TW202309342A - Surface binding agent and method of treating substrate surface - Google Patents
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本發明係關於一種表面結合劑及使用其處理基材表面之方法，尤係關於一種使用表面結合劑處理非金屬面(如玻璃、矽晶、聚醯亞胺(PI)膜等的表面)及金屬面(如銅與銅合金、鐵鑄、鋁、鋼、鎳、鋅、鎳鐵合金等的表面)，以提升基材之表面與光阻、油墨或待增金屬層(以濺鍍、蒸鍍等方式形成)等塗佈材料之間的附著力之方法。 The present invention relates to a surface binding agent and a method for using it to treat the surface of a substrate, especially to a method of using a surface binding agent to treat a non-metallic surface (such as the surface of glass, silicon crystal, polyimide (PI) film, etc.) and Metal surface (such as the surface of copper and copper alloy, cast iron, aluminum, steel, nickel, zinc, nickel-iron alloy, etc.), to enhance the surface of the substrate and photoresist, ink or metal layer to be added (by sputtering, evaporation Formed in other ways) and other methods of adhesion between coating materials.
通常，為了增進基材表面與塗佈材料之間的附著力，會採用預先粗化處理基材表面的方法，例如，在印刷電路板的粗化銅箔上形成光阻，然後曝光使光阻具有特定圖案形狀，使部分的銅箔表面外露出，接著蝕刻除去外露的銅，當除去光阻後，保留未被蝕刻除去的銅，形成所期望的銅線路圖案於印刷電路板上。 Usually, in order to improve the adhesion between the surface of the substrate and the coating material, a method of pre-roughening the surface of the substrate is used, for example, forming a photoresist on the roughened copper foil of the printed circuit board, and then exposing the photoresist to With a specific pattern shape, part of the copper foil surface is exposed, and then the exposed copper is etched away. When the photoresist is removed, the unetched copper remains to form the desired copper circuit pattern on the printed circuit board.
然而，若採用粗化處理，表面粗糙的銅表面會保形於線路圖案上，而高頻高速傳輸的訊號傳遞路徑通常發生於線路表面(集膚效應)，若線路表面不平整，將產生訊號不良的問題。而且，粗化處理通常伴隨汙染廢水，亦存在有環保的問題。另一方面，隨著線路圖案逐漸線細化、縮小化，粗化處理的銅表面 和圖案化光阻的附著力問題更趨嚴重。因此，在目前趨向高頻高速傳輸時代中，業界期望以不粗化基材導體表面的方式來製作線路。 However, if roughening is used, the rough copper surface will conform to the circuit pattern, and the signal transmission path of high-frequency and high-speed transmission usually occurs on the surface of the circuit (skin effect). If the surface of the circuit is uneven, it will generate signal bad question. Moreover, roughening treatment is usually accompanied by polluted wastewater, which also has environmental protection problems. On the other hand, as the circuit pattern gradually becomes thinner and smaller, the roughened copper surface The adhesion problem with patterned photoresist is more serious. Therefore, in the current era of high-frequency and high-speed transmission, the industry expects to fabricate circuits in a manner that does not roughen the surface of the substrate conductor.
目前，已知有使用表面處理組成物預先處理金屬表面的方法，然而先前技術所揭示的表面處理組成物，仍存在有表面處理組成物過度腐蝕或不均勻腐蝕基材表面、或附著力提升效果不明顯等問題。 At present, there are known methods of using surface treatment compositions to pre-treat metal surfaces. However, the surface treatment compositions disclosed in the prior art still have the effect of excessive corrosion or uneven corrosion of the surface of the substrate, or the effect of improving adhesion. Not obvious issues.
為了解決上述問題，本發明提供一種表面結合劑，係用於提升非金屬基材之表面附著力，該表面結合劑包括***化合物及咪唑化合物。 In order to solve the above problems, the present invention provides a surface binding agent, which is used to improve the surface adhesion of non-metallic substrates. The surface binding agent includes triazole compounds and imidazole compounds.
於一具體實施態樣中，該***化合物包括選自苯並***及5-甲基苯並***之至少一者，該咪唑化合物包括選自咪唑、二氫咪唑及1,2-二甲基咪唑之至少一者。 In a specific embodiment, the triazole compound includes at least one selected from benzotriazole and 5-methylbenzotriazole, and the imidazole compound includes at least one selected from imidazole, dihydroimidazole, and 1,2-di at least one of methylimidazoles.
於一具體實施態樣中，表面結合劑復包括吡啶化合物，且於另一具體實施態樣中，該吡啶化合物包括選自2-甲基吡啶及2-巰基吡啶之至少一者。 In one embodiment, the surface binding agent further includes a pyridine compound, and in another embodiment, the pyridine compound includes at least one selected from 2-picoline and 2-mercaptopyridine.
於一具體實施態樣中，***化合物、咪唑化合物以及吡啶化合物各者之濃度介於0.05g/L至50g/L之間。 In an embodiment, the concentration of each of the triazole compound, the imidazole compound and the pyridine compound is between 0.05 g/L and 50 g/L.
於一具體實施態樣中，表面結合劑復包括二甲基乙醯胺，以作為催化劑，且於另一具體實施態樣中，二甲基乙醯胺之濃度介於5mL/L至100mL/L之間。 In one embodiment, the surface binding agent further includes dimethylacetamide as a catalyst, and in another embodiment, the concentration of dimethylacetamide is between 5 mL/L and 100 mL/L Between L.
於一具體實施態樣中，表面結合劑不包括酸類化合物。 In a specific embodiment, the surface binding agent does not include acid compounds.
於一具體實施態樣中，表面結合劑復可用於提升金屬基材之表面附著力，且於另一具體實施態樣中，表面結合劑復包括無機酸化合物及有機酸化合物之至少一者。 In one embodiment, the surface bonding agent can be used to improve the surface adhesion of the metal substrate, and in another embodiment, the surface bonding agent includes at least one of an inorganic acid compound and an organic acid compound.
於一具體實施態樣中，無機酸化合物包括選自由硫酸、鹽酸、硝酸、磷酸所組成群組之至少一者。 In a specific embodiment, the inorganic acid compound includes at least one member selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
於一具體實施態樣中，有機酸化合物包括選自由甲酸、乙酸、丙酸、丁酸、戊酸、己酸、草酸、丙烯酸、丁烯酸、異丁烯酸、乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、順丁烯二酸、苯甲酸、苯二甲酸、肉桂酸、乙醇酸、乳酸、蘋果酸、水楊酸、甘胺酸、酒石酸、檸檬酸、胺磺酸、β-氯丙酸、菸鹼酸、抗壞血酸、羥基三甲基乙酸及乙醯丙酸所組成群組之至少一者。 In a specific embodiment, the organic acid compound includes a compound selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oxalic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, butyric acid Diacid, glutaric acid, adipic acid, pimelic acid, maleic acid, benzoic acid, phthalic acid, cinnamic acid, glycolic acid, lactic acid, malic acid, salicylic acid, glycine, tartaric acid, lemon At least one member of the group consisting of acid, sulfamic acid, β-chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid and levulinic acid.
