201120152 六、發明說明： I：發明戶斤屬之技術領域3 發明領域 本發明係有關於一種墨水組成物者，特別是有關於採 用壓印方法或滾印方法形成基板之圖案時，可以抑制酸的 攻擊以保護微細圖案，且增進微細圖案及薄膜之精密度， 減少不良率，藉以改善收率及提高步驟之效率性的墨水組 成物者。 L· 發明背景 一般在形成信息保存、小型傳感器、光結晶及光學元 ' 件、微電子機械元件、顯示元件、顯示器以及半導體所應 用之微細圖案的步驟，係採用利用光形成微細圖案的光刻 (photolithography)方法。 最近，替代複雜光刻步驟之次世代步驟正在興起。代 表例可以例舉滾印步驟。滾印步驟係替代現有的用光刻形 成圖案時所使用的高解析度掩膜，利用以無機物及高分子 製成之包覆層（blanket)與錯版(cliche)在欲形成微細圖案之 基板上直接轉印以形成圖案。作為替代方案提出了這種滾 印方法，因其利用以無機物及高分子製成之包覆層而改善 匹配以及離型性，透過應用熱硬化步驟以提高生產性及作 業效率，另外，可以突破性地減少伴隨經歷光刻之漏光或 顯像作業之類的各種步驟所實行的複雜步驟及因其而產生 之附帶的步驟費用。 201120152 這種滾印方法在大韓民國專利申請第2006-0005482號 (公開專利公報第10-2007-76292號）中揭示有關滾印裝置及 利用其之顯示裝置之製造方法。前述文獻中揭示滾印方法 可應用在 FED(Field Emission Display)、有機 EL(Electro Luminescent)、PDP(Plasma Display Panel)裝置，製造步驟 係簡單涉及’反復印刷後依然可確保圖案之精密度。 滾印步驟所應用之墨水組成物大體可以區分為熱硬化 性樹脂組成物與光硬化性樹脂組成物。為使用熱硬化性樹 月曰組成物要將熱硬化性樹脂組成物加熱到特定溫度以上以 確保流動性，同時將無機物及高分子製成之包覆層加壓以 形成薄膜或微細圖案，由於利用高溫，所以容易在快速時 間内確保薄膜或微細圖^另外’光硬化性樹脂組成物係 在無氧的氮氣氛圍狀態下透過光騎來形成薄膜或微細圖 案之方式。該方式係藉由在光硬化性樹脂組成物中引起交 聯’可以增進薄膜或微細圖案之精密度。 為形成用於現有的TFT型液晶顯示元件、有機τρΓ型液 晶顯示元件、QLED型液晶顯示元件、可撓性顯示器之液晶 顯示元件所常用的面板等之薄膜或微細圖案，可適當應用 滚：方法。但是，因此-次性滾印用墨水組成物之物性就 不=不優異’制是為形成TFT_顯示器在料步驟時， 不保護之金屬層與墨水組成物之界面就不能產生因強 西文汉透所造成之触刻而產生的圖案不良。但是，在現有的 滚印步驟中，圖案轉印後以低溫加熱後，在濕式餘刻或乾 式敍刻步驟時，因紐渗透使金屬層之微細__部分不 201120152 會形成，同時微細圖案之精密度不良，在以高溫加熱之情 形，微細圖案之厚度會減少，濕式蝕刻或乾式蝕刻步驟時 會產生不得不保護之金屬層之微細圖案消失的問題。 先前技術文獻 專利文獻 專利文獻1 :大韓民國專利申請第2006-0005482號（公開 專利公報第10-2007-76292號） 【發明内容】 發明概要 發明欲解決之課題 從而，為解決如前所述之習知技術的問題，本發明之 目的在於提供一種墨水組成物以及利用其之基板圖案的形 成方法，該墨水組成物藉由添加矽烷偶合劑作為耐酸性強 化劑，在採用壓印方法或滾印方法形成基板之圖案時可以 抑制酸的攻擊以保護微細圖案，且增進微細圖案及薄膜之 精密度，減少不良率，藉以改善收率及提高步驟之效率性。 用以欲解決課題之手段 為達成前述目的，本發明提供一種墨水組成物，其特 徵為， 在包含a)高分子樹脂，b)賦黏劑，以及c)有機溶媒之墨 水組成物中， 含有d)矽烷偶合劑作為耐酸性強化劑。 合適的是，耐酸性強化劑d)矽烷偶合劑含有0.01至10 5 201120152 ，另外，本發明提供-種利用前述墨水組成物之基板的 圖案形成方法。 合適的是’前述圖案形成方法採用壓印方法或滾印方法。 另外，本發明提供一種基板，其具有利用前述圖案形 成方法形成之圖案。 發明效果 本發明之墨水組成物係藉由添加石夕烧偶合劑作為对酸 性強化劑’在制壓印方法或滾印方法形成純之圖案時， 可以抑制酸的攻擊以保護微細圖案，且增進微細圖案及薄 膜之精密度，減少不良率，藉以改善收率及提高步驟之效 率性。 圖式簡單說明 第1圖係利用依據本發明之實施例丨製成之墨水組成物 形成微細圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水 洗淨’之後觀察其表面之光學顯微鏡照片。 第2圖係利用依據本發明之實施例2製成之墨水組成物 形成微細圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水 洗淨，之後觀察其表面之光學顯微鏡照片。 第3圖係利用依據比較例1製成之墨水組成物形成微細 圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水洗淨，之 後觀察其表面之光學顯微鏡照片。 第4圖係利用依據比較例2製成之墨水組成物形成微細 圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水洗淨，之 後觀察其表面之光學顯微鏡照片。 201120152 C實施方式：j 較佳實施例之詳細說明 以下’將詳細說明本發明。 本發明之墨水組成物，其特徵為，在包含約高分子樹 脂，b)賦黏劑，以及c)有機溶媒之墨水組成物中，含有d) 石夕烧偶合劑作為对酸性強化劑。 在本發明之墨水組成物中，前述a)高分子樹脂可以使 用通常墨水組成物所使用之酚醛清漆樹脂、丙烯酸樹脂等。 則述酚醛清漆樹脂可以使用令間曱酚、對曱酚、2,3,5-三曱 基苯酚、2,3-二曱苯、3,5_二曱苯等的芳香族醇與甲醛或聚 曱越發生反應合成之高分子。另外，前述丙稀酸樹脂可以 使用不飽和敌酸、芳香族單體、丙烯酸單體等發生聚合而 成者。 月’J述南分子樹脂之重量平均分子量以2,〇〇〇至1〇〇 〇〇〇 為佳’ 2,000至45,000更佳。 相對於本發明之墨水組成物，前述高分子樹脂以含5至 45重$ %為佳，含7至3〇重量％更佳。在前述範圍内時，會 提南圖案支持體之作用與圖案之轉印率，可以改善收率及 提局步驟之效率性。 另外，本發明之墨水組成物中，前述b)賦黏劑係維持 墨水組成物之圖案形成能優異。 前述賦黏劑之具體例可以使用選自於新戊四醇、沒食 子酸曱酯、沒食子酸丙酯、沒食子酸月桂酯、沒食子酸辛 略、密妥耳(metol)、酿胺鹽酸鹽(tyramine hydrochloride)、 201120152 1- (3-經本基)*»底嘻、4-'/臭-2-(5-異°惡唾基）苯g分(4-bromo-2-(5-彳寸y U A〇phenol)、4-(咪唑-1-基）苯酚、芹菜素 (apigenin)、2-(4,5-二氫-1H-咪唑-2-基）苯紛、3-(4,5-二氫-1H-咪。坐-2-基）苯酚、4-(4,5-二氫-1H-咪唑-2-基）苯酚、4-硝基 -2-(1Η-°比唑-3-基）苯酚、2-(2-羥苯基)-1Η-苯并咪唑、4-(4-甲.基-4,5-二氫-1H-咪坐_2_基)苯酴、1-胺基-2-萘盼鹽酸鹽、 2,4-二胺基苯酌·二鹽酸鹽、2-乙醯胺苯紛、2-胺基-3-确基紛、 2- 胺基-4-氣-5-硝基酿·、2-胺基-5-硝基盼、3-胺基-2-萘酴、 3- 曱氧基酪胺鹽酸鹽、4,7-二甲氧基-1，1〇-啡啉、4-胺基-1-蔡·:酴鹽酸鹽、4-胺基-3-氣苯盼鹽酸鹽、4-胺苯紛鹽酸鹽、 4- 二本甲基本紛、8-胺基-2-奈酿、鹰嘴旦芽素A(bi〇chanin A)、氣酿、五漠’紛（pentabromophenol)、雙水合懈皮素 (quercetin dihydrate)、黃榼素、1，3,5-三曱基_2,4,6-三（3,5- 一二級丁基-4-經卞基）苯、三（3,5-二三級丁基_4_經节基）三 聚異氰酸酯、十八烷基_3_(3,5_二三級丁基_4_羥苯基）丙酸 酯、2,5-雙（1,1-二甲基丙基)苯二酚三_(2甲基_4_ 經基-5-三級丁基苯基）丁烧、三乙二醇_雙(3_三級丁基冰經 基-5-甲基苯基）丙酸酯、2,2_伸甲基雙(4_甲基_6(1甲基環 己基)-苯盼）以及三(2,4_二三級丁基苯基)磷酸自旨組成之族 群中的1種以上者。 别述賦黏劑在本發明之墨水組成物中宜含5至45重量 %，更佳的疋含7至3〇重量％。在前述範圍内時，會固定地 維持圖案之線寬及線間隔，在欲形成微細®案之基板上發 揮增進圖案之精密度的效果。 201120152 另外，本發明之墨水組成物中，前述C)有機溶媒宜使 用可以容易地溶解本發明之墨水組成物所使用之成分者。 作為具體例，前述有機溶媒可以單獨或混合2種以上使 用丙烯腈、乙腈、甘油、二甲亞砜、硝基曱烷、二曱基曱 醯胺S K)、苯酚、N-甲基吡咯啶酮、吡啶 全氟三丁胺、全氟萘烷、2-丁酮、碳酸亞曱基酯（methylene carbonate)、甲醇、乙醇、乙二醇、三乙二醇、四乙二醇、 丙二醇、丙稀乙二醇(propylene ethylene glycol)、二乙二醇、 丁二醇、苄醇、正己醇、烯丙醇等的醇類；碳酸丙烯酯、 四氫α夫喃、茴香醚、1,4-二°惡烧、1-甲氧基-2-丙醇、茴香醚、 二丁醚、二苯醚等的醚類；醋酸乙酯、醋酸甲酯、醋酸丙 酯、醋酸丁酯、丙酸乙酯（工于少7° 口匕°才^)、乙酯、丁酯、 2-羥基異丁酸甲酯、丙二醇曱醚醋酸酯 (2-methoxy-l-methylethyl ester)、2-甲氧基醋酸乙醋 (2-methoxyethanol acetate)、醋酸-2-乙氧基乙醋 (2-ethoxyethanol acetate)等的醋類；乙二醇曱醚醋酸醋、乙 二醇乙醚醋酸酯等的乙二醇烷基醚醋酸酯類；乙二醇曱醚 丙酸酯、乙二醇乙醚丙酸酯等的乙二醇烷基醚丙酸酯類； 乙二醇甲醚、乙二醇乙醚等的乙二醇單烷基醚類；二乙二 醇單曱醚、二乙二醇單乙醚、二乙二醇二甲醚、二乙二醇 甲乙醚等的二乙二醇烷基醚類；丙二醇甲醚醋酸酯、丙二 醇乙醚醋酸酯、丙二醇丙醚醋酸酯等的丙二醇烷基醚醋酸 酯類；丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙 醚丙酸酯等的丙二醇烷基醚丙酸酯類；丙二醇曱醚、丙二 201120152 酵乙醚丙—醇丙ϋ、丙二醇τ 二丙二醇_ 寸的丙二醇單烷基醚類 内*一甲醚'二丙二醇二乙 Ψ jfep -T- 、一丙二醇烷基醚類 ΜΤΜ、丁二醇單⑽ 二醇二曱醚、二丁n 7 ^厂〜醇早甲醚類丨二丁 特別是前it古 °一 ：的二丁二醇烷基醚類等。 