201224073 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種溶劑或 戈冷劑組成物，其係難 且具優越之樹脂溶解性、於藉e 我 使用。 ^ ^所 【先前技術】 習知之配線基板或顯示器等之電子零件的圖案开， 大多為利用所謂的光刻之方法所形成。光刻係將糊組： 物塗布於基板上，進行微細圖案之曝光後烘烤，利用 刻而去除不要之部分後進行圖案形成之方法。 蝕 疋—般 而S ’問題係由於必須具有餘刻廢液處理設備，拳置 身變得龐大，且必須具有巨額之設備投資，材料之使本 效率也差’由於製造步驟多而導致生產性差。另外用 於受裝置之容3：所限制，對大面積基板難以形成圖案 因此’近年來圖案形成方法並不需要龐大的裳置且 材料之使用效率佳’也容易對應於大面積基板的 J I墨法 、網板印刷法、凸版印刷法、膠版印刷法、昭知 4 ^ “、、相凹版印 刷法、微接觸印刷法' 奈米印跡法等之印刷法而森 目。可用於印刷法之糊組成物所使用的溶劑大客 夕馬使用 -醇8s|系 乙基鱗、二内 丁基鍵等之丙二醇醚系溶劑等 之例子。但是’由於乙二醇醚系溶劑係具有生態毒性 故有不便使用之問題（非專利文獻1)。 另一方面，針對丙二醇醚系溶劑，習知形戌 \襌成太 溶劑；， 醇二丙基醚 醇 二乙二醇二曱基醚或二乙二醇二丁基醚等之乙 丙二醇二曱基醚、二丙二醇 二·丙 201224073 陽能電池之元件的糊組成物中係當做溶劑使用（專利文 獻1)，於專利文獻2中’於丙二醇二烧基謎之中也已記載 使用親油性強的丙二醇二丁基喊。 另外’於形成構成有機薄膜電晶體、電子紙及電漿 顯示器之元件的糊組成物中，習知係將丙二醇二甲基醚 、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚 等之丙二醇二烷基醚當做溶劑所使用（專利文獻3、4、5) 〇 [先前技術文獻] [專利文獻] [專利文獻1]國際公開W02003/052003號公報 [專利文獻2]日本特開2010 — 135140號公報 [專利文獻3]曰本特開2007-167834號公報 [專利文獻4]日本特開2004-6191 1號公報 [專利文獻5]曰本特開2007-3 14376號公報 [非專利文獻] [非專利文獻1]國際化學物質簡潔評估文件N〇.41 乙一醇二曱基贼（Diethylene Glycol Dimethyl Ether) (2002) 【發明内容】 [發明所欲解決之課題] 得知丙二醇二烷基醚係具優越之揮發性，但尤其由 於丙二醇二甲基醚係親水性高且容易吸濕，若於形成太 陽能電池、有機薄膜電晶體、電子纸、或電漿顯示器之 几件圖案的糊組成物中當做溶劑使用時，將有使元件劣 201224073 化之虞，另一方面，丙二醇二丁基醚係親油性高且吸 性低’但由於糊組成物中所含有的乙基纖維素或丙烯 樹脂等之黏著劑樹脂的溶解性低，難以當做印刷用溶 使用" 因而’本發明之目的係在於提供一種黏著劑樹脂 之樹脂添加物之溶解性高且吸濕性低的太陽能電池、 機薄膜電晶體、電子紙、或電漿顯示器圖案印刷用溶 或〉容劑組成物。 本發明之其他目的係提供一種含有該太陽能電池 有機薄膜電晶體、電子紙、或電漿顯示器之圖案印刷 溶劑或溶劑組成物之太陽能電池、有機薄膜電晶體、 子紙、或電漿顯示器圖案形成用糊組成物。 另外’本發明之其他目的係在提供一種使用該太 能電池、有機薄膜電晶體、電子紙、或電漿顯示器圖 形成用糊組成物而進行圖案形成之圖案形成方法。 [解決課題之手段] 本發明人等係為了解決上述問題而鑽研探討之結 發現：丙二醇二烷基醚之一側末端烷基為曱基，且另 側末端烧基為直鏈狀或分枝鏈狀烧基之c3-5^基的化 物係具優異的樹脂添加物之溶解性、及吸濕性的均衡 若於形成構成太陽能電池、有機薄膜電晶體、電子紙 或電漿顯示器之元件圖案之際，將該化合物當做溶劑 用時，能夠藉印刷法而對進行元件圖案之形成發揮充 之黏著劑樹脂溶解性；且能夠藉吸濕而形成難以劣化 元件。本發明係基於此等之見解而使其完成者。 渴 酸 劑 等 有 劑 用 電 陽 案 果 合 > % 使 分 之 201224073 亦即，本發明係提供一種太陽能電池、有機薄膜電 晶體、電子紙、或電漿顯示器圖案印刷用溶劑或溶劑組 成物(以後，冑簡稱為「圖案印刷用溶劑或溶劑組成物」 之情形）’其係用於藉印刷法而形成構成太陽能電池、有 機薄膜電晶體（以後有稱為「有機TFT」之情形）、電子紙 、或電聚顯不器之元件圖案之際的溶劑或溶劑組成物； 其特徵為含有丙二醇二烷基醚之二個末端烷基之一側為 甲基’另一側為碳數3至5之直鏈狀或分枝鏈狀烷基的化 合物。 該印刷法較佳為由喷墨法、網板印刷法、凸版印刷 法、膠版印刷法、照相凹版印刷法、微接觸印刷法、奈 米印跡法所構成之群組中所選出的至少一種方法。 另外’本發明更提供一種至少含有該圖案印刷用溶 劑或溶劑組成物與黏著劑樹脂之太陽能電池、有機薄膜 電晶體、電子紙、或電漿顯示器圖案形成用糊組成物（ 以後’有簡稱為「圖案形成用糊組成物」之情形）。 該黏著劑樹脂較佳為纖維素系樹脂及/或丙烯酸系 樹脂。 另外’本發明更提供一種圖案形成方法，其係構成 太陽能電池、有機TFT、電子紙、或電漿顯示器之元件 的圖案形成方法；其特徵為具有：藉由利用印刷法將該 太陽能電池、有機TFT、電子紙、或電漿顯示器圖案形 成用糊組成物塗布於基板上而形成圖案層之步驟；與硬 化或燒製該圖案層之步驟。 [發明之效果] 201224073 由於本發明之圖案印刷用溶劑或溶劑組成物係含有 上述丙二醇二烷基醚之二個末端烷基之一側為甲基，另 一側為碳數3至5之直鏈狀或分枝鏈狀烷基的化合物，具 優越之黏著劑樹脂等之樹脂添加物的溶解性，另外吸濕 性極低。 因此，本發明之含有圖案印刷用溶劑或溶劑組成物 之圖案形成用糊組成物，即使對於大面積及/或可撓性之 基板，藉印刷法也能夠有效地均勻塗布，於構成太陽能 電池、有機TFT、電子紙、或電漿顯示器等之元件的製 中，旎夠咼精確度地形成微細之元件圖案。另外，由 於難吸濕，能夠抑制因濕氣所造成的元件之劣化。 【實施方式】 [用於實施發明之形態] [圖案印刷用溶劑或溶劑組成物] 有關本發明之圖案印刷用溶劑或溶劑組成物係用於 藉印刷法而形成構成太陽能電池、有機TFT、電子紙、 或電漿顯示器之元件圖案之際的溶劑或溶劑組成物；其 特徵為含有丙二醇二烷基醚之二個末端烷基之一側為曱 基’另一側為碳數3至5之直鏈狀或分枝鏈狀烷基的化合 物。 例如’該印刷法可舉例：喷墨法、網板印刷法、凸 版印刷法、膠版印刷法、照相凹版印刷法、微接觸印刷 法、奈米印跡法等。 在丙二醇二院基醚之末端烧基的碳數3至5之直鍵狀 或分枝鍵狀炫基，例如，可舉例：正丙基、正丁基、正 201224073 戍基等之直鏈狀烧基；異丙基、異丁基、二級丁基、三 級丁基、異戊基、二級戊基、三級戊基等之分枝鏈狀烷 基。於本發明中，其中較佳為碳數3至5的直鏈狀烷基， 尤其基於容易供應原料之觀點，較佳為正丙基、正丁基 、正戊基。 在本發明之丙二醇二烷基醚之二個末端烷基之一側 為曱基，另一側為碳數3至5之直鏈狀或分枝鏈狀烷基的 化合物，例如’可舉例：丙二醇甲基正丙基醚、丙二醇 甲基正丁基醚、丙二醇曱基正戊基醚等。此等可單獨地 使用’亦可混合二種以上而使用。 另外’有關本發明之圖案印刷用溶劑或溶劑組成物 較佳為採取親水性與親油性均衡者，例如含水率較佳為 3%以下（其中，更佳為15%以下）。若含水率超過上述範 圍時，將有使得使用有關本發明之圖案印刷用溶劑或溶 劑組成物所形成的元件變得容易劣化之傾向。 另外’有關本發明之圖案印刷用溶劑或溶劑組成物 較佳為乙基纖維素等之具優越之樹脂添加物的溶解性， 例如較佳為溶解5重量％以上乙基纖維素。若乙基纖維素 等之樹脂添加物的溶解量低於上述範圍時，將有黏度變 得過低且觸變性及印刷物之形狀安定性不足之傾向。 除了上述丙一醇二院基喊以外’本發明之圖案印刷 用溶劑或溶劑組成物係在不損害親水性或親油性之均衡 的範圍内’視需要亦可混合其他溶劑後使用。其他溶劑 的摻合比例能夠適當選擇。 其他溶劑能夠使用在印刷用途一般所用之溶劑，例 201224073 如，可舉例：己酸、辛酸等之羧酸類；異丙醇、1 -辛醇 、1-壬醇、苄醇等之醇類；乙二醇單甲基醚、乙二醇單 乙基醚、乙二醇單丙基醚、乙二醇單丁基醚等之乙二醇 單烷基醚類；乙二醇單曱基醚乙酸酯、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等之乙二醇單烷基醚乙酸酯 類；二乙二醇單曱基醚、二乙二醇單乙基醚、二乙二醇 單丙基醚、二乙二醇單丁基醚等之二乙二醇單烷基醚類 ;二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯 等之二乙二醇單烷基醚乙酸酯類；二乙二醇二曱基醚、 二乙二醇二乙基醚等之二乙二醇二烷基醚類；苄基乙基 醚、二己基醚、四氫呋喃等之其他醚類；丙二醇單甲基 醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丁基醚乙 酸酯等之丙二醇單烷基醚乙酸酯類；二丙二醇曱基醚乙 酸酯等之二丙二醇單烷基醚乙酸酯類；丙二醇丙基醚、 丙二醇丁基醚等之丙二醇單烷基醚類；二丙二醇甲基醚 、二丙二醇丙基醚、二丙二醇丁基醚等之二丙二醇單烷 基醚類；三丙二醇曱基醚、三丙二醇丁基醚等之三丙二 醇單烷基醚類；丙二醇二曱基醚、丙二醇二乙基醚等之 上述以外之丙二醇二烷基醚；二丙二醇曱基丙基醚、二 丙二醇甲基丁基醚、二丙二醇甲基戊基醚、二丙二醇二 甲基醚等之二丙二醇二烷基醚類；三丙二醇二曱基醚等 之三丙二醇二烷基醚類；丙二醇二乙酸酯、1，3 -丁二醇 二乙酸酯、1，6-己二醇二乙酸酯、1，4-丁二醇二乙酸酯等 之二乙酸酯類；環己醇乙酸酯、3 -曱氧基丁基乙酸酯、 -10- 201224073 乳酸乙基乙酸8旨、甘，，由3 其他乙酸醋類酸醋、乙酸二氫祐 酮基丙酮、環己_、異佛酮 甲=丁 ;2-經基丙酸甲S旨、_、3-庚_ 乙醯基乳酸酯、安自香土 @夂乙酯、乙酸苄 尿酸二乙S旨”丁内醋曰、草馱二乙醋、 經基-2-甲基丙酸乙酿、3;:乙歸醋、碳酸丙 酸乙醋、3-乙氧基丙酸甲：氣基丙酸甲醋、％ 基乙酸乙酯、羥基乙酸：3_乙氧基丙酸乙 3-甲基_3·甲氧丁基乙酸V::7:基T基丁 I甲氧丁基丙㈣旨、乙酸^^丁基乙酸雖 甲酸戊酯、乙酸戊酯、 日&酸丙酯、乙 丁自旨、丁酸乙酷、 、丁酸丁酯、丙_酸甲酯、 鲛乙酉曰 7硫7辦田内酮酸乙醋、丙_ 乙酿乙酸"曰、乙醯乙酸Μ 類；甲苯、二曱笨等 扠丞丁鲛乙 Ν，Ν-二甲基甲醯胺、Ν，Ν•二=頰；Ν-甲基。