於一具體實施態樣中，表面結合劑復包括選自由乙醇胺、二乙二醇單丁醚、二甲氧基乙烷所組成群組之至少一者。 In a specific embodiment, the surface binding agent includes at least one member selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, and dimethoxyethane.
本發明還提供一種處理基材表面之方法，係包括使本發明之表面結合劑與基材之表面接觸，以提升該基材之表面與覆於該基材之表面上之層之間的附著力，其中，該基材為金屬基材或非金屬基材，且該覆於該基材之表面上之層為金屬層或非金屬層。 The present invention also provides a method for treating the surface of a substrate, comprising contacting the surface bonding agent of the present invention with the surface of the substrate to enhance the adhesion between the surface of the substrate and a layer overlying the surface of the substrate Force, wherein, the substrate is a metal substrate or a non-metal substrate, and the layer covering the surface of the substrate is a metal layer or a non-metal layer.
於一具體實施態樣中，金屬基材與金屬層之材質包括選自銅、鋁、鎳、鋅、鐵、鉻及其合金所組成群組之至少一者。於一具體實施態樣中，非金屬基材與非金屬層之材質為玻璃、聚醯亞胺膜、預浸體、可成像之介電體、可成像之樹脂、防焊材、蝕刻光阻或矽晶。 In a specific implementation, the material of the metal substrate and the metal layer includes at least one material selected from the group consisting of copper, aluminum, nickel, zinc, iron, chromium and alloys thereof. In a specific embodiment, the materials of the non-metal substrate and the non-metal layer are glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder mask, etch photoresist or silicon.
於一具體實施態樣中，表面結合劑通過旋塗、浸泡或噴灑的方式與基材之表面接觸。 In a specific embodiment, the surface binding agent is in contact with the surface of the substrate by means of spin coating, soaking or spraying.
於一具體實施態樣中，使表面結合劑與基材之表面接觸時，反應溫度係介於20℃至60℃之間。 In an embodiment, when the surface binding agent is brought into contact with the surface of the substrate, the reaction temperature is between 20°C and 60°C.
於一具體實施態樣中，使表面結合劑與基材之表面接觸時，反應時間係介於30秒至900秒之間。 In an embodiment, when the surface binding agent is brought into contact with the surface of the substrate, the reaction time is between 30 seconds and 900 seconds.
於一具體實施態樣中，基材之表面係未預先粗化處理之表面。 In a specific embodiment, the surface of the substrate is a surface that has not been roughened in advance.
於一具體實施態樣中，表面結合劑係預先稀釋至10%至20%後再與基材之表面接觸。 In one embodiment, the surface binding agent is pre-diluted to 10% to 20% before contacting with the surface of the substrate.
於一具體實施態樣中，本發明處理基材表面之方法復包括於表面結合劑與基材之表面接觸後，進行水洗洗淨多餘的表面結合劑，之後熱烘乾燥該基材。 In a specific embodiment, the method for treating the surface of the substrate of the present invention further includes washing the excess surface bonding agent with water after the surface bonding agent is in contact with the surface of the substrate, and then drying the substrate with heat.
本發明之表面結合劑具有以下特點： The surface binding agent of the present invention has the following characteristics:
1.表面結合劑施用於基材之表面上形成有機層，有效提升未預先粗化處理之基材表面與覆於其上之材料之間的附著力，避免覆於其上之材料脫落、剝離； 1. The surface binding agent is applied on the surface of the substrate to form an organic layer, which can effectively improve the adhesion between the surface of the substrate that has not been pre-roughened and the material covering it, and prevent the material covering it from falling off and peeling off ;
2.由於可排除粗化處理(例如刷磨、噴砂、微蝕刻等)製程，避免產生粗化處理用廢棄物(重金屬廢水、腐蝕性強酸等)，同時，基材表面具有較佳的平整性； 2. Since roughening treatment (such as brushing, sandblasting, micro-etching, etc.) can be eliminated, waste for roughening treatment (heavy metal wastewater, corrosive strong acid, etc.) can be avoided. At the same time, the surface of the substrate has better flatness ;
3.所適用之基材及覆於其上之層的種類廣泛，包括玻璃、聚醯亞胺膜、預浸體、可成像之介電體、可成像之樹脂、防焊材、蝕刻光阻及矽晶等的非金屬、以及銅、鋁、鎳、鋅、鐵、鉻及其合金的金屬； 3. A wide range of applicable substrates and layers covering them, including glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder resist, etch photoresist Nonmetals such as silicon and silicon, and metals such as copper, aluminum, nickel, zinc, iron, chromium and their alloys;
4.表面結合劑所形成的有機層為透明無色，不會改變基材表面之顏色，於使用銅做為基材時，不會有銅面色差，有利於AOI檢測； 4. The organic layer formed by the surface binder is transparent and colorless, and will not change the color of the substrate surface. When copper is used as the substrate, there will be no color difference on the copper surface, which is conducive to AOI detection;
5.表面結合劑具有重工性，重複使用本發明之表面結合劑仍具有優異之效果； 5. The surface binding agent is reworkable, and the repeated use of the surface binding agent of the present invention still has excellent effects;
6.基材表面經表面結合劑處理後形成的有機層具有疏水性，於使用銅作為基材時，能改善後續塗佈防焊油墨於導通孔中所產生的油墨吹孔問題。 6. The organic layer formed after the surface of the substrate is treated with a surface binder is hydrophobic, and when copper is used as the substrate, it can improve the problem of ink blowing caused by subsequent coating of solder resist ink in the via hole.
圖1至圖3係比較例3至5之測試結果。 1 to 3 are the test results of Comparative Examples 3 to 5.
圖4至圖6係本發明表面結合劑實施例17至19之測試結果。 Figures 4 to 6 are test results of Examples 17 to 19 of the surface binding agent of the present invention.