L單=改善後述之外偶合劑之性能，與 Π:，合使用2種以上之溶媒會使圖案轉印 相對於墨水組成物，前述有機溶媒宜含50至89 99重量 %更佳的疋360至80重量％。在前述範圍内時，就可以同 時有助於轉性、步驟之效率性的提高。 另外’本發明之墨水組成物含有d)石夕烧偶合劑作為耐 〇㈣力魏偶合劑在形成基板之圖案時所實 行的㈣步驟具有耐強酸的耐性，會保護金屬層 ’提if)圖 案之精密度且減少不良率。前述石找偶合劑之具體例可以 使用選自於甲基三乙氧基石夕烧、γ-縮水甘油醚氧丙基甲基 二乙氧基石夕烧、縮水甘油醚氧丙基三乙氧基矽烷、Ν-(2-胺乙基)-3-胺丙基三乙氧基矽烷、雙（三乙氧基矽基丙基）四 硫化物、雙（二乙氧基矽基丙基)二硫化物、γ-胺丙基三乙氧 基矽烷、乙烯基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基 石夕炫、β-(3,4-環氧環己基）乙基三甲氧基矽烷、7_縮水甘油 醚氧丙基三甲氧基矽烷、γ甲基丙烯醯氧基丙基三甲氧基 石夕炫、Ν~苯基个胺丙基三曱氧基矽烷、Ν-(2-胺乙基)-3-胺 丙基甲基二甲氧基矽烷、N-(2-胺乙基)-3-胺丙基三甲氧基 石夕烧、3-氯丙基三甲氧基矽烷、3酼丙基甲基二甲氧基矽烷、 10 201120152 毓丙基三曱氧基矽烷、γ-胺丙基三甲氧基矽烷、乙烯基三 曱氧基矽烷、丙基三甲氧基矽烷、γ-丙烯醯氧基丙基三甲 氧基石夕烧、辛基三乙氧基石夕烧、3 -氯丙基三乙氧基石夕烧、 乙稀基-二(2-甲氧基乙氧基)石夕烧、3-婉丙基三乙氧基石夕烧、 γ-醯脲丙基三曱氧基矽烷、3-氣丙基曱基二曱氧基矽烷、乙 烯基曱基二乙氧基矽烷、乙烯基曱基二甲氧基矽烷以及正 十八烷基三曱氧基矽烷組成之族群中的1種以上者。 本發明中相對於本發明之墨水組成物，前述矽烷偶合 劑之含量以使用0.01至10.0重量％為佳，合適的是使用0.1 至3.0重量％為佳。當前述矽烷偶合劑不足0.01重量％時，耐 酸性就下降，當超過10.0重量％時，與輥(作為一例是包覆 _ 層）之膨潤現象就變激烈，步驟時間增長，形成微細圖案之 時間增加，會產生微細圖案之精密度下降之問題。 由如前所述之成分構成之本發明的墨水組成物可以選 擇性地使用界面活性劑、密合性調整劑或者可視認化合物。 前述界面活性劑會防止因使用矽烷偶合劑而產生的墨 水材料之染色及孔痕，發揮確保完好的塗覆性之作用。 前述界面活性劑可以使用石夕系界面活性劑或全氟烧基 低聚物之類的氟系列之界面活性劑，相對於墨水組成物其 含量在0.01至3重量％，宜使用0.1至1.5重量％為佳。 前述密合性調整劑係為提高對於下部膜之密合特性而 加以使用。前述密合性調整劑可以使用一般的黑色素系交 聯劑，黑色素系交聯劑可以使用尿素與曱醛之縮合生成物、 三聚氰胺與甲醛之縮合生成物、由醇獲得之羥甲基尿素烷 201120152 基醚類或羥曱基三聚氰胺烷基醚類等。 具體地說’前述尿素與甲醛之縮合生成物可以使用單 羥甲基尿素、二羥曱基尿素等。前述三聚氰胺與甲醛之縮 合生成物可以使用六羥曱基三聚氰胺，除此以外亦可使用 三聚氰胺與曱醒·之部分縮合生成物。另外，前述經基尿素 烷基醚類係尿素與曱醛之縮合生成物中羥曱基之部分或全 部與醇類發生反應所製得者，其具體例可以使用單甲基尿 素甲基醚、二曱基尿素甲基醚等。前述羥甲基三聚氰胺烷 基醚類係二聚氰胺與甲醛之縮合生成物中羥曱基之部分或 全部與醇類發生反應所製得者，其具體例可以使用六經甲 基一聚氛膝六曱醚、六羥甲基三聚氰胺六丁醚等。另外， 亦可使用二聚氰胺之胺基的氫原子被羥基甲基以及甲氧基 甲基所取代之結構的化合物、三聚氰胺之胺基的氫原子被 丁氧土曱基以及甲氧基甲基所取代之結構的化合物等，特 別 '使用_甲基三聚氰胺烧基&E類為佳。 田使用前述密合性調整劑時，其含量以使用〇 〇1至5重 里％為佳，合適的係以使用〇.5至2 5重量％為佳。在前述範 圍内時，本發明之墨水組成物就會與下部基板具有優異之 密合性。 、 、 另外，前述可視認化合物可以使用染料或顏料或感光 性化合物以麵墨水㈣物之可視認性，與高分子樹脂溶 解、匕圖案轉印能之狀態形成，會發揮作用用來容易地 確保與所需之基板的接著力。前述可視認化合物在二疊氮 系化&物中可以單獨或混合使用三羥二苯基鲷與2重氮 12 201120152 萘酚-5-磺酸發生酯化反應所製成之2,3,4-三羥二苯基酮 -1,2-萘醌二疊氮-5-磺酸酯、四羥二苯基酮與2-重氮-1-萘酚 -5-磺酸發生酯化反應所製成之2,3,4,4-四羥二苯基酮 -1，2,3,5-三甲基苯酚等。 當使用前述可視認化合物時，相對於本發明之墨水組 成物其含量以使用0.001至3.0重量％為佳，合適的係以使用 0.001至2.0重量％為佳。 包含如前所述之成分的本發明之墨水組成物可以應用 在利用公知的一般壓印步驟（作為一例係大韓民國專利公 開公報第10-2005-0019557號）或滾印步驟（作為一例係大韓 民國專利公開公報第10-2007-0076292號)之圖案形成中，在 基板形成圖案。 具體例可以採用旋轉塗佈、輥塗、狹縫塗佈等之適當 方法，以0.5-10μιη之厚度塗佈後，在壓印步驟中係可以與 具有欲形成形狀之圖案的矽高分子印模接觸後，在矽基板、 陶瓷基板、金屬層、高分子層等的基板上轉印圖案，在滾 印步驟中係可以利用具有欲形成形狀之圖案的鉛版與矽高 分子接觸後，在矽基板、陶瓷基板、金屬層、高分子層等 的基板上轉印圖案。 接下來，可以利用紫外線實行光硬化步驟，或者在 90-200°C之溫度實施熱處理之熱硬化步驟，或者可以一併 實施光硬化步驟與熱硬化步驟。實施前述熱處理步驟係為 不令墨水組成物中的固體成分發生熱分解的同時蒸發（增 發)溶媒。一般來說，利用熱處理步驟使溶媒之濃度最少化 13 201120152 為佳，貫施直到基板上殘留厚度1〇μιη以下之墨水膜是合適 的。這種步驟會增進墨水膜與基板之接著性以及耐化學性。 用敍刻溶液或氣體電漿對完成如前所述之步驟的基板進行 處理，處理露出的基板部位，此時，基板未露出之部位係 因墨水膜而受到保護。這樣地處理基板之後，利用以適當 的脫模機除去墨水膜可以在基板上形成微細電路圖案。 以下，為本發明之理解將提出合適的實施例，下述之 實施例不過是例示本發明者，本發明之範圍並不限定於下 述之實施例。 實施例 實施例1 以如下表1所述之成分與組成均勻地混合，製造實施例 1-2與比較例1-2之墨水組成物。下述表丨之單位為重量份。 下述表1中使用的高分子樹脂為重量平均分子量20,000之 酚醛清漆(示，y，）樹脂，賦黏劑為沒食子酸丙酯，有機溶 媒為曱醇，矽炫偶合劑為甲基三乙氧基石夕烧，界面活性劑 為石夕系列’密合性調整劑為六經曱基三聚氰胺六曱鱗。 表1 項目 實施例1 實施例2 比較例1 比較例2 高分子樹脂 15.0 15.0 15.0 15.0 賦黏劑 5.0 5.0 5.0 5.0 .有機溶媒 76.8 73.9 76.9 61.9 车夕炫偶合劑 0.1 3.0 0 15.0 界面活性剤 0.1 0.1 0.1 0.1 密合性調整劑 3.0 3.0 3.0 3.0 利用前述表1中製造的實施例1-2與比較例1-2之墨水組 201120152 成物以如下所述之方法評估物性。 A.微細圖案轉印率 在沒有圖案的矽高分子之上塗覆前述實施例1-2與比 較例1-2之墨水組成物。在10秒鐘自然乾燥後，矽高分子邊 通過鉛版邊在欲形成之基板上轉印微細圖案，將圖案之轉 印率示於下述表2。圖案之轉印率係以具有lxlmm之大小的 100個單元中依據圖案形成明確表示為0-100%。 表2 區分 實施例1 實施例2 比較例1 比較例2 圖案轉印率 98 97 95 92 如前述表2所示，依據本發明獲得之實施例1及實施例2 的墨水組成物，其圖案轉印率在97%以上，可以確認與比 較例相比優異。 B.耐酸性評估 在沒有圖案的矽高分子之上塗覆前述實施例1-2與比 較例1-2之墨水組成物。一定時間自然乾燥後，矽高分子邊 通過鉛版邊在欲形成之基板上轉印微細圖案。將轉印有微 細圖案之基板在150°C的高溫熱處理3分鐘後，在40°C強酸 浸潰1分鐘後用蒸餾水洗淨，之後通過光學顯微鏡確認圖案 部分，將其結果分別示於第1圖至第4圖。 如第1圖至第4圖所示，依據本發明獲得之實施例1(第1 圖）及實施例2(第2圖）中形成有微細圖案之金屬層沒有因強 酸發生線寬變化，微細圖案係精密地形成，可以確認為耐 酸性優異之墨水組成物，相反，比較例1及2之情形中，形 15 201120152 成有微細圖案之金屬層確認到因強酸造成的線寬之變化激 烈，且可以確認沒有精密地形成微細圖案。 【圖式簡單說明3 第1圖係利用依據本發明之實施例1製成之墨水組成物 形成微細圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水 洗淨，之後觀察其表面之光學顯微鏡照片。 第2圖係利用依據本發明之實施例2製成之墨水組成物 形成微細圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水 洗淨，之後觀察其表面之光學顯微鏡照片。 