比 品醇、二氫蔥品醇、丙 ：醯胺等之醯 薄荷腦等之格烯類；礦 幹稼烯 c 1<Λ友竑頌'由精、石油輕油S-100、 -安四風$、松節油等之高沸點溶劑等。 [圖案形成用糊組成物3 d t 有關本發明之圓案形成用糊組成…特 含有上达圖案印刷用溶劑或溶劑組成物與黏著 黏著劑樹脂並未予以特別限定能夠使用 陽能電池、有機TFT、電子紙、或電毁顯示器 形成所使用的習用之樹脂，例如， J舉例：甲 品醋等之 基嗣、丙 等之酮類 酯、乙基 順丁烯一 烯酯、2-甲氧基丙 酯、乙氧 酸曱酯、 、3-甲基 酸丁酯、 丁酸丙醋 酸丙S旨、 酯等之酯 咯啶酮、 胺類；蔥 、萜烷、 石油輕油 徵為至少 劑樹脂。 在形成太 之元件之 基纖維素 •11- 201224073 、乙基纖維素、經基纖維素、甲基㈣纖維素等之纖維 素系樹脂；丙烯酸系樹脂、聚乙烯乙酸酯、聚乙烯醇等 之乙烯樹脂等。此等能夠單獨地或混合二種以上而使用 。於本發明中，其中基於塗布時之版剝離性佳且具優越 之觸變性及印刷物之形狀安定性之觀點，較佳為使用纖 維素系樹脂。 圖案形成用糊組成物中之上述圖案印刷用溶劑或溶 劑組成物之含量，例如為丄至”重量％左右，較佳為3至 75重量％左右《若圖案印刷用溶劑或溶劑組成物之含量 低於上述範圍時’將有圖案形成用糊組成物之黏度變得 過高且用於印刷用途變得困難之傾向。另一方面，若圖 案印刷用溶劑或溶劑組成物之含量超過上述範圍時，將 有乾燥費時、作業效率降低之傾向。 圖案形成用糊組成物中之黏著劑樹脂之含量，例如 為0.1至15重量％左右，較佳為⑴。重量％左右。若黏著 劑樹脂之含量低於上述範圍時，將有觸變性及印刷物之 形狀安定性不足之傾向；另—方面，若點著劑樹脂之含 量超過上述範圍時’將有點度變得過高而 用變得困難之傾向。 I W π使 有關本發明之圖案形成用糊組成物亦可為 機能、絕緣機能、半導體機能令之任一種，除上述之 ’也可以摻合其他添加物。其他添加物，例如，；舉例 :金：氧化物、介電體材料等之金屬材料；有機TFT材 枓、導電性兩分子材料、離子導體 Μ工道触^ . 有機•無機混雜 離子導體材料、有機或無機顏料、分散劑、消泡劑、安 -12- 201224073 疋劑、抗氧化劑、硬化加速劑、增感劑、填充劑、紫外 線吸收劑、抗凝聚劑等。只要其他添加物之摻合量為不 損害本發明之效果的範圍内即可’例如整體圖案形成用 糊組成物之〇.1至99重量％左右。 有關本發明之圖案形成用糊組成物係例如藉由使用 混合撥拌機等之攪拌裝置而摻合上述圖案印刷用溶劑或 溶劑組成物、黏著劑樹脂、及視需要之其他添加物後充 分混授、均勻分散而能夠調製。 由於有關本發明之圖案形成用糊組成物係藉由利用 印刷法塗布於基材等之上而能夠形成圖案，故能夠容易 而有效且廉價地在大面積且可撓性的基板表面上形成元 件。 [圖案形成方法] 有關本發明之圖案形成方法係構成太陽能電池、有 機TFT、電子紙、或電漿顯示器之元件圖案形成方法， 其特徵為具有藉由利用印刷法，將上述圖案形成用糊組 成物塗布於基板上而形成圖案層之步驟（圖案印刷步驟） :及使該圖案層硬化或燒製之步驟（圖案硬化或燒製步驟 )0 在圖案印刷步驟中之印刷法，可舉例：由喷墨法、 網板印刷法、凸版印刷法、膠版印刷法、照相凹版印刷 法、微接觸印刷法、奈米印跡法所構成之群組中所選出 的至少一種方法。 利用上述印刷法所形成的圖案層係藉由進行乾燥， 其後進行加熱處理及/或光照射而能夠使其硬化。另外乾 -13- 201224073 燥後，亦可不使其硬化而進行燒製。乾燥方法，例如， 可舉例：在8G至20(TC左右之溫度，例如加熱〇」至3小時 左右之方法等。進行加熱處理之情形，其溫度係按照供 給反應之成分或觸媒之種類等而能夠適當調整，例如為 50至200°C左右。另外，加熱時間係例如〇」至3小時左右 。進行光照射之情形，其光源能夠使用例如水銀燈、氙 燈、碳弧燈、金屬鹵化物燈、陽光、電子線、雷射光等 。光照射時間例如為〇.5至30分鐘左右。進行燒製之情形 ，燒製溫度例如為200至丨50(rc左右。另外，燒製時間例 如為0.1至5小時左右。 利用上述方法所獲得的圖案層厚度係按照用途而能 夠適當調整，例如為數11111至2〇〇 μπι左右。 I成圖案層之基板較佳為具有耐熱性及对溶劑性， ^如’可舉例：聚對苯：甲酸乙二醋、聚萘二甲酸乙二 -曰聚’曰》乙烯、聚丙烯、聚苯乙烯、聚醯胺、聚醯 亞胺、聚乙烯醇、聚乙烯縮丁醛、聚氣乙烯、聚偏二氣 稀聚氟乙稀等之含氟樹脂；聚碳酸酯、丙稀酸樹脂 、甲基丙烯酸樹脂、環烯烴共聚物、導電性聚合物 '耐 网纖，准素、玻璃、1Τ0等。基板厚度例如為0.1至50 mm 左右。 般而S ，太陽能電池（尤其，有機太陽能電池）係 ^有包含n型半導體層與P型半導體層之光電轉換層被光 入侧電極（主線電極及指狀電極所構成）與背面側電極 所夾住之構造。 太陽能電池能夠利用例如下列方法而製造。若根據 -14- 201224073 有關本發明之圖案形成方法，能夠精 太陽能電池之元件。 又佳地形成構成 1 .藉印刷法而形成將B(硼原子卷 的p型半導體。 *做雜質所添加 2.在所獲得的p型半導體表面實 之後，藉印刷法而積層將P(碳原子）等當做^凹凸）加工 η型半導體。 雜質所添加的 3 :在ρ型半導體表面形成氮化矽、 射膜》 氧化鈦等之抗反 4 :藉印刷法而在η型半導體表 狀電極（光射入側電極）。 $成主線電極與指 -般而言’有機TFT係由電極層(間極層、源極層、 没極層）及有機半導體層所構成。若根據有關本發明之圖 案形成方法的話，能夠精確度佳地形成構成有機Μ之 元件。 一般而言’電子紙係具有顯示層與控制此顯示層之 驅動層被基板所夾住之構造。而且’藉由驅動層採用上 述有機TFT而能夠實現可撓性的顯示器。 -般而言，電漿顯示器係具有在狹窄的間隔而使在 表面已形成電極的前面玻璃基板、與已形成電極及螢光 體層之背面電極基板對向後封入稀有氣體之構造。 電漿顯示器能夠利用例如下列方法 有關本發明之圖案形成方法，能夠精確度佳地形成；： 電漿顯示器之元件。 1 :在前面玻璃基板上形成顯示電極、主線電極。 -15- 201224073 2·進一步形成介電體層、MgO層。 、3:在背面玻璃基板上形成資料電極，形成介電體層 ’進一步形成阻隔壁（barrier rib)、螢光體層。 4:在貼合前面玻璃基板與背面破璃基板、排氣、封 入放電氣體之後，構裝印刷基板。 由於有關本發明之圖案形成方法係利用印刷法，能 夠以非接觸之狀態而對基板形成圖案，故能夠在大面積 及/或可撓性基板也容易地進行圖案形成。因此，尤其在 構成太陽能電池、有機TFT、電子紙、或電漿顯示器等 之兀件的製造中’能夠高精確度地形成微細之元件圖案 。另外’不經由作成遮罩等之複雜的步驟而能夠直接地 描繪’無須使用微細加工技術…，能夠在常溫常麼 環境下製造。因此，能夠大幅簡化製程、簡化設備、削 減製造成本。 [實施例] 以下’藉實施例而更具體說明本發明但本發明並 不受此等之實施例所限定。 實施例1 將丙·一醇曱基正丁某触『亦σ交「1^ J 丞醚（商 口口名「ΡΜΝΒ」、Daicel 化學工業（股）製，以後右摇i Γΐ)λ/ΓΧΤΰ 傻有稱為「ΡΜΝΒ」之情形）20 g、蒸 館水2 0 g倒入5 0 m 1燒概φ，撼妯奶】Λ、 從瓶甲，攪拌約1〇分鐘後’靜置1〇分 鐘，進行有機相之水公泪I丨金，A 〇 < 八刀幻疋在2 5 c環境下之水分濃度 為 0.7 %。 將該PMNB各2〇〇〇g分別置入4個5〇^燒瓶中分別 追加 1.05 g(5%溶液）、i 28 g(6%溶液）、i 5i 溶液） -16- 201224073 、1.74 g(8%溶液）之商品名「ETH〇CEL」（註冊商標）（乙 基纖維素、DOW(股）製）。之後，在65艺攪拌後靜置自 然冷卻至25°C止之後，以目視確認乙基纖維素之溶解性 ，依照下列基準進行評估。 評估基準 乙基纖維素完全溶解：〇 乙基纖維素一部分不溶、或完全不溶：X 實施例2 將丙二醇甲基正丙基醚（商品名「p]VINp」、Daicel 化學工業（股）製’以後有稱為「PMNP」之情形）2〇g、蒸 餾水20 g倒入50 ml燒瓶中，攪拌約10分鐘後，靜置1〇分 鐘’進行有機相之水分測定，在251環境下之水分濃度 為 1.0%。 除了使用該PMNP以取代PMNB以外，進行與實施例1 同樣方式而評估乙基纖維素之溶解性。 比較例1 將丙二醇二曱基醚（商品名「HISOLVEMMPOM」、 東邦化學工業（股）製，以後有稱為「MMPOM」之情形）20 g、蒸餾水2 0 g倒入5 0 m 1燒瓶中，攪拌約1 〇分鐘後，靜 置10分鐘，進行有機相之水分測定，在25°C環境下之水 分濃度為7.3 %。 除了使用該MMPOM以取代PMNB以外，進行與實施 例1同樣方式而評估乙基纖維素之溶解性。 比較例2 將依照「第5版實驗科學講座1 4」（丸善股份有限公 -17- 201224073 司出版、P239-2 41)記載之方法所合成的丙二醇二丁基醚 (以後有稱為「PDB」之情形）20 g、蒸餾水20 g倒入50 ml 燒瓶中，攪拌約1 〇分鐘後，靜置1 〇分鐘，進行有機相之 水分測定，在25 °C環境下之水分濃度為0.1%。 除了使用該PDB以取代PMNB以外，進行與實施例1 同樣方式而評估乙基纖維素之溶解性。 將上述結果彙整而顯示於下表中。 [表1]201224073 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a solvent or a geo-coolant composition which is difficult and has excellent resin solubility and is used by me. ^ ^ 所 [Prior Art] The patterning of electronic components such as a wiring board or a display is conventionally formed by a so-called photolithography method. The photolithography method is a method in which a paste group is applied onto a substrate, and a fine pattern is exposed and baked, and an unnecessary portion is removed by etching to form a pattern. The problem of 蚀 而 而 S S S S S S S S S S S S S S S S S 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于In addition, it is limited by the device 3: it is difficult to form a pattern for a large-area substrate. Therefore, in recent years, the pattern forming method does not require a large skirt and the material is used efficiently. It is also easy to correspond to the JI ink of the large-area substrate. Method, screen printing method, letterpress printing method, offset printing method, Zhaozhi 4 ^ ",, gravure printing method, micro-contact printing method", nano-printing method, etc., can be used for printing paste. The solvent used in the composition is an example of a propylene glycol ether solvent such as an ethyl scaly or a di-n-butyl bond, which is used as a solvent. However, it is inconvenient to use because the glycol ether solvent is ecologically toxic. The problem (Non-Patent Document 1). On the other hand, for the propylene glycol ether solvent, the conventional form is a solvent; the alcohol dipropyl ether alcohol diethylene glycol didecyl ether or diethylene glycol A paste composition of a component such as a propylene ether diethylene ether or a dipropylene glycol di-caprol 201224073 cation battery is used as a solvent (Patent Document 1), and in Patent Document 2, a propylene glycol secondary burning riddle is used. Among It has been described that propylene glycol dibutyl ketone which is strongly lipophilic is used. In addition, in the paste composition for forming an element constituting an organic thin film transistor, an electronic paper, and a plasma display, propylene glycol dimethyl ether and propylene glycol diethyl phthalate are conventionally known. A propylene glycol dialkyl ether such as a hydroxy ether, a propylene glycol dipropyl ether or a propylene glycol dibutyl ether is used as a solvent (Patent Documents 3, 4, and 5) 〇 [Prior Art Document] [Patent Document] [Patent Document 1] International Japanese Laid-Open Patent Publication No. 2007-167834 (Patent Document 4) Japanese Patent Application Publication No. 2004-6191 No. 5] Unexamined Patent Publication No. 2007-3 14376 [Non-Patent Document] [Non-Patent Document 1] Concise Evaluation Document for International Chemical Substances N〇.41 Diethylene Glycol Dimethyl Ether (2002) [Invention Contents] [Problems to be Solved by the Invention] It is known that propylene glycol dialkyl ether has superior volatility, but in particular, propylene glycol dimethyl ether is highly hydrophilic and easily absorbs moisture, and is formed into a solar cell or an organic thin film. crystal When the solvent composition of several patterns of electronic paper or plasma display is used as a solvent, there will be a problem that the component is inferior to 201224073. On the other hand, propylene glycol dibutyl ether is highly lipophilic and low in suction. However, since the solubility of the adhesive resin such as ethyl cellulose or acryl resin contained in the paste composition is low, it is difficult to use it as a printing solution. Thus, the object of the present invention is to provide a resin addition of an adhesive resin. A solar cell, an organic thin film transistor, an electronic paper, or a solvent or a capacitor composition for pattern printing of a plasma display having high solubility and low hygroscopicity. Another object of the present invention is to provide a solar cell, an organic thin film transistor, a sub-paper, or a plasma display pattern comprising the pattern printing solvent or solvent composition of the solar cell organic thin film transistor, electronic paper, or plasma display. Use a paste composition. Further, another object of the present invention is to provide a pattern forming method for patterning using the solar cell, the organic thin film transistor, the electronic paper, or the paste composition for forming a plasma display. [Means for Solving the Problem] The present inventors have found that in order to solve the above problems, it is found that one terminal alkyl group of propylene glycol dialkyl ether is a mercapto group, and the other terminal alkyl group is linear or branched. The c3-5^ group of the chain-shaped alkyl group has an excellent solubility of the resin additive and a balance of hygroscopicity in forming a component pattern constituting a solar cell, an organic thin film