成該金屬層。該用於形成金屬層之方法可藉由將該導電性金屬無電電鍍在該聚合物樹脂基材而進行，且該無電電鍍製程的方法及條件可藉由一般方法和條件來進行。
例如，該電鍍製程係藉由使用含有以下物質之電鍍溶液來進行：用於形成該金屬層之導電性金屬(例如金屬來源、諸如銅、及類似者)、錯合劑、pH調節劑、還原劑、及類似者，以在包括第一區和第二區之該聚合物樹脂基材上形成該金屬層。在此，可在如上述之經成長的導電性晶種上形成該金屬層。
可順利地藉由優越之黏合性在該第一區上形成該金屬層；同時，由於與該聚合物樹脂基材有差的黏合性，可將該金屬層容易地由該第二區移除。
在形成該金屬層後，可將該導電性晶種和該金屬層由該聚合物樹脂基材之第二區選擇性地移除，以在殘留之第一區上形成該導電性圖案。
如上述，因為該金屬層係在明顯容易移除該金屬層之狀態中形成在該第二區上，可藉由簡單方法諸如將弱的物理動力施加在該聚合物樹脂基材上、及類似者，將該金屬層和該導電性晶種由該第二區選擇性地移除。在此，由於
該第一區上該金屬層與該聚合物樹脂基材有優越的黏合性，該金屬層可仍保留以形成該導電性圖案。
如上述，由該第二區移除該導電性晶種和該金屬層的製程可藉由以下方法進行：任何將弱的物理動力施加在該聚合物樹脂基材的方法諸如超音波輻射(超音波處理)、液相清洗、液相淋洗、吹氣、輕拍、刷拂、及使用人力之方法諸如直接用手撣塵或掃除，或這些所選之二或更多者之組合。
例如，清洗或淋洗係在該超音波輻射下於去離子水中進行預定時間，且進行吹氣、及類似者，而可將該第二區之導電性晶種和該金屬層選擇性地移除。
具有藉由上述方法所形成之導電性圖案的樹脂結構可包括該聚合物樹脂基材，其區分成第一區(其經形成以具有約1微米或更大之藉由中心線算術平均粗糙度的絕對值(Ra)所定義之表面粗糙度)和第二區(其具有比該第一區之表面粗糙度小之表面粗糙度)，且含有以碳為底質之黑色顏料；及在該聚合物樹脂基材之第一區上所選擇性地形成之該導電性晶種和該金屬層。
在此，因為該第一和第二區之表面粗糙度係在依照例示具體例之方法中充份描述，將省略其另外的描述。此外，如上述，該第一區可對應於受該電磁波諸如雷射、或類似者輻射的區。
在此樹脂結構中，即使在輻射該電磁波諸如雷射、或類似者之後，該以碳為底質之黑色顏料僅用以改良該電磁
波輻射之吸收率，但不受該電磁波輻射之破壞或不形成由該輻射所衍生之金屬核心、及類似者，此與在先前技藝中所用之具有尖晶石結構CuCr2O4、及類似者的特定無機添加劑不同。另外，該樹脂結構不包括該特定無機添加劑諸如CuCr2O4、及類似者。
結果，在該結構中，該第二區(或在輻射雷射之前的第一區)之聚合物樹脂基材可顯出之XRD圖案不包括由該特定無機添加劑(例如導電性過渡金屬諸如銅或銀、或含有該導電性過渡金屬之金屬化合物)所衍生之峰。該XRD圖案之實例係在圖7中顯示。
同時，如上述之樹脂結構可以是具有用於天線之導電性圖案之不同種類的樹脂產品或樹脂層諸如智慧型手機殼、及類似者，或可以是具有不同種類之具有導電性圖案之樹脂產品或樹脂層諸如其它RFID標籤、不同種類之感測器、或MEMS結構、及類似者。
如上述，依照本發明之例示具體例，即使該聚合物樹脂基材本身不含有高價且特定之無機添加劑諸如具有尖晶石結構之CuCr2O4，及類似者，也可以調整藉由輻射電磁波諸如雷射、或類似者形成導電性圖案之區的表面粗糙度及其與金屬層之黏合性，以致可藉由簡化製程在具有相對低功率之輻射條件下將優越之導電性圖案形成在該聚合物樹脂基材上。
因此，可以降低形成該導電性圖案之製程的製造成本，且藉由該特定無機添加劑可將該聚合物樹脂基材或產
品的物理性質諸如機械性、介電常數、及類似者的惡化可能性降低。另外，容易藉由該以碳為底質之黑色顏料的獨特顏色製造黑色的聚合物樹脂產品。
在下文中，本發明之作用及效果藉由本發明之特定實例來詳細描述。同時，提供這些實例作為實例，且因此不應視為本發明範圍的限制。