第3圖係利用依據比較例1製成之墨水組成物形成微細 圖案後，施加熱處理步驟，浸潰強酸後用蒸顧水洗淨，之201120152 VI. Description of the invention: I: Technical field of the invention of the invention 3 FIELD OF THE INVENTION The present invention relates to an ink composition, particularly when the pattern of the substrate is formed by an imprint method or a roll printing method, the acid can be suppressed The attack is to protect the fine pattern, and to improve the precision of the fine pattern and the film, and to reduce the defect rate, thereby improving the yield and improving the efficiency of the step of the ink composition. BACKGROUND OF THE INVENTION Generally, in the steps of forming fine patterns for information storage, small sensors, photocrystallization, optical elements, microelectromechanical components, display elements, displays, and semiconductors, photolithography using light to form fine patterns is employed. (photolithography) method. Recently, the next generation of steps to replace complex lithography steps is emerging. The representative example can exemplify the roll printing step. The roll printing step replaces the high-resolution mask used in the conventional patterning by photolithography, and uses a blanket made of inorganic materials and polymers and a cliche on the substrate on which the fine pattern is to be formed. Direct transfer on top to form a pattern. As an alternative, this method of printing is proposed because it improves the matching and the release property by using a coating layer made of inorganic materials and polymers, and improves the productivity and work efficiency by applying a heat hardening step. The complex steps involved in the various steps associated with light leakage or imaging operations undergoing lithography are reduced, and the attendant steps incurred therefrom are expensed. The method of manufacturing a printing apparatus and a display apparatus using the same is disclosed in the Korean Patent Application No. 2006-0005482 (Publication No. 10-2007-76292). The above-mentioned document discloses that the roll printing method can be applied to an FED (Field Emission Display), an organic EL (Electro Luminescent), or a PDP (Plasma Display Panel) device, and the manufacturing steps are simple. The precision of the pattern can be ensured after repeated printing. The ink composition to which the roll printing step is applied can be roughly classified into a thermosetting resin composition and a photocurable resin composition. In order to use the thermosetting tree composition, the thermosetting resin composition is heated to a specific temperature or higher to ensure fluidity, and the inorganic layer and the polymer-made coating layer are pressed to form a film or a fine pattern, Since the high temperature is utilized, it is easy to ensure a film or a fine pattern in a rapid time. In addition, the 'photocurable resin composition is formed by a light riding in an oxygen-free nitrogen atmosphere to form a film or a fine pattern. This method can improve the precision of the film or the fine pattern by causing crosslinking in the photocurable resin composition. In order to form a film or a fine pattern for a conventional TFT type liquid crystal display element, an organic τρΓ type liquid crystal display element, a QLED type liquid crystal display element, a panel commonly used for a liquid crystal display element of a flexible display, etc., a roll method can be suitably applied. . However, the physical properties of the ink composition for the secondary printing are not = not excellent. In order to form the TFT_display, the interface between the unprotected metal layer and the ink composition cannot be produced due to the strong Western language. The pattern created by the exposure of Han Tseng is poor. However, in the existing printing step, after the pattern is transferred and heated at a low temperature, in the wet residual or dry sculpt step, the fine layer of the metal layer is formed by the infiltration of the lining, and the fine pattern is formed at the same time. The precision is poor, and when heated at a high temperature, the thickness of the fine pattern is reduced, and the wet pattern or the dry etching step causes a problem that the fine pattern of the metal layer to be protected disappears. CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Application No. 2006-0005482 (Patent Publication No. 10-2007-76292) SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The problem of the present invention is to provide an ink composition and