transistor, an electronic paper or a plasma display. In this case, when the compound is used as a solvent, it is possible to impart an adhesive resin solubility to the formation of the element pattern by a printing method, and it is possible to form a device which is difficult to deteriorate by moisture absorption. The present invention has been made based on such findings. The use of a reagent such as a thirsty acid agent and the like is as follows: <%, 201224073, that is, the present invention provides a solvent or solvent composition for printing a solar cell, an organic thin film transistor, an electronic paper, or a plasma display pattern. (hereinafter, hereinafter abbreviated as "the solvent or solvent composition for pattern printing") is used to form a solar cell or an organic thin film transistor (hereinafter referred to as "organic TFT" by a printing method), A solvent or solvent composition of an electronic paper or a component pattern of an electropolymer; characterized in that one side of the two terminal alkyl groups containing a propylene glycol dialkyl ether is a methyl group and the other side is a carbon number of 3 A compound of a linear or branched chain alkyl group of up to 5. The printing method is preferably at least one selected from the group consisting of an inkjet method, a screen printing method, a letterpress printing method, an offset printing method, a gravure printing method, a microcontact printing method, and a nanoprinting method. . Further, the present invention further provides a paste composition (hereinafter referred to as "a solar cell, an organic thin film transistor, an electronic paper, or a plasma display pattern" containing at least the solvent or solvent composition for pattern printing and an adhesive resin. "The case of the paste composition for pattern formation"). The adhesive resin is preferably a cellulose resin and/or an acrylic resin. In addition, the present invention further provides a pattern forming method, which is a pattern forming method for forming an element of a solar cell, an organic TFT, an electronic paper, or a plasma display; and is characterized in that: the solar cell is organically produced by using a printing method. a step of forming a pattern layer by applying a paste composition for forming a TFT, an electronic paper, or a plasma display pattern onto a substrate; and a step of hardening or firing the pattern layer. [Effects of the Invention] 201224073 The solvent or solvent composition for pattern printing of the present invention contains one of the two terminal alkyl groups of the propylene glycol dialkyl ether as a methyl group, and the other side has a carbon number of 3 to 5. The compound of a chain or branched chain alkyl group has a solubility of a resin additive such as a superior adhesive resin, and has extremely low hygroscopicity. Therefore, the paste composition for pattern formation containing the solvent or solvent composition for pattern printing of the present invention can be uniformly applied uniformly by a printing method for a large-area and/or flexible substrate, thereby constituting a solar cell. In the manufacture of components such as organic TFTs, electronic papers, or plasma displays, fine element patterns are formed with precision. Further, since it is difficult to absorb moisture, deterioration of components due to moisture can be suppressed. [Embodiment] [Forms for carrying out the invention] [Solvent or solvent composition for pattern printing] The solvent or solvent composition for pattern printing of the present invention is used to form a solar cell, an organic TFT, and an electron by a printing method. a solvent or solvent composition of a paper, or a component pattern of a plasma display; characterized in that one side of the two terminal alkyl groups containing propylene glycol dialkyl ether is a mercapto group and the other side is a carbon number of 3 to 5. A compound of a linear or branched chain alkyl group. For example, the printing method can be exemplified by an inkjet method, a screen printing method, a letterpress printing method, an offset printing method, a gravure printing method, a microcontact printing method, a nanoimprint method, or the like. The direct bond or branched bond group having a carbon number of 3 to 5 at the terminal of the propylene glycol bis-terminated ether, for example, a straight chain such as n-propyl group, n-butyl