須知，本說明書中任何比例關係之改變或大小之調整，在不影響本發明所能產生之功效及所能達成之目的下，均應仍落在本發明所揭示之技術內容得能涵蓋之範圍內。同時，本說明書中所引用之如「上」等之用語，亦僅為便於敘述之明瞭，而非用以限定本發明可實施之範圍，其相對關係之改變或調整，在無實質變更技術內容下，當亦視為本發明可實施之範疇。 It should be noted that any change in the proportional relationship or adjustment of the size in this specification should still fall within the scope covered by the technical content disclosed in the present invention without affecting the effects and goals that can be achieved by the present invention. Inside. At the same time, the terms such as "above" quoted in this specification are only for the convenience of description, and are not used to limit the scope of the present invention. The change or adjustment of the relative relationship does not substantially change the technical content. Below, it should also be regarded as the scope where the present invention can be implemented.
本發明之表面結合劑包括***化合物以及咪唑化合物。 The surface binding agent of the present invention includes triazole compounds and imidazole compounds.
***化合物與咪唑化合物是提升基材表面與塗佈材料之間的附著力的主要成分，其於基材表面上形成有機層。***化合物例如為苯並***及5-甲基苯並***等，咪唑化合物例如為咪唑、二氫咪唑及1,2-二甲基咪唑等。***化合物與咪唑化合物可作為橋連配體，其以N-1以及N-3為配位原子，分別連接至基材表面上的原子以及塗佈材料的原子形成鍵結，從而達到橋接基材表面與塗佈材料的效果。 The triazole compound and the imidazole compound are the main components to enhance the adhesion between the surface of the substrate and the coating material, and form an organic layer on the surface of the substrate. Examples of triazole compounds include benzotriazole and 5-methylbenzotriazole, and examples of imidazole compounds include imidazole, dihydroimidazole, and 1,2-dimethylimidazole. Triazole compounds and imidazole compounds can be used as bridging ligands, which use N-1 and N-3 as coordinating atoms, respectively connected to the atoms on the surface of the substrate and the atoms of the coating material to form bonds, so as to achieve the bridging group The effect of the material surface and the coating material.
本發明之表面結合劑復包括吡啶化合物，其作為提升基材表面與塗佈材料之間的附著力的次要成分。吡啶化合物例如為2-甲基吡啶及2-巰基吡啶等。 The surface bonding agent of the present invention further includes a pyridine compound as a secondary component to enhance the adhesion between the surface of the substrate and the coating material. Pyridine compounds include, for example, 2-picoline, 2-mercaptopyridine, and the like.
表面結合劑中，***化合物、咪唑化合物以及吡啶化合物各者之濃度介於0.05g/L至50g/L之間、0.1g/L至40g/L之間、0.25g/L至30g/L之間、0.5 g/L至25g/L之間、或者1g/L至25g/L之間，濃度例如可為0.05、0.06、0.07、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.6、0.7、0.8、0.9、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50g/L，但不限於此。 In the surface binding agent, the concentration of each of the triazole compound, imidazole compound and pyridine compound is between 0.05g/L and 50g/L, between 0.1g/L and 40g/L, and between 0.25g/L and 30g/L Between, 0.5 Between g/L and 25g/L, or between 1g/L and 25g/L, the concentration can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 , 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36 , 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50g/L, but not limited thereto.
提升附著力之化合物之總濃度可介於0.05g/L至200g/L之間、0.1g/L至200g/L之間、1g/L至150g/L之間、10g/L至100g/L之間、或者25g/L至100g/L之間，濃度例如可為0.05、0.06、0.07、0.08、0.09、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.6、0.7、0.8、0.9、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7、7.5、8、8.5、9、9.5、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、55、60、65、70、75、80、85、90、95、100、105、110、115、120、125、130、135、140、145、150、155、160、165、170、175、180、185、190、195、200g/L，但不限於此。 The total concentration of the compound for improving adhesion can be between 0.05g/L and 200g/L, between 0.1g/L and 200g/L, between 1g/L and 150g/L, between 10g/L and 100g/L Between, or between 25g/L and 100g/L, the concentration can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200g/L, but not limited thereto.
使***化合物、咪唑化合物以及吡啶化合物溶解於溶劑中以配製成表面結合劑。溶劑之種類並無限定，只要是可使其以適當的濃度溶解的溶劑即可。於一具體實施態樣中溶劑為水，於其他實施態樣中溶劑可為其他有機溶劑，溶劑亦可為同時包含有機溶劑及水。 A triazole compound, an imidazole compound, and a pyridine compound are dissolved in a solvent to formulate a surface-binding agent. The type of solvent is not limited as long as it can be dissolved at an appropriate concentration. In one embodiment, the solvent is water, and in other embodiments, the solvent may be other organic solvents, or the solvent may include both organic solvents and water.
作為溶劑，例如可選用苯、甲苯、二甲苯、乙基苯、甲酚及氯苯等之芳香族類；甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、n-己醇及環己醇等之脂肪族醇類；乙二醇、二乙二醇、丙二醇及二丙二醇等之二醇類；丙三醇；丙酮、 甲基乙基酮、二乙基酮、甲基異丁基酮、乙基異丁基酮、及環己酮等之酮類；二乙基醚、二丙基醚、二丁基醚、二己基醚、苄基甲基醚、苄基乙基醚、及四氫呋喃等之醚類；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚及二乙二醇單苯基醚等之二醇單醚類；乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚及二乙二醇二丙基醚等之二醇二醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯及二乙二醇單乙基醚乙酸酯等之二醇單乙酸酯類；二乙二醇單丙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇單苯基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、2-甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-甲氧基丁基乙酸酯、2-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-乙基-3-甲氧基丁基乙酸酯、2-乙氧基丁基乙酸酯、4-乙氧基丁基乙酸酯、4-丙氧基丁基乙酸酯、2-甲氧基戊基乙酸酯、3-甲氧基戊基乙酸酯、4-甲氧基戊基乙酸酯、2-甲基-3-甲氧基戊基乙酸酯、3-甲基-3-甲氧基戊基乙酸酯、3-甲基-4-甲氧基戊基乙酸酯及4-甲基-4-甲氧基戊基乙酸酯等之二醇類之單醚單乙酸酯類；丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基、甲基-3-甲氧基丙酸酯、乙基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯、乙基-3-丙氧基丙酸酯、丙基-3-甲氧基丙酸酯、異丙基-3-甲氧基丙酸酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸甲酯、乙酸乙酯、乙酸 丙酯、乙酸異丙酯、乙酸丁酯、乙酸異戊酯、碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、及γ-丁內酯等之酯類；N,N,N’,N’-四甲基脲、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、六甲基磷醯胺、1,3-二甲基-2-咪唑啉酮、及二甲基亞碸等之非質子性極性有機溶劑。於一具體實施態樣中，溶劑例如水及二乙二醇單丁醚。 As solvents, for example, aromatics such as benzene, toluene, xylene, ethylbenzene, cresol and chlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol can be used and aliphatic alcohols such as cyclohexanol; diols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; glycerol; acetone, Ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, and cyclohexanone; diethyl ether, dipropyl ether, dibutyl ether, di Ethers such as hexyl ether, benzyl methyl ether, benzyl ethyl ether, and tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Glycol monoethers such as monopropyl ether, diethylene glycol monobutyl ether and diethylene glycol monophenyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di Propyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, etc. Glycol diethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, Ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and other glycol monoacetates; diethylene glycol monopropyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate, Diethylene Glycol Monophenyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropylene Base ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl Ethyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4- Ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate ester, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate and monoether monoacetates of glycols such as 4-methyl-4-methoxypentyl acetate; methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl Ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethoxy Ethyl glycolate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl acetate, ethyl acetate, acetic acid Propyl ester, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, pyruvate Esters of butyl ester, methyl acetyl acetate, ethyl acetyl acetate, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, and γ-butyrolactone; N,N ,N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, Aprotic polar organic solvents such as 1,3-dimethyl-2-imidazolinone and dimethylsulfoxide. In a specific embodiment, the solvent is, for example, water and diethylene glycol monobutyl ether.
