200938598 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種ITO(摻錫氧化銦）墨水。 【先前技術】 於玻璃基板上形成透明導電膜之方法已知有減鑛法。該 方法中有：對ITO歡之表面施加磁場而使電漿穩定化之磁 控濺鍍（magnetron sputtering)法，或者將反應性氣體供給 至基板附近而控制成膜成分之反應性濺鍍法等。於賤錢法 中’由於真空管路為必要者’因此設備投資額或維持成本 變高。又，自作為原料的ITO靶至最終可作為透明導電膜 使用的ITO之比例約為4〜6%左右，良率明顯偏低因而經濟 性欠佳。進而’為了藉由濺鍍法形成透明導電性電路，必 不可少的是光阻劑塗布步驟、蝕刻步驟、清洗步驟等，自 該等步驟排出之蝕刻液等產業廢棄物之處理亦必不可少， 因此不僅製造成本増大，而且在環境方面亦成問題。 濺鍍法以外的透明導電膜之形成技術已知有例如使用透 明導電性高分子之技術。但是，透明導電性高分子雖然透 明性高，但是電阻率為約1〇2〜約1〇3左右，電阻稱不上充分 低。 透明導電膜之另外的形成技術亦已知有如專利文獻丨及2 所記載，將ITO粒子製成漿料或墨水狀組合物，藉由旋塗 等塗布法使其形成透明導電膜之技術。又，本申請人以前 提出有利用喷墨法代替旋塗法由含有IT〇粒子之墨水形成 透明導電膜之技術（參照專利文獻3)。但是，使透明導電膜 136688.doc 200938598 之透明性與低電阻並存的要求進一步提高。200938598 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to an ITO (tin-doped indium oxide) ink. [Prior Art] A method of forming a transparent conductive film on a glass substrate is known as a method of reducing ore. In this method, a magnetron sputtering method in which a magnetic field is applied to the surface of the ITO layer to stabilize the plasma, or a reactive sputtering method in which a reactive gas is supplied to the vicinity of the substrate to control the film formation component, or the like is used. . In the money method, 'the vacuum line is necessary', so the equipment investment or maintenance cost becomes higher. Further, the ratio of the ITO target as the raw material to the ITO which can be finally used as the transparent conductive film is about 4 to 6%, and the yield is remarkably low, so that the economy is unsatisfactory. Furthermore, in order to form a transparent conductive circuit by a sputtering method, it is indispensable to apply a photoresist coating step, an etching step, a cleaning step, etc., and it is also necessary to treat industrial waste such as an etching liquid discharged from these steps. Therefore, not only is the manufacturing cost large, but it is also a problem in terms of the environment. A technique of forming a transparent conductive film other than the sputtering method is known, for example, using a transparent conductive polymer. However, although the transparent conductive polymer has high transparency, the specific resistance is about 1 〇 2 to about 1 〇 3 , and the electric resistance is not sufficiently low. Further, as another technique for forming a transparent conductive film, there is known a technique in which an ITO particle is formed into a slurry or an ink composition as described in Patent Documents 2 and 2, and a transparent conductive film is formed by a coating method such as spin coating. Further, the present applicant has previously proposed a technique of forming a transparent conductive film from an ink containing IT cerium particles by an inkjet method instead of a spin coating method (see Patent Document 3). However, the requirement for the transparency of the transparent conductive film 136688.doc 200938598 to coexist with low resistance is further enhanced.