a method for forming a substrate pattern using the same, which is an acid resistance enhancer by adding a decane coupling agent, by using an imprint method or a roll printing method. When the pattern of the substrate is formed, the attack of the acid can be suppressed to protect the fine pattern, and the precision of the fine pattern and the film can be improved, and the defect rate can be reduced, thereby improving the yield and improving the efficiency of the step. Means for Solving the Problems In order to achieve the above object, the present invention provides an ink composition characterized by comprising an ink composition comprising a) a polymer resin, b) an adhesive, and c) an organic solvent. d) A decane coupling agent is used as an acid resistance enhancer. Suitably, the acid-resistant enhancer d) decane coupling agent contains 0.01 to 10 5 201120152. Further, the present invention provides a pattern forming method of a substrate using the ink composition. Suitably, the aforementioned pattern forming method employs an imprint method or a roll printing method. Further, the present invention provides a substrate having a pattern formed by the above-described pattern forming method. Advantageous Effects of Invention The ink composition of the present invention can suppress the attack of an acid to protect a fine pattern by adding a sulphur coupling agent as an acid strengthening agent to form a pure pattern in a embossing method or a printing method. The precision of the fine pattern and the film reduces the defect rate, thereby improving the yield and improving the efficiency of the step. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an optical micrograph showing the surface of an ink composition prepared according to an embodiment of the present invention, after forming a fine pattern, applying a heat treatment step, immersing a strong acid, and then washing it with distilled water. Fig. 2 is a view showing an optical micrograph of the surface of the ink composition prepared in accordance with Example 2 of the present invention after forming a fine pattern, applying a heat treatment step, immersing the strong acid, and then washing it with distilled water. Fig. 3 shows the formation of a fine pattern by using the ink composition prepared in Comparative Example 1, and then applying a heat treatment step, immersing the strong acid, and then washing it with distilled water, and then observing the optical micrograph of the surface. Fig. 4 shows the formation of a fine pattern by using the ink composition prepared in Comparative Example 2, followed by applying a heat treatment step, immersing the strong acid, and then washing it with distilled water, and then observing the optical micrograph of the surface. 201120152 C Embodiment: j Detailed Description of Preferred Embodiments Hereinafter, the present invention will be described in detail. The ink composition of the present invention is characterized in that d) a sulphur coupling agent is contained as an acid strengthening agent in an ink composition comprising about a polymer resin, b) a binder, and c) an organic solvent. In the ink composition of the present invention, the a) polymer resin of the above a) may be a novolak resin or an acrylic resin used in a usual ink composition. The novolak resin may be an aromatic alcohol such as m-nonylphenol, p-nonylphenol, 2,3,5-tridecylphenol, 2,3-diphenylbenzene, 3,5-diphenylene or the like and formaldehyde or The polymer that reacts and reacts with the polymerization. Further, the acrylic resin may be polymerized by using an unsaturated acid, an aromatic monomer, an acrylic monomer or the like. The weight average molecular weight of the month's molecular resin is preferably from 2, 〇〇〇 to 1 〇〇 ’ 2,000 to 45,000. The polymer resin is preferably contained in an amount of 5 to 45 wt%, more preferably 7 to 3 wt%, based on the ink composition of the present invention. When it is within the above range, the effect of the south pattern support and the transfer rate of the pattern are improved, and the efficiency of the yield and the progress of the step can be improved. Further, in the ink composition of the present invention, the b) tackifier is excellent in maintaining the pattern formation ability of the ink composition. Specific