製備聚碳酸酯樹脂基材，其含有總量少於2重量%之UV穩定劑、熱穩定劑、及衝擊強化劑，且含有0.25重量%之碳黑。在具有25%之功率比的輻射條件(平均功率：6.7W)下，將具有1064奈米波長之雷射一次輻射在聚碳酸酯樹脂基材之預定區上。在此，將在該聚碳酸酯樹脂基材之該雷射輻射軌跡的中心部份之間的間隔藉由控制該雷射之輻射間隔以控制成約50微米。
因此，藉由雷射所輻射之聚碳酸酯樹脂基材在該預定區上具有預定之表面粗糙度。測量藉由雷射所輻射之區及未藉由雷射所輻射之區的中心線算術平均粗糙度之絕對值(Ra)。藉由使用光學剖面儀(Nano view E1000,Nanosystem，韓國)在0.2毫米×0.3毫米面積中測量這些Ra。由於該測量，藉由雷射所輻射之區具有約5630奈米之Ra且未藉由雷射所輻射之區具有約226奈米之Ra。如以上所製造之聚碳酸酯樹脂基材的照片係在圖2a中顯示，且藉由雷射所輻射形成以具有該表面粗糙度之區的光
學顯微照片係在圖2b中顯示。
然後，將該聚碳酸酯樹脂基材浸漬於以水為底質的聚合物溶液(其包括含有Pd之化合物粒子以具有Pd離子)5分鐘，以將包括Pd之導電性晶種粒子形成在該基材上。其次，該基材係以去離子水清洗，且藉由使用銅作為導電性金屬以進行無電電鍍。在該無電電鍍時，使用含有銅源(硫酸銅)、錯合劑(羅雪(Rochelle)鹽)、pH調節劑(氫氧化鈉水溶液)、及還原劑(甲醛)的電鍍溶液。在室溫下進行無電電鍍1小時，接著超音波清潔，以形成該金屬層。能確認：可順利地將該金屬層形成在藉由雷射所輻射之區上；然而，在其餘區中的金屬層由於差的黏合性以致明顯容易被移除，故係形成為剝離狀態。
然後，將該基材浸漬於該去離子水中，接著超音波輻射(超音波處理)20分鐘，且吹氣，以選擇性地將未受雷射所輻射之區的金屬層移除。因此，將具有該金屬層之導電圖案選擇性地形成在藉由雷射所輻射之區，且其照片係在圖3a中顯示，且經由無電電鍍形成在藉由雷射所輻射之區上的金屬層的光學顯微照片係顯示在圖3b中。
同時，依照ISO 2409標準方法之橫切測試係藉由在藉由雷射所輻射之區(亦即具有該金屬層和形成於該金屬層上之該導電圖案的區)中使用具有約4.9N/10毫米寬度之帶(3M scotch膠帶#371)來進行。在此，在該基材與該導電性圖案之間的黏合性係藉由以下方式測試：將該金屬層裁切成10×10的圖形(約2毫米或更小之間隔)，且
測量藉由貼合並拆離該帶所剝離之金屬層的面積。顯示進行該黏合性測試所得的結果的照片係在圖4中顯示。
由於該黏合性測試能確認：在測試下該標的金屬層的剝離面積對應於該金屬層之面積的約0%(ISO 0級)，且順利地藉由優越之黏合性將該金屬層和該導電圖案形成在藉由雷射所輻射之區上。
藉由與實例1相同之方法形成實例2之導電圖案，除了使用聚碳酸酯/ABS樹脂之多層基材而非使用該聚碳酸酯樹脂基材。
在實例2中，在輻射雷射後，藉由雷射所輻射之區和未藉由雷射所輻射之區的中心線算術平均粗糙度之絕對值(Ra)係藉由與實例1相同之方法測量，且藉由雷射所輻射之區具有約5370奈米之Ra且未藉由雷射所輻射之區具有約183奈米之Ra。
此外，在實例2中形成該金屬層和該導電圖案之後，藉由與實例1相同之方法，在具有金屬層和形成在該金屬層上之導電圖案之區中進行橫切測試。由於該黏合性測試，能確認：在測試下之標的金屬層之剝離面積對應於該金屬層之面積的約5%或更低(ISO 1級)，且藉由優越黏合性，順利地將該金屬層和該導電圖案形成在藉由雷射所輻射之區。
藉由與實例1相同之方法形成比較實例1之導電圖案，除了並不進行在實例1中形成包括Pd之導電性晶種粒子之製程。依照比較實例1，經由該無電電鍍，在藉由雷射所輻射之區上所形成之金屬層之光學顯微照片係在圖5中顯示。