專利文獻 1 : JP6-232586APatent Document 1: JP6-232586A
專利文獻 2 : US5,318,724A 專利文獻 3 : JP2006-152203A 【發明内容】 因此，本發明之目的在於提供一種各種性能較上述先前 ’技術進一步提昇之ITO墨水。 本發明提供一種ITO墨水，其特徵在於：其係於分散介 〇 質中分散有1το粒子而成者，並含有鈦偶合劑、及具有吟 〇坐琳基且可三維交聯之丙稀酸系樹脂。 又’本發明提供一種導電膜之製造方法，其特徵在於： 其係使用ITO墨水製造導電膜者，其中形成該IT〇墨水之塗 膜，並於100~350ec下煅燒該塗膜。 【實施方式】 以下’基於較好的實施形態對本發明加以說明。本發明 ❹之墨水係於分散介質中分散有IT〇粒子而成者。墨水中含 有鈦偶合劑、及具有特定結構之丙烯酸系樹脂。 作為ΙΤ0(摻錫氧化銦）粉，可無特別限制地使用與在該 技術領域中通常所使用者相同者。ΙΤΟ粒子例如可藉由以 下方式獲得：於含有銦鹽及錫鹽之酸性水溶液中添加鹼性 水溶液而使共沈氫氧化物析出，進行清洗、固液分離後， 於微還原性氣體環境下，在300〜100(rc下對該共沈氫氧化 物進行一次煅燒，繼而於微還原性氣體環境下或惰性氣體 環境下，在600〜looot：下進行二次煅燒。藉由此種方法所 136688.doc 200938598 該氧空位有 製造之ITO粒子因其製造方法會產生氧空位 助於提咼ΙΤΟ奈米粒子之導電性。 右考慮到本發明之墨水係藉由喷墨方式而使用者，則本 發明中所用之ΙΤΟ粒子的-次粒子之平均粒徑越微細，引 起喷墨之喷嘴堵塞之可能性越低，越適合形成細節距之微 細電路。具體而言，-次粒子之平均粒徑較好的是刚⑽ 以下，特別好的是5〜40 nm »本發明中一次粒子之平均粒 徑，係指藉由穿透式電子顯微鏡進行觀察時，觀察一個視 野中所含最低200個粉粒之粒徑，將該等加以累計並進行 平均而求得之粒徑。 ITO之一次粒子之平均粒徑較小則表示該粒子較細。但 是，即便是微粒，在墨水中粒子彼此亦會進行凝聚，若二 次結構髏之粒徑變大，則由該墨水所形成之導電膜之表面 平滑性降低。又，於藉由喷墨印刷方式等使用本發明之墨 水時，可能會引起喷嘴堵塞。就該等觀點而言，較好的是 使墨水中ITO粒子之二次結構體的凝聚粒之最大粒徑為〇 2 μιη以下。 ΙΤΟ粒子之形狀並無特別限制。例如可使用球狀ιτ〇粒 子。 墨水中ΙΤΟ粒子之調配量較好的是卜8〇重量％，更好的 是5〜80重量％。藉由使ΙΤΟ粒子之調配量在該範圍内，可 提高由該墨水形成之導電膜之表面平滑性，又可使導電膜 充分薄膜化。 本發明之墨水中所用之鈦偶合劑係用以提昇由該墨水所 136688.doc 200938598 形成之塗膜與基板之密接性。又，鈦偶合劑亦具有促進後 述丙烯酸系樹脂之三維交聯的交聯劑之功能。 作為鈦偶合劑，較好的是使用具有上述作用者。特別好的 是鈦偶合劑不含鹽。藉由使用不含鹽之鈦偶合劑，會有不易 阻礙墨水中ITO粒子之分散性的優點。所謂含鹽之鈦偶合 劑，例如為二羥基雙（乳酸錄）欽(Ti(〇H)2(〇C2H5C〇〇-)2(NH4+)2) ，等。 作為不含鹽之鈦偶合劑之較好例，可列舉烷氧化鈦、鈦 ® 螯合物、醯化鈦等。該等可單獨使用1種，或將2種以上加 以組合而使用。 作為烷氧化鈦，例如可列舉Ti(〇R)4(式中，尺表示相同 或不同之烷基）所示者。作為其具體例，可列舉：鈦酸四 異丙酯、鈦酸四正丁酯、鈦酸丁酯二聚物、鈦酸四辛酯 等。 作為鈦螯合物’例如可列舉Ti(OR)n(X)4-n(式中，r表示 相同或不同之烧基’ X表示螯合物配位基，η表示〇〜3之整 數）所示者。作為其具體例，可列舉：乙醯丙酮酸鈦 ((C3H70)2Ti(C5H702)2)、羥乙酸辛酯鈦（titanium octyl glycolate)((C8HnO)2Ti(C8H〗702)2)、四乙醯丙酮酸鈦 (Ti(C5H702)4)、乙醯乙酸乙酯鈦（（C3H7〇)2Ti(C6H903)2) 作為醯化鈦，例如可列舉TKORJJOCOHn(式中，R, 及R2表示院基，n表示〇〜3之整數。）所示者。作為其具體 例’可列舉聚羥基硬脂酸鈦等》 136688.doc 200938598 本發明中所用之鈦偶合劑根據其與墨水中所含ITO粒子 之調配量的關係而確定調配量。具體而言，較好的是調配 鈦偶合劑使鈦偶合劑/ΙΤΟ粒子之重量比為〇.〇1〜1〇、特別 是〇·1〜0.5。藉由使鈦偶合劑之調配量在該範圍内，可使由 本發明之墨水所形成之導電膜與基板的密接性充分提高， 又可使該導電膜之表面平滑性充分提高。而且，可使該導 電膜之導電性充分提高。鈦偶合劑相對於ΙΤ〇粒子之重量 比如上所述，但墨水中之鈦偶合劑本身之濃度係以滿足上 述重量比為條件，較好的是〇.〇1〜40重量％，特別好的是 0·1〜40重量％ 〇 本發明之墨水中所用之丙烯酸系樹脂係具有噚唑啉基且 可三維交聯者。該丙烯酸系樹脂係用以提昇由本發明之墨 水所形成之導電膜的表面硬度及耐酸性。又，該丙烯酸系 樹脂由於透明性較高，因此亦有助於提昇由本發明之墨水 所形成之導電膜的透明性。 上述丙烯酸系樹脂所含之哼唑啉基具有以下結構： [化1]Patent Document 2: US Pat. No. 5,318,724 A Patent Document 3: JP2006-152203A SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an ITO ink having various properties which are further improved over the above-described prior art. The present invention provides an ITO ink which is obtained by dispersing 1το particles in a dispersed medium and containing a titanium coupling agent, and a three-dimensionally crosslinked acrylic acid system Resin. Further, the present invention provides a method for producing a conductive film, which is characterized in that a conductive film is produced