本發明的表面結合劑還可包括催化劑，催化劑之種類並無限制，具體可舉例為二甲基乙醯胺。催化劑加速表面結合劑與基材表面之間的作用，可縮短處理時間，有利製程的控制。催化劑之濃度可介於5mL/L至100mL/L之間，濃度例如為5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100mL/L，但不限於此。 The surface binding agent of the present invention may also include a catalyst, and the type of the catalyst is not limited, specifically, dimethylacetamide may be exemplified. The catalyst accelerates the interaction between the surface binder and the surface of the substrate, which can shorten the processing time and facilitate the control of the process. The catalyst concentration can be between 5mL/L and 100mL/L, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 , 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100mL/L, but not limited thereto.
本發明的表面結合劑的pH值一般可介於7至8之間，但不限於此。pH值例如可為7.0、7.1、7.2、7.3、7.4、7.5、7.6、7.7、7.8、7.9、8.0。上述表面結合劑的pH值係不含有酸類化合物時所測量得到者，即本發明的表面結合劑可不含有無機酸及/或有機酸。不過，於其他具體實施態樣中，本發明的表面結合劑還可包括無機酸化合物，其可調整表面結合劑之pH值，另一方面，無機酸化合物亦可有微蝕刻的作用，使基材之表面形成極細微的腐蝕痕跡，從而增加與塗佈材料的接觸面積，提升附著力。 The pH value of the surface binding agent of the present invention can generally be between 7 and 8, but is not limited thereto. The pH can be, for example, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0. The pH value of the above-mentioned surface binding agent is measured when it does not contain acid compounds, that is, the surface binding agent of the present invention may not contain inorganic acid and/or organic acid. However, in other specific implementations, the surface binding agent of the present invention may also include an inorganic acid compound, which can adjust the pH value of the surface binding agent. On the other hand, the inorganic acid compound may also have a micro-etching effect to make the base Form very fine corrosion traces on the surface of the material, thereby increasing the contact area with the coating material and improving adhesion.
無機酸化合物之種類不無特別限定，例如可為選自由硫酸、鹽酸、硝酸及磷酸所組成群組中之至少一者，於使用無機酸混合物時，各酸可以任何適當比例組合。於一具體實施態樣中，表面結合劑中包含硫酸。 The type of the inorganic acid compound is not particularly limited. For example, it may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. When using a mixture of inorganic acids, the acids may be combined in any appropriate ratio. In a specific embodiment, the surface binding agent includes sulfuric acid.
無機酸化合物之濃度可介於50g/L至400g/L之間，濃度例如為50、55、60、65、70、75、80、85、90、95、100、105、110、115、120、125、130、135、140、145、150、155、160、165、170、175、180、185、190、195、200、210、220、230、240、250、260、270、280、290、300、310、320、330、340、350、360、370、380、390、400g/L，但不限於此。 The concentration of the inorganic acid compound can be between 50g/L and 400g/L, such as 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120 ,125,130,135,140,145,150,155,160,165,170,175,180,185,190,195,200,210,220,230,240,250,260,270,280,290 , 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400g/L, but not limited thereto.
於其他具體實施態樣中，本發明的表面結合劑還可包括有機酸化合物，其如上述無機酸化合物般可調整表面結合劑之pH值，另一方面，有機酸化合物亦可有微蝕刻的作用，使基材之表面形成極細微的腐蝕痕跡，從而增加與塗佈材料的接觸面積，提升附著力。 In other specific embodiments, the surface binding agent of the present invention may also include an organic acid compound, which can adjust the pH value of the surface binding agent like the above-mentioned inorganic acid compound. On the other hand, the organic acid compound may also have microetching effects. The effect is to form very fine corrosion marks on the surface of the substrate, thereby increasing the contact area with the coating material and improving the adhesion.
有機酸化合物之種類不無特別限定，例如可為選自由甲酸、乙酸、丙酸、丁酸、戊酸、己酸、草酸、丙烯酸、丁烯酸、異丁烯酸、乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、順丁烯二酸、苯甲酸、苯二甲酸、肉桂酸、乙醇酸、乳酸、蘋果酸、水楊酸、甘胺酸、酒石酸、檸檬酸、胺磺酸、β-氯丙酸、菸鹼酸、抗壞血酸、羥基三甲基乙酸及乙醯丙酸所組成群組中之至少一者，於使用有機酸混合物時，各酸可以任何適當比例組合。於一具體實施態樣中，表面結合劑中包含乙酸。 The type of the organic acid compound is not particularly limited, for example, it may be selected from formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, oxalic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, benzoic acid, phthalic acid, cinnamic acid, glycolic acid, lactic acid, malic acid, salicylic acid, glycine, tartaric acid, At least one of the group consisting of citric acid, sulfamic acid, β-chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid and levulinic acid. When using an organic acid mixture, each acid can be any Appropriate proportion combination. In a specific embodiment, the surface binding agent includes acetic acid.
有機酸化合物之濃度可介於5g/L至100g/L之間，濃度例如為5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49、50、55、60、65、70、75、80、85、90、95、100g/L，但不限於此。 The concentration of the organic acid compound can be between 5g/L and 100g/L, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 , 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100g/L, but not limited thereto.