由圖5能領會：並不形成該導電性晶種粒子，以致僅在藉由雷射所輻射之區的一部份進行該電鍍。為供引用，僅圖5中完全暗的部份之間的發亮部份是完全進行該電鍍之部份。亦即，在比較實例1中確認：即使在藉由雷射所輻射之區中並沒有完全地進行該無電電鍍，以致該金屬層和該導電性圖案並沒有完全地形成。
藉由與實例1相同之方法形成比較實例2之導電圖案，除了不使用該碳黑且將該雷射之輻射條件改成具有約70%之功率比率的輻射條件(平均功率：18.6W)。
在比較實例2中，在輻射雷射後，藉由雷射所輻射之區和未藉由雷射所輻射之區的中心線算術平均粗糙度之絕對值(Ra)係藉由與實例1相同之方法測量，且藉由雷射所輻射之區具有約830奈米之Ra且未藉由雷射所輻射之區具有約223奈米之Ra。
此外，在比較實例2中形成該金屬層和該導電圖案之後，藉由與實例1相同之方法，在具有金屬層和形成在該
金屬層上之導電圖案之區中進行橫切測試。由於該黏合性測試，能確認：在測試下之標的金屬層之剝離面積對應於該金屬層之面積的約5%以上至15%或更少(ISO 2級)，且因此將該金屬層和該導電圖案形成在藉由雷射所輻射之區；然而，該導電圖案藉由與該基材之相對差的黏合性並未順利地被維持。
藉由使用5重量%之CuCr2O4而非使用實例1之碳黑以進行參照實例1。然後，在具有25%之功率比的輻射條件(平均功率：6.7W)下，進行雷射之輻射。藉由與實例1相同之方法形成參照實例1之導電圖案，除了在輻射雷射後不進行形成該導電性晶種粒子之製程，且在該無電電鍍製程後不進行超音波清潔。
在參照實例1中，在輻射雷射後，藉由與實例1相同之方法，測量藉由雷射所輻射之區及未藉由雷射輻射之區的中心線算術平均粗糙度之絕對值(Ra)，且藉由雷射所輻射之區具有約6200奈米之Ra且未藉由雷射所輻射之區具有約213奈米之Ra。
此外，在該金屬層和該導電性圖案在參照實例1中被形成之後，藉由與實例1相同之方法在具有該金屬層和形成在該金屬層上之該導電圖案之區中進行橫切測試。由於該黏合性測試能確認：在測試下該標的金屬層的剝離面積
對應於該金屬層之面積之約5%或更小(ISO 0級)，且將該金屬層和該導電性圖案順利地形成在該藉由雷射所輻射之區中。同時，能確認：需要使用具有相對高含量(5重量%)之該特定無機添加劑，且需要與實例1相當之雷射輻射條件，以形成優越導電圖案。
藉由與參照實例1相同之方法形成參照實例2之導電圖案，除了雷射輻射條件改成具有20%之功率比的輻射條件(平均功率：5.3W)。
在參照實例2中，在輻射雷射後，藉由與實例1相同之方法，測量藉由雷射所輻射之區及未藉由雷射輻射之區的中心線算術平均粗糙度之絕對值(Ra)，且藉由雷射所輻射之區具有約970奈米之Ra且未藉由雷射所輻射之區具有約197奈米之Ra。
此外，在該金屬層和該導電性圖案在參照實例2中被形成之後，藉由與實例1相同之方法在具有該金屬層和形成在該金屬層上之該導電圖案之區中進行橫切測試。顯示上述測試之結果的照片係在圖6中顯示。由於該黏合性測試能確認：在測試下該標的金屬層的剝離面積對應於該金屬層之面積之約5%以上至15%或更小(ISO 2級)，且因此將該金屬層和該導電性圖案形成在該藉由雷射所輻射之區中；然而，由於與該基材之相對差的黏合性，該導電圖案並未順利地被維持。
由如上述之實例、比較實例、和參照實例之測試結果能確認：依照實例，即使在具有相對低功率之雷射的輻射條件下，能將優越之導電性圖案形成在藉由雷射所輻射而不使用該特定無機添加劑之區上。
由比較實例能確認：因為不使用碳黑或不進行用於形成該導電性晶種粒子的製程，即使在具有相對高功率之雷射的輻射條件下也不能形成優越之導電性圖案。
此外，能確認：在參照實例1中，在相當於實例1之雷射輻射條件下形成優越之導電圖案；然而，需要具有相對高含量之該特定無機添加劑，且當雷射之輻射條件類似參照實例2稍微降低時，難以形成優越之導電圖案。