using ITO ink, wherein a coating film of the IT 〇 ink is formed, and the coating film is fired at 100 to 350 ec. [Embodiment] Hereinafter, the present invention will be described based on preferred embodiments. The ink of the present invention is obtained by dispersing IT ruthenium particles in a dispersion medium. The ink contains a titanium coupling agent and an acrylic resin having a specific structure. As the ΙΤ0 (tin-doped indium oxide) powder, the same as those generally used in the art can be used without particular limitation. The ruthenium particles can be obtained, for example, by adding an alkaline aqueous solution to an acidic aqueous solution containing an indium salt and a tin salt to precipitate a coprecipitated hydroxide, washing, solid-liquid separation, and then under a microreducing gas atmosphere. The co-precipitated hydroxide is calcined once at 300 to 100 (rc), and then subjected to secondary calcination under a microreducing gas atmosphere or an inert gas atmosphere at 600 tolooot: by this method 136688 .doc 200938598 The oxidized ITO particles produced by the oxygen vacancies will produce oxygen vacancies to promote the conductivity of the nanoparticles. The right consideration is given to the ink of the present invention by the inkjet method. The finer the average particle diameter of the secondary particles of the ruthenium particles used in the invention, the lower the possibility of clogging of the nozzle of the ink jet, and the more suitable it is to form a fine circuit of fine pitch. Specifically, the average particle diameter of the secondary particles is smaller. Preferably, it is just below (10), particularly preferably 5 to 40 nm. » The average particle diameter of the primary particles in the present invention means that when viewed by a transmission electron microscope, observation is included in one field of view. The particle size of the lowest 200 particles, which is accumulated and averaged to obtain the particle size. The smaller average particle size of the primary particles of ITO indicates that the particles are finer. However, even particles are in the ink. When the particle size of the secondary structure is increased, the surface smoothness of the conductive film formed by the ink is lowered. When the ink of the present invention is used by an inkjet printing method or the like, In view of the above, it is preferable that the maximum particle diameter of the agglomerated particles of the secondary structure of the ITO particles in the ink is 〇2 μηη or less. The shape of the ruthenium particles is not particularly limited. The spherical iota particles can be used. The blending amount of the niobium particles in the ink is preferably 8% by weight, more preferably 5 to 80% by weight, and the blending amount of the cerium particles is increased within the