group, or 201224073 fluorenyl group a branched alkyl group such as isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl, secondary pentyl or tertiary pentyl. In the present invention, a linear alkyl group having 3 to 5 carbon atoms is preferred, and n-propyl, n-butyl and n-pentyl groups are preferred from the viewpoint of easily supplying a raw material. In the propylene glycol dialkyl ether of the present invention, one of the two terminal alkyl groups is a fluorenyl group, and the other side is a compound having a linear or branched chain alkyl group having 3 to 5 carbon atoms, for example, ' Propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, propylene glycol decyl n-pentyl ether, and the like. These may be used singly or in combination of two or more. Further, the solvent or solvent composition for pattern printing of the present invention preferably has a balance of hydrophilicity and lipophilicity, and for example, the water content is preferably 3% or less (more preferably 15% or less). When the water content exceeds the above range, there is a tendency that the element formed by using the solvent or the solvent composition for pattern printing of the present invention is easily deteriorated. Further, the solvent or solvent composition for pattern printing of the present invention is preferably a solubility of a superior resin additive such as ethyl cellulose. For example, it is preferred to dissolve 5% by weight or more of ethyl cellulose. When the amount of the resin additive such as ethyl cellulose is less than the above range, the viscosity tends to be too low, and the thixotropy and the shape stability of the printed matter tend to be insufficient. The solvent or solvent composition for pattern printing of the present invention is used in the range of not impairing the balance of hydrophilicity or lipophilicity, and may be used by mixing other solvents as needed. The blending ratio of other solvents can be appropriately selected. Other solvents can be used in the solvent generally used for printing purposes. For example, 201224073 can be exemplified by carboxylic acids such as caproic acid and caprylic acid; alcohols such as isopropanol, 1-octanol, 1-nonanol and benzyl alcohol; Ethylene glycol monoalkyl ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; ethylene glycol monodecyl ether acetic acid Ethylene glycol such as ester, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate Monoalkyl ether acetates; diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, etc. Alkyl ethers; diethylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; diethylene glycol didecyl ether Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether; other ethers such as benzyl ethyl ether, dihexyl ether, tetrahydrofuran; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ethyl acetate, a propylene glycol monoalkyl ether acetate such as diol monobutyl ether acetate; a dipropylene glycol monoalkyl ether acetate such as dipropylene glycol decyl ether acetate; propylene glycol propyl ether, propylene glycol butyl ether, etc. a propylene glycol monoalkyl ether; a dipropylene glycol monoalkyl ether such as dipropylene glycol methyl ether, dipropylene glycol propyl ether or dipropylene glycol butyl ether; a tripropylene glycol such as tripropylene glycol decyl ether or tripropylene glycol butyl ether; a monoalkyl ether; a propylene glycol dialkyl ether other than the above, such as propylene glycol dimercapto ether or propylene glycol diethyl ether; dipropylene glycol decyl propyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol methyl amyl Dipropylene glycol dialkyl ethers such as ether and dipropylene glycol dimethyl ether; tripropylene glycol dialkyl ethers such as tripropylene glycol didecyl ether; propylene glycol diacetate, 1,3-butanediol diacetic acid Diacetate such as ester, 1,6-hexanediol diacetate or 1,4-butanediol diacetate; cyclohexanol acetate, 3-methoxybutyl acetate, -10- 201224073 Ethyl lactate 8 is intended to be sweet, and is made up of 3 other acetic acid vinegars, dihydrogen acetate Ketoacetone, cyclohexanyl, isophorone A = dibutyl; 2-pyridyl propionate, S, _, 3-gly-ethlyl lactate, Anzixiang@夂ethyl, benzyl urate乙乙 S的"丁内醋, 驮 驮 乙 、 经, 经 -2- 2-methyl propionic acid, brewing, 3;: 乙 vinegar, ethyl acetonate, 3-ethoxypropionate: Methyl methacrylate, ethyl acetate, glycolic acid: 3-ethoxypropionic acid, ethyl 3-methyl-3, methoxybutylacetic