在添加有機酸化合物、無機酸化合物等酸類化合物的情況，本發明的表面結合劑的pH值大幅降低，例如pH為小於4、小於3、或小於2，但不限於此。具體地，添加有機酸及/或無機酸時的表面結合劑的pH值可為3.9、3.8、3.7、3.6、3.5、3.4、3.3、3.2、3.1、3.0、2.9、2.8、2.7、2.6、2.5、2.4、2.3、2.2、2.1、2.0、1.9、1.8、1.7、1.6、1.5、1.4、1.3、1.2、1.1、1.0。當本發明的表面結合劑不包括酸類化合物時，通常較適合用於非金屬之基材表面上；當本發明的表面結合劑包括酸類化合物時，通常較適合用於金屬之基材表面上，但不限於此。 When acid compounds such as organic acid compounds and inorganic acid compounds are added, the pH value of the surface binding agent of the present invention is greatly reduced, for example, the pH is less than 4, less than 3, or less than 2, but not limited thereto. Specifically, the pH value of the surface binding agent when adding organic acid and/or inorganic acid can be 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5 , 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0. When the surface binding agent of the present invention does not include acid compounds, it is generally more suitable for use on the surface of non-metallic substrates; when the surface binding agent of the present invention includes acid compounds, it is generally more suitable for use on the surface of metal substrates, But not limited to this.
本發明的表面結合劑還可包括選自由乙醇胺、二乙二醇單丁醚、二甲氧基乙烷所組成群組中之至少一者的其他成分。在不阻礙本發明之目的的情況下，還可添加各種添加劑，可列舉例如pH調整劑、分散劑、界面活性劑、防腐劑、黏度調整劑、抗氧化劑、紫外線吸收劑、穩定劑及著色劑等。 The surface binding agent of the present invention may also include at least one other component selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, and dimethoxyethane. In the case where the object of the present invention is not hindered, various additives may be added, for example, pH adjusters, dispersants, surfactants, preservatives, viscosity adjusters, antioxidants, ultraviolet absorbers, stabilizers and coloring agents wait.
本發明提供一種處理基材表面之方法，包括清潔基材之表面；使表面結合劑與基材之表面接觸；視需要以水清洗多餘之表面結合劑；以及進行熱烘乾燥或光固化以於該基材之表面上形成有機層。通過表面結合劑處理基材表面，以提升該基材與覆該基材之表面上之材料之間的附著力。 The invention provides a method for treating the surface of a substrate, including cleaning the surface of the substrate; contacting the surface bonding agent with the surface of the substrate; washing the excess surface bonding agent with water if necessary; An organic layer is formed on the surface of the substrate. The surface of the substrate is treated with a surface binding agent to improve the adhesion between the substrate and the material overlying the surface of the substrate.
清潔基材之表面可通過使用有機溶劑或酸性清潔劑來達成，具體地，例如可使用硫酸、磷酸等溶液、異丙酮，但不限於此。 Cleaning the surface of the substrate can be achieved by using an organic solvent or an acidic cleaner. Specifically, for example, sulfuric acid, phosphoric acid and other solutions, isopropyl ketone, but not limited thereto.
清潔完基材之表面後，使表面結合劑與基材之表面接觸。接觸的方法無特別限定，可採用濺鍍、蒸鍍、浸泡或浸漬、旋塗、或噴霧等方法，可視需要選擇合適的接觸方法。從形成均勻的有機層的觀點來看，可優先選用浸泡或浸漬處理。 After cleaning the surface of the substrate, the surface bonding agent is brought into contact with the surface of the substrate. The method of contact is not particularly limited, methods such as sputtering, vapor deposition, immersion or immersion, spin coating, or spraying can be used, and an appropriate contact method can be selected according to need. From the viewpoint of forming a uniform organic layer, soaking or immersion treatment is preferably used.
本發明的表面結合劑可適用基材之種類廣泛，可為金屬基材或非金屬基材，而後續覆於該基材之表面上之層之種類亦廣泛，可為金屬層或非金屬層。金屬基材及金屬層之材質例如銅、鋁、鎳、鋅、鐵、鉻及其合金等，非金屬基材及非金屬層之材質例如玻璃、聚醯亞胺膜、預浸體、可成像之介電體、可成像之樹脂、防焊材、蝕刻光阻及矽晶等。由於使用表面結合劑大幅強化了基材之表面附著力，故基材之表面可為未預先粗化處理之表面。 The surface bonding agent of the present invention can be applied to a wide range of substrates, which can be metal substrates or non-metal substrates, and the types of layers subsequently coated on the surface of the substrate are also wide, which can be metal layers or non-metal layers . Materials of metal substrates and metal layers such as copper, aluminum, nickel, zinc, iron, chromium and their alloys, etc. Materials of non-metal substrates and non-metal layers such as glass, polyimide film, prepreg, imageable Dielectrics, imageable resins, solder resists, etch photoresists and silicon crystals. Since the use of the surface binder greatly strengthens the surface adhesion of the substrate, the surface of the substrate can be a surface that has not been roughened in advance.
當採用浸漬處理時，表面結合劑的溫度較佳介於20℃至60℃之間，更佳介於30℃至50℃之間；浸漬時間較佳介於60秒至900秒之間，更佳介於60秒至600秒之間。通常在浸漬處理之後進行視需要之水洗步驟，最後進行乾燥步驟。 When dipping is used, the temperature of the surface binder is preferably between 20°C and 60°C, more preferably between 30°C and 50°C; the dipping time is preferably between 60 seconds and 900 seconds, more preferably between 60 seconds to 600 seconds. The dipping treatment is usually followed by an optional water washing step and finally a drying step.
當採用噴霧處理時，表面結合劑的溫度較佳亦介於20℃至60℃之間，更佳介於30℃至50℃之間。噴霧壓力較佳介於0.01MPa至0.3MPa之間且噴霧時間介於15至600秒的條件下進行處理，更佳為噴霧壓力介於0.05MPa至0.2MPa且噴霧時間介於30至300秒的條件下進行處理。通常在浸漬處理之後進行視需要之水洗步驟，以洗淨多餘表面結合劑，最後進行熱烘乾燥或光固化步驟以令該表面結合劑於基材之表面上形成有機層。 When spraying is used, the temperature of the surface binding agent is also preferably between 20°C and 60°C, more preferably between 30°C and 50°C. The spray pressure is preferably between 0.01MPa and 0.3MPa and the spray time is between 15 and 600 seconds, and the spray pressure is preferably between 0.05MPa and 0.2MPa and the spray time is between 30 and 300 seconds. below for processing. Usually after the immersion treatment, an optional water washing step is performed to remove excess surface adhesive, and finally a thermal drying or photocuring step is performed to allow the surface adhesive to form an organic layer on the surface of the substrate.