range. The surface smoothness of the conductive film formed by the ink can further sufficiently thin the conductive film. The titanium coupling agent used in the ink of the present invention is used to enhance the coating film and the substrate formed by the ink 136688.doc 200938598. Further, the titanium coupling agent also has a function of a crosslinking agent which promotes three-dimensional crosslinking of an acrylic resin to be described later. As the titanium coupling agent, those having the above-described effects are preferably used. Particularly preferably, the titanium coupling agent does not. Salt. By using a salt-free titanium coupling agent, there is an advantage that it is difficult to hinder the dispersibility of ITO particles in the ink. The so-called salt-containing titanium coupling agent is, for example, dihydroxy double (lactic acid) (Ti (〇H) 2(〇C2H5C〇〇-)2(NH4+)2), etc. As a preferable example of the salt-free titanium coupling agent, titanium alkoxide, titanium® chelate, titanium telluride, etc. may be mentioned. One type may be used alone or two or more types may be used in combination. Examples of the titanium alkyl oxides include those represented by Ti(〇R) 4 (wherein the squares indicate the same or different alkyl groups). Specific examples thereof include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, and tetraoctyl titanate. Examples of the titanium chelate compound include Ti(OR)n(X)4-n (wherein, r represents the same or different alkyl group 'X represents a chelate ligand, and η represents an integer of 〇~3) Shown. Specific examples thereof include titanium acetylacetonate ((C3H70)2Ti(C5H702)2), titanium octyl glycolate ((C8HnO)2Ti (C8H〗 702) 2), and tetraethyl hydrazine. Titanium pyruvate (Ti(C5H702)4), acetonitrile ethyl acetate ((C3H7〇)2Ti(C6H903)2)) As the titanium telluride, for example, TKORJJOCOHn (wherein R, and R2 represent a hospital base, n Indicates the integer of 〇~3.). Specific examples thereof include titanium polyhydroxystearate and the like. 136688.doc 200938598 The titanium coupling agent used in the present invention determines the blending amount based on the relationship with the amount of ITO particles contained in the ink. Specifically, it is preferred to formulate the titanium coupling agent so that the weight ratio of the titanium coupling agent/cerium particles is 〇.〇1 to 1〇, particularly 〇·1 to 0.5. When the amount of the titanium coupling agent is within this range, the adhesion between the conductive film formed by the ink of the present invention and the substrate can be sufficiently improved, and the surface smoothness of the conductive film can be sufficiently improved. Further, the conductivity of the conductive film can be sufficiently improved. The weight of the titanium coupling agent relative to the cerium particles is as described above, but the concentration of the titanium coupling agent itself in the ink is such that the above weight ratio is satisfied, preferably 〇1 to 40% by weight, particularly preferably It is 0. 