acid V::7:yl T-butyl methoxybutyl Propylene (IV), acetic acid ^ butyl acetic acid, although amyl formate, amyl acetate, daily & propyl ester, ethyl butyrate, butyrate, butyl butyrate, methyl acrylate, methyl hydrazine曰7 77 办 内 酮 酮 乙 、 、 、 、 、 & & & & 乙酸 乙酸 乙酸 乙酸 乙酸 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Ν•2=cheek; Ν-methyl. Compared with terpineol, dihydro onionol, c: guanamine, etc., menthol, etc.; ore cumene c 1<Λ友竑颂' from fine, petroleum light oil S-100, - Ansi High-boiling solvent such as wind $, turpentine, etc. [Pattern-forming paste composition 3 dt] The paste-forming paste composition of the present invention is particularly limited to a solvent or solvent composition for pattern printing, and an adhesive resin is not particularly limited. A solar battery or an organic TFT can be used. , e-paper, or electro-destruction display to form a conventional resin used, for example, J: a base vinegar, etc., ketone esters such as propyl, ethyl methacrylate, 2-methoxy propyl Ester, butyl ethoxylate, butyl 3-methyl acrylate, propionic acid propionate, ester ketone, amines, etc.; onion, decane, petroleum light oil is at least a resin. Cellulose resin such as cellulose, 11-201224073, ethyl cellulose, cellulose based cellulose, methyl (tetra) cellulose, etc.; acrylic resin, polyvinyl acetate, polyvinyl alcohol, etc. Vinyl resin and the like. These can be used singly or in combination of two or more. In the present invention, it is preferred to use a cellulose-based resin from the viewpoint of excellent peelability at the time of coating and excellent thixotropy and shape stability of a printed matter. The content of the solvent or solvent composition for pattern printing in the paste composition for pattern formation is, for example, about 重量 to about 5% by weight, preferably about 3 to 75% by weight, if the content of the solvent or solvent composition for pattern printing is When the content is less than the above range, the viscosity of the paste composition for pattern formation is too high and it is difficult to be used for printing. On the other hand, when the content of the solvent or solvent composition for pattern printing exceeds the above range The content of the adhesive resin in the paste for pattern formation is, for example, about 0.1 to 15% by weight, preferably about (1) by weight. If the content of the adhesive resin is used, the drying time is lowered. When the content is less than the above range, the thixotropy and the shape stability of the printed matter tend to be insufficient. On the other hand, when the content of the dot resin exceeds the above range, the tendency to become too high is difficult. The IW π composition of the paste for pattern formation according to the present invention may be any of functions, insulation functions, and semiconductor functions, and may be blended in addition to the above. Other additives, other additives, for example; examples: gold: metal materials such as oxides and dielectric materials; organic TFT materials, conductive two-molecule materials, ionic conductors, and the like. Ionic conductor materials, organic or inorganic pigments, dispersants, defoamers, An-12-201224073 tinctures, antioxidants, hardening accelerators, sensitizers, fillers, UV absorbers, anti-agglomerants, etc. The blending amount of the material is not less than the range of the effect of the present invention, for example, about 1 to 99% by weight of the paste composition for the overall pattern formation. The paste composition for pattern formation of the present invention is, for example, The solvent or solvent composition for pattern printing, the adhesive resin, and other additives as needed may be blended by using a stirring device such as a mixing machine, and then sufficiently mixed and uniformly dispersed to prepare the pattern. Since the paste composition for formation can be formed by patterning on a substrate or the like by a printing method, it is possible to easily and efficiently and inexpensively have a large area and flexibility. [Forming method] The pattern forming method of the present invention constitutes a component pattern forming method of a solar cell, an organic TFT, an electronic paper, or a plasma display, characterized in that it has a printing method. a step of applying the pattern forming paste composition onto a substrate to form a pattern layer (pattern printing step): and a step of