examples of the above-mentioned viscosity-increasing agent may be selected from the group consisting of neopentyl alcohol, decyl gallate, propyl gallate, lauryl gallate, gallic acid, and metol. , tyramine hydrochloride, 201120152 1- (3- via the base) *» bottom 4-, 4-' / odor-2-(5-iso oxazino) benzene g (4-bromo- 2-(5-inch y UA〇phenol), 4-(imidazol-1-yl)phenol, apigenin, 2-(4,5-dihydro-1H-imidazol-2-yl)benzene , 3-(4,5-dihydro-1H-miso.yt-2-yl)phenol, 4-(4,5-dihydro-1H-imidazol-2-yl)phenol, 4-nitro-2- (1Η-°Bizozol-3-yl)phenol, 2-(2-hydroxyphenyl)-1Η-benzimidazole, 4-(4-methyl-4,5-dihydro-1H-miso 2_yl)phenylhydrazine, 1-amino-2-naphthalene hydrochloride, 2,4-diaminobenzene dihydrochloride, 2-acetamide, 2-amino-3- Exactly, 2-amino-4-gas-5-nitro-branched, 2-amino-5-nitropan, 3-amino-2-naphthoquinone, 3-decyloxytyramine hydrochloride Salt, 4,7-dimethoxy-1,1 〇-morpholine, 4-amino-1-lane: hydrazine hydrochloride, 4-amino-3-benzene benzene hydrochloride, 4- Amine benzene hydrochloride, 4-dimethyl phthalate, 8-amine -2-Nano, 〇 旦 A A ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Base 2,4,6-tris(3,5-first-diethylbutyl-4-sulfonyl)benzene, tris(3,5-di-tri-butyl-4-yl)-polyisocyanate, Octadecyl_3_(3,5-ditributyl -4- hydroxyphenyl) propionate, 2,5-bis(1,1-dimethylpropyl)benzenediol III_(2 Methyl_4_ mercapto-5-tertiary butylphenyl) butadiene, triethylene glycol _bis(3_tert-butylbutyl peroxy-5-methylphenyl)propionate, 2,2 One or more of the group consisting of methyl bis(4_methyl_6(1methylcyclohexyl)-benzene) and tris(2,4-ditriphenyl)phosphoric acid The adhesive is preferably contained in the ink composition of the present invention in an amount of 5 to 45% by weight, more preferably 7 to 3 % by weight, and within the above range, the line width and line of the pattern are fixedly maintained. In the ink composition of the present invention, the above-mentioned C) organic solvent should be used to accommodate the effect of improving the precision of the pattern on the substrate to be formed into a fine film. Dissolving the ink composition of the present invention by the use thereof. As a specific example, the organic solvent may be used alone or in combination of two or more kinds of acrylonitrile, acetonitrile, glycerin, dimethyl sulfoxide, nitrononane, dimethyl decyl amide, phenol, and N-methylpyrrolidone. , pyridine perfluorotributylamine, perfluorodecalin, 2-butanone, methylene carbonate, methanol, ethanol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, propylene Alcohols such as propylene ethylene glycol, diethylene glycol, butanediol, benzyl alcohol, n-hexanol, allyl alcohol; propylene carbonate, tetrahydro α-pentan, anisole, 1,4-two ° Ether, 1-methoxy-2-propanol, anisole, dibutyl ether, diphenyl ether and other ethers; ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate (Working in less than 7 ° mouth 匕 ° ^), ethyl ester, butyl ester, methyl 2-hydroxyisobutyrate, 2-methoxy-l-methylethyl ester, 2-methoxyacetic acid Ethylene glycol such as 2-methoxyethanol acetate or 2-ethoxyethanol acetate; glycol oxime ether acetate vinegar, ethylene glycol ethyl ether acetate, etc. Ethylene glycol alkyl ether acetate; glycol alkyl ether propionate such as ethylene glycol oxime ether propionate, ethylene glycol ethyl ether propionate; ethylene glycol methyl ether, ethylene glycol ether, etc. Ethylene glycol monoalkyl ethers; diethylene glycol alkyl ethers such as diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; a propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate or propylene glycol propyl ether acetate; a propylene glycol alkyl group such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate or propylene glycol propyl ether propionate; Ether propionate; propylene glycol oxime ether, propylene 2 201120152 leaven ether, propanol propionate, propylene glycol τ dipropylene glycol _ inch propylene glycol monoalkyl ether type * methyl ether 'dipropylene glycol diethyl hydrazine jfep -T- A propylene glycol alkyl ether hydrazine, a butane diol mono (10) diol dioxime ether, a dibutyl n 7 ^ plant ~ alcohol early methyl ether bismuth, especially a dibutyl diol alkyl ether Classes, etc. L single = improving the performance of the coupling agent described below, and Π: using two or more kinds of solvents together to