1 to 40% by weight. The acrylic resin used in the ink of the present invention has an oxazoline group and can be three-dimensionally crosslinked. The acrylic resin is used to enhance the surface hardness and acid resistance of the conductive film formed by the ink of the present invention. Further, since the acrylic resin has high transparency, it also contributes to enhancing the transparency of the conductive film formed by the ink of the present invention. The oxazoline group contained in the acrylic resin has the following structure: [Chemical Formula 1]
具有十坐琳基之丙稀酸系樹脂藉由啊琳基之開環而進 行三維交聯。本發明巾所用之丙料纟樹隸據本發明之 墨水所含介質之種類，可制水溶性或油溶性者。作為此 種丙稀酸系樹脂，例如可列舉：彳自位於日本國大阪府之 136688.doc 200938598 日本觸媒獲得的含呤唑啉基之丙烯酸系樹脂即 「EPOCROS」（註冊商標）等。 上述丙烯酸系樹脂根據其與墨水中所含ιτ〇粒子之調配 量的關係而確定調配量。具體而言，較好的是調配丙稀酸 系樹脂使丙烯酸系樹脂（固形分）/ΙΤ〇粒子之重量比為 0.01 1，〇、特別是0.1〜0.5。II由使丙烤酸系樹脂之調配量 在該範圍m由本發明之墨水所形成之導電膜的表面The acrylic resin with ten-sand-based base is cross-linked by three-dimensional cross-linking. The eucalyptus eucalyptus used in the towel of the present invention can be made water-soluble or oil-soluble according to the type of medium contained in the ink of the present invention. As such an acrylic acid-based resin, for example, "EPOCROS" (registered trademark) which is an oxazoline group-containing acrylic resin obtained from Japan Catalyst 136688.doc 200938598 Japan. The acrylic resin is determined in accordance with the relationship between the amount of the acrylic resin and the amount of the iota particles contained in the ink. Specifically, it is preferred to formulate the acrylic resin so that the weight ratio of the acrylic resin (solid content) / cerium particles is 0.01 1, 〇, particularly 0.1 to 0.5. II is a surface of a conductive film formed by the ink of the present invention in which the amount of the acrylic acid resin is adjusted in the range m
硬度及耐酸性充分提高，又可使該導電臈之透明性充分提 高。丙烯酸系樹脂相對於ITO粒子之重量比如上所述，但 墨水中之丙稀酸系樹脂（固形分）本身之漢度係以滿足上述 重量比為條件，較好的是0.01〜40重量％，特別好的是 0.1〜40重量％。 本發明之墨水係將上述ΙΤ〇粒子分散於分散介質中而成 者。作為該分散介質，可使W種或2種以上有機溶劑。作 為分散介質中之主溶劑，較好的是使用一元醇類 類。所謂主溶劑，於分散介質包含2種以上有機 ， 未必係比率最高之有機溶劑。 IF两 _ _ 〜 A畔、環麄疋 醇、苄醇、3_甲基丁醇、4-甲基-2-戊醇、孓甲 醇、2_乙氧基乙醇、2-正丁氧基乙醇、2•苯氣基乙醇、乙 必醇、乙基卡必醇、正丁基卡必醇、二丙嗣醇等。其卡 較好的是常塵下之沸點為1〇〇〇c以上，且室溫常堡 易氣化者，更好的是使用丁醇、卜戍醇、 I不 醇2_乙氧基乙醇、2-正丁氧基乙醇、2_苯氧基乙醇乙 136688.doc 200938598 丙酮醇。 作為二醇類’例如可列舉：乙二醇、二乙二醇、三乙二 酵、四乙二醇、丙二醇、13_丙二醇、二丙二醇、三丙二 醇、1,2·丁二醇、丁二醇、1，4-丁二醇、戊二醇、己二 醇等。該等可使用！種或將2種以上加以組合而使用。其 中較好的是常溫（20〇c )下之黏度為1〇〇 以下者。 其原因在於.若黏度過高，則難以調整適合噴墨之黏度。 作為二醇類，特別好的是使用乙二醇、二乙二醇、丙二 醇丨，4-丁二醇，極好的是使用乙二醇。 於本發明之墨水中，較好的是調配5〜80重量°/◦之主溶 劑，更好的是調配35〜80重量％之主溶劑。 於本發明之墨水中’除了上述主溶劑外，可含有其他有 機心劑作為分散介質。其他有機溶劑主要具有作為表面張 力調整劑、或黏度調整劑之功能。藉由在墨水中含有具有 作為表Φ張力冑整劑或黏度調整劑之功能的有機溶劑，可 使本發明之墨水之表面張力及黏度達到適合喷墨印刷方式 之範圍。