hardening or firing the pattern layer (pattern hardening or firing step) 0 in the pattern printing step The printing method may, for example, be at least one selected from the group consisting of an inkjet method, a screen printing method, a letterpress printing method, an offset printing method, a gravure printing method, a microcontact printing method, and a nanoprinting method. The pattern layer formed by the above printing method can be dried by heating, and then heat-treated and/or irradiated with light. Further, after dry--13-201224073, it can be fired without being cured. . The drying method may, for example, be a method of from 8 G to 20 (temperature of about TC, for example, heating enthalpy) to about 3 hours, etc. In the case of heat treatment, the temperature is based on the kind of the component or the catalyst to be supplied to the reaction. Further, it can be appropriately adjusted, for example, to about 50 to 200 ° C. The heating time is, for example, about 3 to about 3 hours. In the case of light irradiation, the light source can use, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, or a metal halide lamp. , sunlight, electron beam, laser light, etc. The light irradiation time is, for example, about 5 to 30 minutes. In the case of firing, the firing temperature is, for example, about 200 to 丨50 (rc). In addition, the firing time is, for example, 0.1. The thickness of the pattern layer obtained by the above method can be appropriately adjusted according to the use, for example, about 11111 to 2 〇〇μπι. The substrate of the I-patterned layer is preferably heat-resistant and solvent-resistant, ^ For example, 'polyphenylene: formic acid ethyl vinegar, polyethylene naphthalate, bismuth-poly" 乙烯 ethylene, polypropylene, polystyrene, polyamine, polyimine, polyvinyl alcohol, poly Fluorine resin such as vinyl butyral, polystyrene, polyvinylidene fluoride, etc.; polycarbonate, acrylic resin, methacrylic resin, cyclic olefin copolymer, conductive polymer Fiber, quasi-prime, glass, 1 Τ 0, etc. The thickness of the substrate is, for example, about 0.1 to 50 mm. Generally, a solar cell (especially, an organic solar cell) has a photoelectric conversion layer including an n-type semiconductor layer and a P-type semiconductor layer. A structure in which the light-input side electrode (which is composed of the main line electrode and the finger electrode) and the back side electrode are sandwiched. The solar cell can be manufactured by, for example, the following method. According to the pattern forming method of the present invention according to -14 to 201224073, A component of a fine solar cell. A composition is formed. 1. A B-type semiconductor is formed by a printing method. * Adding impurities as an impurity 2. After the surface of the obtained p-type semiconductor is solidified, the printing method is used. On the other hand, P (carbon atoms) and the like are processed as n-type semiconductors. The addition of impurities 3: formation of tantalum nitride on the surface of the p-type semiconductor, film "TiO 2 and other anti-reverse 4: by printing In the case of an n-type semiconductor surface electrode (light incident side electrode), the main electrode and the finger are generally referred to as an organic electrode layer (electrode layer, source layer, and electrode layer) and an organic semiconductor layer. According to the pattern forming method of the present invention, an element constituting the organic germanium can be formed with high precision. Generally, the electronic paper has a display layer and a driving layer for controlling the display layer is sandwiched by the substrate. And a display capable of realizing flexibility by using the above-described organic TFT by the driving layer. - Generally, the plasma display has a front glass substrate which has been formed on the surface at a narrow interval, and has been formed. The electrode and the back electrode substrate of the phosphor layer have a structure in which a rare gas is sealed backward. The plasma display can be formed with a pattern forming method according to the present invention by, for example, the following method: It can be accurately formed; 1 : A display electrode and a main line electrode were formed on the front glass substrate. -15- 201224073 2. Further forming a dielectric layer and a MgO layer. 3: Forming a data electrode on the back glass substrate to form a dielectric layer' further forming a barrier rib and a phosphor layer. 