在依照實例1和比較實例2輻射雷射之前和之後，分析該基材之XRD圖案且顯示在圖7中。參照圖7，能確認在輻射雷射之前和之後的XRD圖案分別與實例1中者相同，與不使用個別之添加劑的比較實例2類似。
此外，參照圖7，能確認：在實例1和比較實例2之XRD圖案中，不顯示由該特定無機添加劑(例如該導電性過渡金屬諸如銅或銀或含有該導電性過渡金屬之金屬化合物)所衍生之峰。
Claims (17)
- 一種藉由電磁波之直接輻射以形成導電圖案之方法，該方法包含：藉由使該電磁波選擇性地輻射在含有碳黑之以碳為底質之黑色顏料的聚合物樹脂基材上以形成具有預定表面粗糙度之第一區；在該整個聚合物樹脂基材上形成導電性晶種(conductive seed)；藉由電鍍具有導電性晶種形成於其上的該聚合物樹脂基材以形成金屬層；及由該聚合物樹脂基材之第二區移除該導電性晶種和該金屬層，其中該第二區所具有之表面粗糙度小於該第一區之表面粗糙度。
- 如申請專利範圍第1項之方法，其中該以碳為底質之黑色顏料的含量以該聚合物樹脂基材之重量計係0.01至10重量%。
- 如申請專利範圍第1項之方法，其中該以碳為底質之黑色顏料以具有10奈米至1微米之粒徑的粒子狀態被包含。
- 如申請專利範圍第1項之方法，其中當依照ISO 2409標準方法藉由使用具有4.0至6.0N/10毫米寬之黏合性的帶以進行具有2毫米或更短之間隔的橫切(cross-cut)測試時，該聚合物樹脂基材之第一區具有藉由黏合 性所限定之表面粗糙度，在該黏合性下，標的金屬層之剝離面積在測試下係對應於該金屬層面積之5%或更小。
- 如申請專利範圍第1項之方法，其中當依照ISO 2409標準方法藉由使用具有4.0至6.0N/10毫米寬之具有黏合性的帶以進行具有2毫米或更短之間隔的橫切測試時，該聚合物樹脂基材之第二區具有藉由黏合性所定義之表面粗糙度，在該黏合性下，標的金屬層之剝離面積在測試下係對應於該金屬層面積之65%或更大。
- 如申請專利範圍第1項之方法，其中該聚合物樹脂基材之第一區具有1微米或更大之藉由中心線算數平均粗糙度之絕對值(Ra)所定義之表面粗糙度，且該第二區所具有之中心線算數平均粗糙度之絕對值(Ra)小於該第一區者。
- 如申請專利範圍第1項之方法，其中該聚合物樹脂基材含有選自由ABS樹脂、聚對苯二甲酸亞烷基酯樹脂、聚碳酸酯樹脂、聚丙烯樹脂及聚鄰苯二甲醯胺樹脂所組成之組群中之至少一種。
- 如申請專利範圍第1項之方法，其中該電磁波之輻射係藉由在平均功率為2至20瓦之輻射條件下輻射雷射電磁波而進行。
- 如申請專利範圍第1項之方法，其中該導電性晶種含有金屬奈米粒子、金屬離子或金屬錯合離子。
- 如申請專利範圍第9項之方法，其中該導電性晶種含有選自由銅(Cu)、鉑(Pt)、鈀(Pd)、銀 (Ag)、金(Au)、鎳(Ni)、鎢(W)、鈦(Ti)、鉻(Cr)、鋁(Al)、鋅(Zn)、錫(Sn)、鉛(Pb)、鎂(Mg)、錳(Mn)及鐵(Fe)、彼等之離子或錯合離子所組成之組群中之至少一種金屬。
- 如申請專利範圍第9項之方法，其中該導電性晶種之形成包括：將含有該金屬奈米粒子、該金屬離子、或該金屬錯合離子之分散液或溶液施加在該聚合物樹脂基材上；及使該金屬奈米粒子沉澱且乾燥或使該金屬離子或該金屬錯合離子還原且乾燥以形成粒子形式之該導電性晶種。
- 如申請專利範圍第11項之方法，其中該金屬離子或該金屬錯合離子之還原係在選自由以醇為底質之還原劑、以醛為底質之還原劑、以次磷酸鹽為底質之還原劑、以聯胺為底質之還原劑、硼氫化鈉及氫化鋰鋁所組成之組群之至少一種還原劑存在下進行。
- 如申請專利範圍第11項之方法，其另包含在該電磁波輻射與該導電性晶種形成之間，以具有比該分散液或溶液之表面張力低之表面張力的表面活性劑來表面處理該聚合物樹脂基材。
- 如申請專利範圍第1項之方法，其中該金屬層之形成包括將導電性金屬無電電鍍在該聚合物樹脂基材上。