可用作表面張力調整劑或黏度調整劑之有機溶劑 較好的是與主溶劑具有相溶性β 關於表面張力調整劑，較好的是使用其表面張力為 15〜40 mN/m者。具體可列舉：h 丁醇、卜戊醇、‘甲基 戊醇、2-乙氧基乙醇、2-正丁氧基乙醇、正丁基卡1醇 等。該等之中，若使用2-正丁氧基乙醇等，則可容易維持 作為ITO墨水的長期品質穩定性，因此較好。再者，根據 所用表面張力調整劑之種類，有時前面已說明之主溶劑可 136688.doc •12· 200938598 兼作表面張力調整劑β此種情报性 ^ 時’無須調配與主溶劑不 同的表面張力調整劑。 關於黏度調整劑，較好的Β並 疋具本身黏度於25〇c下為 〇·6〜60 mPa’sec。具體而言，較奸 权好的疋可使用碳數為2〜8之 驗作為黏度調整劑。作為此# _ 々凡裡蹲’例如可列舉：1,4-二嘮 烷、γ-丁内酯、二正丁醚等。再去 丹考’根據所用黏度調整劑 ❹ 之種類，有時前面已說明之主溶劑可兼作黏度調整劑。此 種情形時，無須調配與主溶劑不同的黏度調整劑。 表面張力調整劑及黏度調整劑根據其與主溶劑之調配量 的關係而確定調配量。具體而言，關於表面張力調整劑， 較好的是進行調配使表面張力調整劑/主溶劑之重量比為 0·1〜1.2、特別是〇.1〜〇·5。另一方面，關於黏度調整劑， 較好的疋進行調配使黏度調整劑/主溶劑之重量比為 〇.1〜1.2、特別是〇.5〜12 ^藉由使表面張力調整劑及黏度 調整劑之調配量在該範圍内，可使本發明之墨水適合喷墨 印刷方式。又，可使墨水中之ΙΤ〇粒子的分散性達到良 好。 表面張力調整劑相對於主溶劑之重量比如上所述，但墨 水中表面張力調整劑本身之濃度以滿足上述重量比為條 件’較好的是0.5〜50重量％，更好的是10〜50重量％。另一 方面’墨水中黏度調整劑本身之濃度以滿足上述重量比為 條件’較好的是0.5〜50重量％，更好的是1〇〜50重量％。 包含上述主溶劑、表面張力調整劑及黏度調整劑之分散 介質總體之調配量相對於墨水總體，較好的是2〇〜95重量 136688.doc •13· 200938598 °/〇，更好的是40〜90重量％。 包含上述各成分之本發明之墨水，較好的是於25°(：卞1 表面張力為15~50 mN/m，特別是25~45 mN/m，又，就遠 到適合噴墨印刷法之表面張力及黏度之方面而言，較好的 是於25°C下之黏度為1~150 mPa.sec，特別是卜60 mPa.sec ° 本發明之墨水例如可藉由如下方法進行製備。首先，將 ITO粒子與分散介質加以混合而製備母IT0漿料。使用分散 機對母ΙΤΟ漿料進行分散處理。繼而，使用膜濾器 (membrane filter)等過濾材料除去ΙΤΟ之凝聚粒子。於如此 而得之ITO漿料中調配鈦偶合劑及丙烯酸系樹脂、以及視 需要之表面張力調整劑及黏度調整劑，並充分混合β如此 而獲得目標ΙΤΟ墨水。 藉由喷墨印刷方式或分配器塗布方式，將以上述方式而 得之墨水塗布於以玻璃為代表之各種基材上，將藉由塗布 而形成之塗膜進行煅燒，而獲得目標導電膜。煅燒之氣體 環境並無特別限制，例如可於大氣環境下進行烺燒。又， 視情況，亦可於氮氣環境下、氬氣環境下、氫氣_氮氣混 合氣體環境下等惰性氣體環境下或者還原性氣體環境下進 行緞燒。在使用任一氣體環境時，煅燒時間均較好的是 0.5〜2小時左右。 本發明之墨水所具有之一特徵在於：在導電臈之製造過 程中，即便降低塗膜之煅燒溫度，亦可提高所得導電骐之 表面硬度。具體而言，可使煅燒溫度為較好的是 136688.doc 14 200938598 100〜350°c、更好的是100〜15(TC。由於可於此種低温下進 行煅燒，因此具有以下優點：可於包含除玻璃以外之透明 基板、例如聚碳酸酯樹脂等耐熱溫度為130〜160°C左右的 熱塑性樹脂之基板上形成導電膜。 實施例 以下，藉由實施例對本發明進行更詳細說明。但本發明 ‘之範圍並不限定於該實施例。 [實施例1] Ο (1)漿料之製備 使ITO粉（三井金屬礦業股份有限公司製造、一次粒子之 平均粒徑為20 nm)50 g分散於作為溶劑的乙二醇200 g中， 而製備母ITO漿料250 g。 (2) 分散處理 使用以氧化鍅珠（NIKKATO股份有限公司製造、〇. 1 ηιιηφ)為介質之塗料振盪器（淺田鐵鋼股份有限公司製造）， 將母ΙΤΟ聚料進行分散處理3小時。 (3) 粗粒除去 將所得漿料中所含有之粗粒子通液至膜濾器（Advantec Toyo股份有限公司製造、孔徑0.2 μιη)而加以除去，獲得 不含粗粒之ΙΤΟ漿料。 (4) 導電性墨水之製備 於ΙΤΟ漿料1〇〇 g中添加丙烯酸系樹脂4_〇 g(曰本觸媒公 司製造、EPOCROS(註冊商標）WS500(具有啰唑淋基之可 三維交聯的丙烯酸系樹脂））、以及鈦偶合劑4.〇 g (Matsum〇t〇 136688.doc 15 200938598The hardness and acid resistance are sufficiently improved, and the transparency of the conductive crucible is sufficiently improved. The weight of the acrylic resin relative to the ITO particles is as described above, but the amount of the acrylic resin (solid content) in the ink itself is preferably 0.01 to 40% by weight, based on the weight ratio. Particularly preferably, it is 0.1 to 40% by weight. The ink of the present invention is obtained by dispersing the above-mentioned cerium particles in a dispersion medium. As the dispersion medium, one type or two or more types of organic solvents can be used. As the main solvent in the dispersion medium, it is preferred to use a monohydric alcohol. The main solvent contains two or more kinds of organic substances in the dispersion medium, and