4: After bonding the front glass substrate and the back glass substrate, exhausting, and sealing the discharge gas, the printed circuit board is mounted. According to the pattern forming method of the present invention, the substrate can be patterned in a non-contact state by the printing method, so that pattern formation can be easily performed on a large-area and/or flexible substrate. Therefore, in particular, in the manufacture of a member constituting a solar cell, an organic TFT, an electronic paper, or a plasma display, a fine element pattern can be formed with high precision. In addition, it can be directly drawn without complicated steps such as making a mask. It is possible to manufacture in a normal temperature environment without using a microfabrication technique. Therefore, the process can be greatly simplified, the equipment can be simplified, and the manufacturing cost can be reduced. [Examples] The present invention is more specifically described by the following examples, but the present invention is not limited by the examples. Example 1 The propyl ketone ketone group was touched by "Yi 交 交" 1^ J 丞 ether (Shangkou mouth name "ΡΜΝΒ", Daicel Chemical Industry Co., Ltd., then right i Γΐ) λ / ΓΧΤΰ Stupid is called "ΡΜΝΒ") 20 g, steamed water 20 g poured into 5 0 m 1 burning φ, 撼妯 milk Λ, from the bottle, stirring for about 1 〇 after 'stay 1 〇 Minutes, the organic phase of the water tears I 丨 gold, A 〇 < eight knives illusion in the 2 5 c environment, the water concentration is 0.7%. 2 〇〇〇g of each PMNB was placed in four 5 〇 flasks, respectively, adding 1.05 g (5% solution), i 28 g (6% solution), i 5i solution) -16-201224073, 1.74 g ( The trade name "ETH〇CEL" (registered trademark) of 8% solution) (ethyl cellulose, manufactured by DOW Co., Ltd.). Thereafter, after stirring at 65 °, the mixture was allowed to cool to 25 ° C, and the solubility of ethyl cellulose was visually confirmed and evaluated according to the following criteria. Evaluation of the standard ethyl cellulose is completely dissolved: 〇ethyl cellulose is partially insoluble or completely insoluble: X Example 2 propylene glycol methyl n-propyl ether (trade name "p] VINp", manufactured by Daicel Chemical Industry Co., Ltd. In the future, there is a case called "PMNP". 2〇g, 20 g of distilled water is poured into a 50 ml flask, stirred for about 10 minutes, and then allowed to stand for 1 〇 minutes. The moisture of the organic phase is measured, and the water concentration in the 251 environment is measured. It is 1.0%. The solubility of ethyl cellulose was evaluated in the same manner as in Example 1 except that the PMNP was used instead of PMNB. Comparative Example 1 20 g of propylene glycol dimercapto ether (trade name "HISOLVEMMPOM", manufactured by Toho Chemical Co., Ltd., and later referred to as "MMPOM") and 20 g of distilled water were poured into a 50 ml flask. After stirring for about 1 minute, the mixture was allowed to stand for 10 minutes, and the moisture of the organic phase was measured, and the water concentration at 25 ° C was 7.3%. The solubility of ethyl cellulose was evaluated in the same manner as in Example 1 except that this MMPOM was used instead of PMNB. Comparative Example 2 Propylene glycol dibutyl ether synthesized according to the method described in "The 5th Edition of Experimental Science Lecture 1 4" (Maruzen Co., Ltd., pp. -17-201224073, P239-2 41) (hereinafter referred to as "PDB" In the case of 20 g, 20 g of distilled water was poured into a 50 ml flask, and the mixture was stirred for about 1 〇, and then allowed to stand for 1 〇 minutes to measure the moisture of the organic phase, and the water concentration at 25 ° C was 0.1%. The solubility of ethyl cellulose was evaluated in the same manner as in Example 1 except that the PDB was used instead of PMNB. The above results are summarized and shown in the table below. [Table 1]
丙二醇 二烧基醚 含水率 (%) 乙基纖維素溶解性 5% 6% 7% 8% 實施例1 PMNB 0.7 〇 〇 〇 〇 實施例2 PMNP 1.0 〇 〇 〇 〇 比較例1 MMPOM 7.3 〇. 〇 〇 〇 比較例2 PDB 0.1 X X X X 【圖式簡單說明】 無0 【主要元件符號說明】 無0 1：： -18-Propylene glycol dialkyl ether water content (%) Ethyl cellulose solubility 5% 6% 7% 8% Example 1 PMNB 0.7 〇〇〇〇 Example 2 PMNP 1.0 〇〇〇〇 Comparative Example 1 MMPOM 7.3 〇. 〇 〇〇Comparative example 2 PDB 0.1 XXXX [Simple description of the diagram] No 0 [Description of main component symbols] None 0 1:: -18-