- 如申請專利範圍第1項之方法，其中由該第二區移除該導電性晶種和該金屬層係包括藉由以選自由超音波輻射(超音波處理)、液相清洗、液相淋洗、吹氣、輕 拍、刷拂、及使用人力之方法所組成之組群中之一或二或多項方法之組合將物理動力施加在該聚合物樹脂基材上。
- 一種具有導電圖案之樹脂結構，其包含：聚合物樹脂基材，其係經區分成第一區(其經形成以具有1微米或更大之藉由中心線算數平均粗糙度之絕對值(Ra)所定義之表面粗糙度)和第二區(其具有比該第一區之表面粗糙度小之表面粗糙度)，且含有碳黑之以碳為底質之黑色顏料；及導電性晶種和金屬層，其形成在該聚合物樹脂基材之第一區上，其中該聚合物樹脂基材含有選自由ABS樹脂、聚對苯二甲酸亞烷基酯樹脂、聚碳酸酯樹脂、聚丙烯樹脂及聚鄰苯二甲醯胺樹脂所組成之組群中之至少一種，該導電性晶種含有金屬奈米粒子、金屬離子或金屬錯合離子，且該金屬層包括導電性金屬。
- 如申請專利範圍第16項之樹脂結構，其中該第一區對應於藉由依照申請專利範圍第1項之該電磁波所輻射之區。
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| JP5835947B2 (ja) | 2011-05-30 | 2015-12-24 | セーレン株式会社 | 金属膜パターンが形成された樹脂基材 |
| KR20130023519A (ko) | 2011-08-29 | 2013-03-08 | 도레이첨단소재 주식회사 | 도금입자 크기 및 에칭성을 이용한 세미 에디티브 연성동박적층 필름 및 그 제조방법 |
| KR101377273B1 (ko) | 2011-11-17 | 2014-03-26 | 한국기계연구원 | 레이저를 이용한 연성 회로 기판의 제조 시스템 및 그 제조 방법 |
| JP2014058604A (ja) | 2012-09-14 | 2014-04-03 | Mitsubishi Engineering Plastics Corp | 熱可塑性樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法 |
| KR101250932B1 (ko) * | 2013-02-01 | 2013-04-03 | 이도연 | 모바일기기의 안테나 및 그 제조방법 |
| KR101339640B1 (ko) | 2013-04-02 | 2013-12-09 | 김한주 | 레이저 직접 구조화 방법 |
| KR101823660B1 (ko) * | 2013-08-09 | 2018-01-30 | 주식회사 엘지화학 | 전자기파의 직접 조사에 의한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
| US9668342B2 (en) * | 2013-09-27 | 2017-05-30 | Lg Chem, Ltd. | Composition and method for forming conductive pattern, and resin structure having conductive pattern thereon |
| KR101722744B1 (ko) | 2014-10-23 | 2017-04-03 | 주식회사 엘지화학 | 전자기파 조사에 의한 도전성 패턴 형성용 조성물, 이를 사용한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
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2014
- 2014-07-01 KR KR1020140081917A patent/KR101823660B1/ko active IP Right Grant