於一具體實施態樣中，本發明之表面結合劑於接觸基材之表面前，可以先稀釋成10%至20%的稀釋濃度。 In a specific embodiment, the surface-binding agent of the present invention can be diluted to a concentration of 10% to 20% before contacting the surface of the substrate.
本發明之表面結合劑接觸基材之表面後，於基材之表面上形成有機層，該有機層為透明且疏水性，由於該有機層極薄，肉眼難辨視，故可通過將水滴落在基材之表面上，觀察水是否與表面具有大接觸角而呈現水滴狀來確定有機層是否成功形成。 The surface binding agent of the present invention forms an organic layer on the surface of the substrate after it contacts the surface of the substrate. On the surface of the substrate, it is observed whether the water has a large contact angle with the surface and presents a drop shape to determine whether the organic layer is successfully formed.
具體地，本發明之表面結合劑可與如銅板、銅箔基板等金屬基材之表面接觸，例如將如銅板、銅箔基板等基材浸泡於含有本發明之表面結合劑之浴中，以於該基材之表面上形成有機層，隨後再形成如光阻之聚合物塗覆材料於該有機層上，俾令該有機層介於該塗覆材料與基材之間。另一方面，亦可將表面結合劑與玻璃、聚醯亞胺膜等非金屬基材之表面接觸，形成有機層，隨後再鍍上鎳、鉻、銅等金屬層，俾令該有機層介於該金屬層與基材之間。 Specifically, the surface bonding agent of the present invention can be in contact with the surface of metal substrates such as copper plates and copper foil substrates, for example, substrates such as copper plates and copper foil substrates are soaked in a bath containing the surface bonding agent of the present invention to An organic layer is formed on the surface of the substrate, and then a polymer coating material such as photoresist is formed on the organic layer so that the organic layer is between the coating material and the substrate. On the other hand, the surface binding agent can also be contacted with the surface of non-metallic substrates such as glass and polyimide film to form an organic layer, and then plated with metal layers such as nickel, chromium, copper, etc., so that the organic layer can be separated. between the metal layer and the substrate.
以下藉由特定的具體實施例說明本發明之實施方式，熟悉此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之其他優點及功效。 The implementation of the present invention is described below through specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.
測試例1 test case 1
實施例1之表面結合劑包括苯並***、咪唑以及二氫咪唑等提升附著力之化合物。於室溫下，將未粗化處理之銅板浸泡於實施例1之表面結合劑內15分鐘，使表面結合劑處理銅表面，接著水洗、烘乾，然後於銅表面上塗佈/壓膜乾膜光阻(乾膜光阻E9500，購自長興材料工業股份有限公司)。以3% NaOH溶液作為去膜液，並將塗佈有光阻之銅板浸泡於去膜液內，操作溫度為50℃，觀察光阻自銅面上剝離的情形，當光阻剝離面積達到30%時記錄時間。 The surface binding agent in Example 1 includes compounds that enhance adhesion such as benzotriazole, imidazole, and dihydroimidazole. At room temperature, soak the unroughened copper plate in the surface bonding agent of Example 1 for 15 minutes, so that the surface bonding agent treats the copper surface, then wash with water, dry, and then coat/press the film on the copper surface to dry Film photoresist (dry film photoresist E9500, purchased from Eternal Material Industry Co., Ltd.). Use 3% NaOH solution as the stripping solution, and soak the copper plate coated with photoresist in the stripping solution. The operating temperature is 50°C. Observe the peeling of the photoresist from the copper surface. When the stripping area of the photoresist reaches 30 % time recording time.
實施例2至7係以實施例1相同步驟進行測試，惟調整表面結合劑之組成、表面結合劑浸泡時間等參數如下表1所示。而比較例1係未浸泡表面結合劑，直接使未粗化處理之銅板浸泡於去膜液內。 Examples 2 to 7 were tested with the same steps as in Example 1, but the parameters such as the composition of the surface binding agent and the soaking time of the surface binding agent were adjusted as shown in Table 1 below. In Comparative Example 1, the surface binder was not soaked, and the unroughened copper plate was directly soaked in the film-removing solution.
實施例1至7及比較例1之表面結合劑組成、表面結合劑浸泡時間及光阻剝離時間係如下表1所示。表面結合劑原液組成中，苯並***之濃度介於3g/L至30g/L之間、咪唑之濃度介於0.5g/L至5g/L之間、二氫咪唑之濃度介於0.5g/L至5g/L之間、2-甲基吡啶之濃度介於3g/L至30g/L之間、5-甲基苯並***之濃 度介於0.5g/L至5g/L之間、1,2-二甲基咪唑之濃度介於0.5g/L至5g/L之間、2-巰基吡啶之濃度介於0.5g/L至5g/L之間、二甲基乙醯胺之濃度介於5mL/L至50mL/L之間。以表面結合劑處理基材表面之前，將原液以水稀釋為20%再進行處理。 The surface adhesive composition, surface adhesive soaking time and photoresist stripping time of Examples 1 to 7 and Comparative Example 1 are shown in Table 1 below. In the composition of the surface binding agent stock solution, the concentration of benzotriazole is between 3g/L and 30g/L, the concentration of imidazole is between 0.5g/L and 5g/L, and the concentration of dihydroimidazole is between 0.5g /L to 5g/L, the concentration of 2-picoline is between 3g/L and 30g/L, the concentration of 5-methylbenzotriazole The concentration is between 0.5g/L and 5g/L, the concentration of 1,2-dimethylimidazole is between 0.5g/L and 5g/L, and the concentration of 2-mercaptopyridine is between 0.5g/L and 5g/L, and the concentration of dimethylacetamide is between 5mL/L and 50mL/L. Before treating the surface of the substrate with the surface binding agent, the stock solution is diluted to 20% with water and then treated.