is not necessarily the highest ratio of the organic solvent. IF two _ _ ~ A side, cyclodecyl alcohol, benzyl alcohol, 3-methylbutanol, 4-methyl-2-pentanol, hydrazine methanol, 2-ethoxyethanol, 2-n-butoxyethanol 2, benzene-based ethanol, ethyl alcohol, ethyl carbitol, n-butyl carbitol, dipropanol and the like. The card is preferably a boiling point of 1 〇〇〇c or more under normal dust, and the room temperature is easy to gasify, more preferably butanol, diterpene alcohol, I nonol 2 ethoxyethanol , 2-n-butoxyethanol, 2-phenoxyethanol B 136688.doc 200938598 acetol. Examples of the diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 13-propylene glycol, dipropylene glycol, tripropylene glycol, 1,2, butanediol, and dibutyl. Alcohol, 1,4-butanediol, pentanediol, hexanediol, and the like. These can be used! Two or more types are used in combination. Among them, it is preferred that the viscosity at room temperature (20 〇 c ) is 1 〇〇 or less. The reason is that if the viscosity is too high, it is difficult to adjust the viscosity suitable for inkjet. As the glycol, it is particularly preferable to use ethylene glycol, diethylene glycol, propylene glycol hydride, 4-butanediol, and it is excellent to use ethylene glycol. In the ink of the present invention, it is preferred to formulate a main solvent of 5 to 80% by weight, more preferably 35 to 80% by weight of the main solvent. In the ink of the present invention, in addition to the above main solvent, other organic solvent may be contained as a dispersion medium. Other organic solvents mainly function as surface tension adjusters or viscosity modifiers. By including an organic solvent having a function as a surface tension adjusting agent or a viscosity adjusting agent in the ink, the surface tension and viscosity of the ink of the present invention can be made suitable for the ink jet printing method. The organic solvent which can be used as the surface tension adjusting agent or the viscosity adjusting agent is preferably compatible with the main solvent. β Regarding the surface tension adjusting agent, it is preferred to use a surface tension of 15 to 40 mN/m. Specific examples thereof include h butanol, pentyl alcohol, 'methylpentanol, 2-ethoxyethanol, 2-n-butoxyethanol, n-butylcaptanol and the like. Among these, when 2-n-butoxyethanol or the like is used, it is easy to maintain long-term quality stability as an ITO ink, which is preferable. Furthermore, depending on the type of surface tension adjusting agent used, sometimes the main solvent described above may be 136688.doc •12· 200938598 also serves as the surface tension adjusting agent β. This kind of information is not required to adjust the surface tension different from the main solvent. Conditioner. Regarding the viscosity modifier, a preferred crucible has a viscosity of 〇·6 to 60 mPa'sec