- 2014-07-01 KR KR1020140081915A patent/KR20150018368A/ko active Search and Examination
- 2014-07-24 KR KR1020140093782A patent/KR20150018382A/ko active Application Filing
- 2014-07-24 US US14/910,915 patent/US20160212860A1/en not_active Abandoned
- 2014-07-24 JP JP2016533234A patent/JP6316961B2/ja active Active
- 2014-07-24 EP EP14834164.7A patent/EP3032548A4/en not_active Withdrawn
- 2014-07-24 CN CN201480044106.XA patent/CN105474330B/zh active Active
- 2014-07-24 WO PCT/KR2014/006756 patent/WO2015020332A1/ko active Application Filing
- 2014-08-07 EP EP14833847.8A patent/EP3007182B1/en active Active
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- 2014-08-07 JP JP2016531544A patent/JP6162898B2/ja active Active
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- 2014-08-07 WO PCT/KR2014/007325 patent/WO2015020455A1/ko active Application Filing
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- 2014-08-07 CN CN201480044109.3A patent/CN105453190B/zh active Active
- 2014-08-07 US US14/910,633 patent/US20160201198A1/en not_active Abandoned
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- 2014-08-07 WO PCT/KR2014/007328 patent/WO2015020456A1/ko active Application Filing
- 2014-08-08 TW TW103127268A patent/TWI565740B/zh active
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| TW494420B (en) * | 2000-04-19 | 2002-07-11 | Matsushita Electric Works Ltd | Wiring accessory switching member |
| TW201234462A (en) * | 2010-11-04 | 2012-08-16 | Sankyo Kasei Kk | A manufacture method of forming a circuit unit |
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