表1
由上表1之結果可知，銅面經實施例1之表面結合劑處理可減緩光阻自銅面剝離之時間，由1分01秒延長至2分02秒，顯示實施例1之表面結合劑可有效提升銅面與光阻之間的附著力。另一方面，隨著表面結合劑中之提升附著力之化合物種類增加，銅面與光阻之間的附著力提升效果更加顯著，實施例6的結果顯示光阻自銅面剝離之時間已大幅延長至3分29秒，而且，即便使表面結合劑浸泡時間縮減為3分鐘，如實施例7所示，光阻自銅面剝離之時間仍能維持在3分18秒，遠遠優於未使用表面結合劑之比較例1。 From the results in Table 1 above, it can be known that the copper surface treated with the surface bonding agent of Example 1 can slow down the peeling time of the photoresist from the copper surface, extending from 1 minute 01 seconds to 2 minutes 02 seconds, which shows that the surface bonding agent of Example 1 It can effectively improve the adhesion between the copper surface and the photoresist. On the other hand, with the increase of the types of compounds in the surface bonding agent that improve the adhesion, the effect of improving the adhesion between the copper surface and the photoresist is more significant. The results of Example 6 show that the time for the photoresist to peel off from the copper surface has been greatly reduced. It was extended to 3 minutes and 29 seconds, and even if the soaking time of the surface bonding agent was reduced to 3 minutes, as shown in Example 7, the time for the photoresist to be peeled off from the copper surface can still be maintained at 3 minutes and 18 seconds, which is far better than that of the original Comparative example 1 using a surface binding agent.
測試例2 test case 2
實施例8至15係準備具有1 oz厚度的銅箔基板(FR-4，購自南亞塑膠工業股份有限公司)，並以酸性清潔劑清潔銅箔表面，接著於室溫下使銅箔基板浸泡於表面結合劑內，其中，該表面結合劑包括苯並***、咪唑、二氫咪唑、2-甲基吡啶、5-甲基苯並***、1,2-二甲基咪唑及2-巰基吡啶等提升表面附著力之化合物以及二甲基乙醯胺，且表面結合劑原液各成分比例係如測試例1所述；之後水洗、烘乾；再於銅箔表面上塗佈/壓膜乾膜光阻(乾膜光阻E9500，購自長興材料工業股份有限公司)，形成25μm厚度的光阻；以10*10共計100個圓點圖形對光阻曝光，其中每個圓點圖形的直徑為50μm，且各圓點之間距為50μm；後續以濃度1%(即10g/L)的碳酸鈉溶液作為顯影液，以噴灑的方式對光阻進行顯影，溫度控制為30℃、壓力設置為30psi、噴灑處理時間為60秒，然後水洗、烘乾；最後觀察光阻的圓點圖形的保留情況。比較例2則未浸泡表面結合劑，直接使銅箔基板塗佈光阻後曝光、顯影、水洗、烘乾。實施例8至15及比較例2之參數及結果如下表2所示。 Examples 8 to 15 are to prepare a copper foil substrate (FR-4, purchased from Nan Ya Plastic Industry Co., Ltd.) with a thickness of 1 oz, and clean the surface of the copper foil with an acidic cleaner, and then soak the copper foil substrate at room temperature In the surface binding agent, wherein the surface binding agent includes benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-dimethylimidazole and 2- Compounds such as mercaptopyridine to improve surface adhesion and dimethylacetamide, and the ratio of the components of the surface-binding agent stock solution are as described in Test Example 1; then washed with water and dried; then coated/pressed on the surface of copper foil Dry film photoresist (dry film photoresist E9500, purchased from Eternal Materials Industry Co., Ltd.), forms a photoresist with a thickness of 25 μm; a total of 100 dot patterns of 10*10 are used to expose the photoresist, wherein each dot pattern The diameter is 50 μm, and the distance between the dots is 50 μm; subsequently, a sodium carbonate solution with a concentration of 1% (ie 10g/L) is used as a developing solution to develop the photoresist by spraying, the temperature is controlled at 30°C, and the pressure is set 30psi, spray treatment time is 60 seconds, then wash and dry; finally observe the retention of the dot pattern of the photoresist. In comparative example 2, the surface bonding agent was not soaked, and the copper foil substrate was directly coated with photoresist and then exposed, developed, washed with water, and dried. The parameters and results of Examples 8 to 15 and Comparative Example 2 are shown in Table 2 below.
表2
圓點數量存留之比例愈高，表示銅箔表面與光阻之間的附著力愈佳。表2之結果中，未使用表面結合劑之比較例2其完整之圓點數量僅有71個，而使用表面結合劑之實施例8至15其完整之圓點數量達到92個以上，且隨著浸泡時間的增加及稀釋濃度的提升，完整之圓點數量更可達到100個，擁有極佳的良率。 The higher the ratio of dots remaining, the better the adhesion between the copper foil surface and the photoresist. In the results of Table 2, the number of complete dots in Comparative Example 2 without using surface binding agent is only 71, while the number of complete dots in Examples 8 to 15 using surface binding agent reaches more than 92, and With the increase of soaking time and the increase of dilution concentration, the number of complete dots can reach 100, with excellent yield.
測試例3 Test case 3
另以表面結合劑噴灑處理玻璃基板之表面，其中，該表面結合劑包括苯並***、咪唑、二氫咪唑、2-甲基吡啶、5-甲基苯並***、1,2-二甲基咪唑及2-巰基吡啶等提升表面附著力之化合物以及二甲基乙醯胺，作為實施例16，其中，表面結合劑原液各成分比例係如測試例1所述，且以水稀釋原液為20%使用。接著於該玻璃基板表面上設計形成有數條並行排列且寬度為2μm、厚度為20μm的長條形光阻(壓模參數：壓膜溫度90℃、壓膜壓力3kg，壓膜速度2m/min)，並以測試例2的條件進行曝光顯影。結果顯示顯影後的光阻沒有浮離、脫落的現象發生，即表面結合劑亦能有效提升玻璃表面與光阻之間的附著力。 In addition, the surface of the glass substrate is sprayed with a surface binding agent, wherein the surface binding agent includes benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-bis Compounds such as methimidazole and 2-mercaptopyridine, and dimethylacetamide, which promote surface adhesion, are used as Example 16, wherein the ratio of each component of the surface-binding agent stock solution is as described in Test Example 1, and the stock solution is diluted with water Use for 20%. Then design and form several parallel photoresist strips with a width of 2 μm and a thickness of 20 μm on the surface of the glass substrate (molding parameters: lamination temperature 90°C, lamination pressure 3kg, lamination speed 2m/min) , and the exposure and development were carried out under the conditions of Test Example 2. The results showed that the photoresist after development did not float or fall off, that is, the surface bonding agent can also effectively improve the adhesion between the glass surface and the photoresist.