transfer the pattern relative to the ink composition, and the organic solvent preferably contains 50 to 89 99% by weight of 疋360. Up to 80% by weight. When it is within the above range, it is possible to contribute to the improvement of the efficiency and the efficiency of the steps at the same time. In addition, the ink composition of the present invention contains d. The shixi sinter coupling agent is used as a ruthenium-resistant (tetra) force-wei coupler to perform a pattern of forming a substrate. The step (4) has resistance to strong acid and protects the metal layer. Precision and reduce the rate of non-performing. Specific examples of the above-mentioned stone coupling coupler may be selected from methyl triethoxy zephyr, γ-glycidyloxypropyl methyl diethoxy oxysulfonate, glycidyloxypropyl triethoxy decane. , Ν-(2-Aminoethyl)-3-aminopropyltriethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, bis(diethoxymethylpropyl) disulfide , γ-aminopropyltriethoxydecane, vinyltriethoxydecane, 3-isocyanatepropyltriethoxyxanthene,β-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 7-glycidyloxypropyltrimethoxydecane, γ-methacryloxypropyltrimethoxyxanthene, Ν~phenylaminopropyltrimethoxy decane, Ν-(2-amine Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxycarbazide, 3-chloropropyltrimethoxydecane, 3酼Propylmethyldimethoxydecane, 10 201120152 propyl propyl trimethoxy decane, γ-aminopropyl trimethoxy decane, vinyl trimethoxy decane, propyl trimethoxy decane, γ-acryl hydrazine Oxypropyl trimethoxy zebra, Triethoxy sulphur, 3-chloropropyltriethoxy sinter, ethylene-bis(2-methoxyethoxy) sinter, 3-mercaptopropyltriethoxy sulphur , γ-ureidopropyl tridecyloxydecane, 3-cyclopropyl decyl decyloxydecane, vinyl fluorenyl diethoxy decane, vinyl fluorenyl dimethoxy decane, and n-octadecane One or more of the group consisting of quinone decyloxy decane. In the present invention, the content of the aforementioned decane coupling agent is preferably from 0.01 to 10.0% by weight, particularly preferably from 0.1 to 3.0% by weight, based on the ink composition of the present invention. When the decane coupling agent is less than 0.01% by weight, the acid resistance is lowered. When it exceeds 10.0% by weight, the swelling phenomenon with the roll (as a coating layer) is intense, and the step time is increased to form a fine pattern. When added, there is a problem that the precision of the fine pattern is lowered. The ink composition of the present invention comprising the components as described above may optionally be selected from a surfactant, an adhesion adjuster or a visible compound. The surfactant prevents the dyeing of the ink material and the pore marks caused by the use of the decane coupling agent, and functions to ensure good coatability. The surfactant may be a surfactant of a fluorine series such as a Shishi surfactant or a perfluoroalkyl oligomer, and the content of the ink composition is 0.01 to 3% by weight, preferably 0.1 to 1.5% by weight. % is better. The adhesion adjuster is used to improve the adhesion characteristics to the lower film. As the adhesion adjuster, a general melanin-based crosslinking agent can be used, and a melanin-based crosslinking agent can be a condensation product of urea and furfural, a condensation product of melamine and formaldehyde, and a methylol urea obtained from an alcohol 201120152. An ether or a hydroxymethyl melamine alkyl ether or the like. Specifically, monomethylol urea, dihydroxyindole urea or the like can be used as the condensation product of urea and formaldehyde. As the condensed product of melamine and formaldehyde, hexahydrocarbyl melamine may be used, and in addition to this, a partial condensation product of melamine and awake may be used. Further, in the case where a part or all of the hydroxy group of the condensation product of the urea group-containing alkyl ether type urea and furfural is reacted with an alcohol, a specific example may be a monomethyl urea methyl ether. Dimercapto urea methyl ether and the like. The methylol melamine alkyl ether is obtained by reacting a part or all of a hydroxy thiol group in a condensation product of melamine and formaldehyde with an alcohol, and a specific example thereof may be a hexamethyl group. Knee hexamethylene ether, hexamethylol