測試例4 Test case 4
將聚醯亞胺膜以異丙醇(IPA)處理5分鐘後水洗烘乾，接著於聚醯亞胺膜之表面上濺鍍100nm厚度的鉻層，再濺鍍500nm厚度的銅層，作為比較例3至5。再以3M#610膠帶貼附至鍍層表面上，去除膠帶與鍍層間之氣泡後，於貼附膠帶後1分鐘內以90度垂直拉扯的方式以小於3秒的速度快速將膠帶自鍍層表面撕離，觀察鍍層的剝落情況。其中，3M#600、3M610膠帶之初期黏性為32 oz/inch，約為357g/cm。 Treat the polyimide film with isopropanol (IPA) for 5 minutes, wash and dry it with water, then sputter a chromium layer with a thickness of 100nm on the surface of the polyimide film, and then sputter a copper layer with a thickness of 500nm for comparison Examples 3 to 5. Then attach 3M#610 tape to the surface of the coating, remove the air bubbles between the tape and the coating, and within 1 minute after attaching the tape, pull it vertically at 90 degrees and quickly tear the tape from the coating surface at a speed of less than 3 seconds to observe the peeling off of the coating. Among them, the initial viscosity of 3M#600 and 3M610 tapes is 32 oz/inch, which is about 357g/cm.
適用：CID A-A-113,Type 1,Class B,3M Brand Premium Transparent Film Tape 600,3M Brand Premium Cellophane Tape 610 Applicable: CID A-A-113,Type 1,Class B,3M Brand Premium Transparent Film Tape 600,3M Brand Premium Cellophane Tape 610
依據：IPC-TM-650 Number 2.4.1/2.4.1.1/2.4.1.3/2.4.1.4/2.4.28/2.4.28.1 According to: IPC-TM-650 Number 2.4.1/2.4.1.1/2.4.1.3/2.4.1.4/2.4.28/2.4.28.1
圖1至圖3的結果顯示，在未使用表面結合劑的情形下，膠帶下金屬鍍層的剝落面積達70至99%，表示聚醯亞胺膜與金屬鍍層之間的附著力不足，無法抵抗膠帶的剝離力。 The results in Figures 1 to 3 show that in the absence of a surface adhesive, 70 to 99% of the metal coating peeled off under the tape, indicating that the adhesion between the polyimide film and the metal coating was insufficient to resist The peel force of the tape.
另一方面，將聚醯亞胺膜以界面活性劑處理5分鐘後水洗；其後浸泡於表面結合劑內5分鐘後水洗烘乾，使表面結合劑處理聚醯亞胺膜表面，其中，該表面結合劑包括苯並***、咪唑、二氫咪唑、2-甲基吡啶、5-甲基苯並***、1,2-二甲基咪唑及2-巰基吡啶等提升表面附著力之化合物以及二甲基乙醯胺，其中，表面結合劑原液各成分比例係如測試例1所述，且以水稀釋原液為20%使用；之後水洗、烘乾；接著使用直流濺鍍(功率600W)，濺鍍100nm厚度的鉻層、500nm厚度的銅層為金屬鍍層，作為實施例17至19。最後以3M 610膠帶貼附至金屬鍍層以前述的方法測試金屬鍍層的剝落情況。 On the other hand, the polyimide film is washed with water after being treated with a surfactant for 5 minutes; then soaked in the surface binding agent for 5 minutes, then washed and dried, so that the surface binding agent is used to treat the surface of the polyimide film, wherein the Surface binders include benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-dimethylimidazole and 2-mercaptopyridine, etc. to enhance surface adhesion And dimethylacetamide, wherein, the proportion of each component of the surface-binding agent stock solution is as described in Test Example 1, and the stock solution diluted with water is 20% used; then washed with water and dried; then use DC sputtering (power 600W) , a chromium layer with a thickness of 100nm and a copper layer with a thickness of 500nm are metal plating, as examples 17 to 19. Finally, 3M 610 adhesive tape was attached to the metal coating, and the peeling of the metal coating was tested by the aforementioned method.
圖4至圖6的結果顯示使用表面結合劑處理聚醯亞胺膜表面後，膠帶下金屬鍍層的剝落面積小於1%，此表示聚醯亞胺膜表面通過表面結合劑處理後可實現與金屬層之間的優異結合，可抵抗膠帶的剝離力。 The results of Fig. 4 to Fig. 6 show that after using the surface binding agent to treat the surface of the polyimide film, the peeling area of the metal coating under the adhesive tape is less than 1%, which means that the surface of the polyimide film can be bonded to the metal after being treated with the surface binding agent. Excellent bond between layers, resists tape peel forces.
由上述可知，本發明之表面結合劑可處理基材表面，於基材表面上形成有機層，有效提升未預先粗化處理之基材表面與塗佈材料之間的附著力，避免塗佈材料脫落、剝離。由於可排除粗化處理製程，降低製程成本且避免產生粗化處理用廢棄物(重金屬廢水、腐蝕性強酸等)，而且，所適用之基材及塗佈材料種類廣泛，亦具有重工性，重複使用本發明之表面結合劑仍具有優異之效果。 It can be seen from the above that the surface binding agent of the present invention can treat the surface of the substrate, form an organic layer on the surface of the substrate, effectively improve the adhesion between the surface of the substrate that has not been roughened in advance and the coating material, and avoid the coating material To fall off, to peel off. Because the roughening process can be eliminated, the cost of the process can be reduced and the waste for roughening (heavy metal wastewater, corrosive strong acid, etc.) The use of the surface binding agent of the present invention still has excellent effects.
上述實施例係用以例示性說明本發明之原理及其功效，而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修改。因此本發明之權利保護範圍，應如後述之申請專利範圍所列。 The above-mentioned embodiments are used to illustrate the principles and effects of the present invention, but not to limit the present invention. Any person skilled in the art can modify the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the rights of the present invention should be listed in the scope of the patent application described later.
應當理解地，在本發明所揭示之技術內容得能涵蓋之範圍內，各技術特徵(例如具體實施態樣及實施例所揭示者)可以自由地相互組合以形成新的或更佳的技術方案，為簡潔起見，在此不贅述。且本發明所揭示之由端值所構成之數值範圍中，只要數值落於上下兩端值之間，即應包含在本發明所揭示的範圍內，且其與端點或其他數值所形成之次範圍亦應理所當然地包含在本發明所揭示的範圍內。 It should be understood that within the scope covered by the technical content disclosed in the present invention, various technical features (such as those disclosed in specific implementations and examples) can be freely combined with each other to form new or better technical solutions , for the sake of brevity, it is not repeated here. And in the numerical range formed by the end values disclosed in the present invention, as long as the numerical value falls between the upper and lower end values, it shall be included in the range disclosed in the present invention, and it shall be included in the range formed by the end points or other numerical values. Sub-ranges should also be naturally included in the scope disclosed in the present invention.
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