melamine hexabutyl ether and the like. Further, a compound having a structure in which a hydrogen atom of an amine group of melamine is substituted with a hydroxymethyl group and a methoxymethyl group, a hydrogen atom of an amine group of a melamine may be used, and a methoxy group and a methoxy group may be used. The compound of the structure substituted by the group, etc., is particularly preferably 'using methyl melamine alkyl group & E type. When the above-mentioned adhesion adjuster is used, the content is preferably from 1 to 5 % by weight, more preferably from 5% to 25 % by weight. When it is within the above range, the ink composition of the present invention has excellent adhesion to the lower substrate. Further, the visible compound can be formed by using a dye, a pigment, or a photosensitive compound in the visibility of the surface ink (four), and in a state in which the polymer resin is dissolved and the pattern is transferred, and the function is used to easily ensure The adhesion to the desired substrate. The above-mentioned visible compound can be used in the diazide system and the mixture can be used alone or in combination with the esterification reaction of dihydroxydiphenylfluorene with 2diazo 12 201120152 naphthol-5-sulfonic acid. Esterification of 4-trihydroxydiphenyl ketone-1,2-naphthoquinonediazide-5-sulfonate, tetrahydroxydiphenyl ketone with 2-diazo-1-naphthol-5-sulfonic acid The produced 2,3,4,4-tetrahydroxydiphenyl ketone-1,2,3,5-trimethylphenol and the like. When the above-mentioned visible compound is used, it is preferably used in an amount of from 0.001 to 3.0% by weight, more preferably from 0.001 to 2.0% by weight, based on the ink composition of the present invention. The ink composition of the present invention containing the components as described above can be applied to a known general imprinting step (as an example of the Korean Patent Publication No. 10-2005-0019557) or a printing step (as an example of a Korean Republic patent) In the pattern formation of the publication No. 10-2007-0076292, a pattern is formed on the substrate. Specific examples may be applied by a suitable method such as spin coating, roll coating, slit coating, etc., after coating at a thickness of 0.5 to 10 μm, and in the imprinting step, a tantalum polymer impression having a pattern to be formed into a shape. After the contact, the pattern is transferred onto the substrate such as the ruthenium substrate, the ceramic substrate, the metal layer, or the polymer layer, and in the squeezing step, the lead plate having the pattern to be formed can be contacted with the ruthenium polymer, and then A pattern is transferred onto a substrate such as a substrate, a ceramic substrate, a metal layer, or a polymer layer. Next, the photohardening step may be carried out by ultraviolet rays, or the heat hardening step of heat treatment may be performed at a temperature of 90 to 200 ° C, or the photo hardening step and the heat hardening step may be carried out together. The heat treatment step described above is carried out by evaporating (increasing) the solvent while not thermally decomposing the solid component in the ink composition. In general, it is preferable to use a heat treatment step to minimize the concentration of the solvent. 13 201120152 is preferable, and it is suitable to apply an ink film having a thickness of 1 μm or less or less on the substrate. This step enhances the adhesion of the ink film to the substrate as well as the chemical resistance. The substrate subjected to the above-described steps is treated with a etched solution or a gas plasma to treat the exposed substrate portion. At this time, the portion where the substrate is not exposed is protected by the ink film. After the substrate is processed in this manner, a fine circuit pattern can be formed on the substrate by removing the ink film with a suitable stripper. In the following, a suitable embodiment will be set forth for the understanding of the present invention. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the embodiments described below. EXAMPLES Example 1 The ink compositions of Examples 1-2 and Comparative Examples 1-2 were produced by uniformly mixing the components and compositions described in Table 1 below. The units shown below are parts by weight. The polymer resin used in the following Table 1 is a novolak (y,) resin having a weight average molecular weight of 20,000, the tackifier is propyl gallate, the organic solvent is decyl alcohol, and the oxime coupling agent is methyl. The triethoxy zexi is burned, and the surfactant is the Shixi series. The adhesion adjuster is a hexahydrate-based melamine hexagram scale. Table 1 Project Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polymer resin 15.0 15.0 15.0 15.0 Adhesive 5.0 5.0 5.0 5.0. Organic solvent 76.8 73.9 76.9 61.9 Che Xi Xuan coupling agent 0.1 3.0 0 15.0 Interfacial activity 剤 0.1 0.1 0.1 0.1 Adhesion Adjuster 3.0 3.0 3.0 3.0 The physical properties were evaluated by the method described below using the ink set of the Example 1-2 manufactured in the above Table 1 and the ink set 201120152 of Comparative Example 1-2. A. Fine pattern transfer rate The ink compositions of the above Examples 1-2 and Comparative Examples 1-2 were coated on the uncoated polymer. After drying for 10 seconds, the ruthenium polymer was transferred to a substrate to be formed by a lead plate, and the transfer pattern of the pattern was shown in Table 2 below. The transfer rate of the pattern is clearly expressed as 0-100% in accordance with the pattern formation in 100 cells having a size of lxlmm. Table 2 Distinction Example 1 Example 2 Comparative Example 1 Comparative Example 2 Pattern transfer rate 98 97 95 92 As shown in Table 2 above, the ink compositions of Example 1 and Example 2 obtained according to the present invention were patterned. The printing ratio was 97% or more, and it was confirmed that it was superior to the comparative example. B. Evaluation of acid resistance The ink compositions of the above Examples 1-2 and Comparative Examples 1-2 were coated on the uncoated polymer. After drying for a certain period of time, the ruthenium polymer transfers a fine pattern on the substrate to be formed by the lead plate. The substrate on which the fine pattern was transferred was heat-treated at a high temperature of 150 ° C for 3 minutes, and then immersed in a strong acid at 40 ° C for 1 minute, and then washed with distilled water, and then the pattern portion was confirmed by an optical microscope, and the results were shown in the first. Figure to Figure 4. As shown in FIGS. 1 to 4, the metal layer in which the fine pattern is formed in Example 1 (Fig. 1) and Example 2 (Fig. 2) obtained according to the present invention does not have a line width change due to strong acid, and is fine. The pattern was precisely formed, and it was confirmed that the ink composition was excellent in acid resistance. On the contrary, in the case of Comparative Examples 1 and 2, the metal layer having a fine pattern in the shape of 2011, 2011 and 2015 was confirmed to have a sharp change in line width due to strong acid. Further, it was confirmed that the fine pattern was not formed precisely. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a method of applying a heat treatment step by using an ink composition prepared in accordance with Example 1 of the present invention, applying a heat treatment step, immersing a strong acid, and then washing it with distilled water, and then observing an optical microscope photograph of the surface thereof. . Fig. 2 is a view showing an optical micrograph of the surface of the ink composition prepared in accordance with Example 2 of the present invention after forming a fine pattern, applying a heat treatment step, immersing the strong acid, and then washing it with distilled water. Fig. 3 is a step of forming a fine pattern by using the ink composition prepared according to Comparative Example 1, applying a heat treatment step, immersing the strong acid, and then washing it with steam.
I 後觀察其表面之光學顯微鏡照片。 第4圖係利用依據比較例2製成之墨水組成物形成微細 圖案後，施加熱處理步驟，浸潰強酸後用蒸餾水洗淨，之 後觀察其表面之光學顯微鏡照片。 【主要元件符號說明】 (無） 16After I, observe the optical micrograph of the surface. Fig. 4 shows the formation of a fine pattern by using the ink composition prepared in Comparative Example 2, followed by applying a heat treatment step, immersing the strong acid, and then washing it with distilled water, and then observing the optical micrograph of the surface. [Main component symbol description] (none) 16