at 25 〇c. Specifically, it is better to use a carbon number of 2 to 8 as a viscosity modifier. Examples of the #_々凡里蹲' include, for example, 1,4-dioxane, γ-butyrolactone, di-n-butyl ether, and the like. Going to Dan Khao's depending on the type of viscosity modifier used, sometimes the main solvent described above can double as a viscosity modifier. In this case, it is not necessary to mix a viscosity modifier different from the main solvent. The surface tension adjusting agent and the viscosity adjusting agent determine the blending amount based on the relationship with the amount of the main solvent. Specifically, as for the surface tension adjusting agent, it is preferred to adjust the weight ratio of the surface tension adjusting agent/main solvent to 0·1 to 1.2, particularly 〇.1 to 〇·5. On the other hand, regarding the viscosity modifier, a better enthalpy is adjusted so that the weight ratio of the viscosity modifier/main solvent is 〇.1 to 1.2, particularly 〇.5 to 12 ^ by adjusting the surface tension adjusting agent and viscosity The blending amount of the agent is within this range, and the ink of the present invention can be adapted to the ink jet printing method. Further, the dispersibility of the ruthenium particles in the ink can be made good. The weight of the surface tension adjusting agent relative to the main solvent is as described above, but the concentration of the surface tension adjusting agent itself in the ink satisfies the above weight ratio as a condition of preferably 0.5 to 50% by weight, more preferably 10 to 50%. weight%. On the other hand, the concentration of the viscosity adjusting agent itself in the ink satisfies the above weight ratio as a condition of preferably 0.5 to 50% by weight, more preferably 1 to 50% by weight. The total amount of the dispersion medium containing the above main solvent, surface tension adjusting agent and viscosity adjusting agent is preferably 2 〇 95 95 。 136 688 688 688 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 ~90% by weight. The ink of the present invention comprising the above components preferably has a surface tension of 15 to 50 mN/m, particularly 25 to 45 mN/m, and is far suitable for ink jet printing. In terms of surface tension and viscosity, it is preferred that the viscosity at 25 ° C is 1 to 150 mPa·sec, particularly 60 mPa·sec °. The ink of the present invention can be produced, for example, by the following method. First, a mother IT slurry is prepared by mixing ITO particles and a dispersion medium, and the mother slurry is subjected to dispersion treatment using a disperser, and then a filter material such as a membrane filter is used to remove the agglomerated particles of the crucible. The ITO slurry is prepared by blending a titanium coupling agent and an acrylic resin, and optionally a surface tension adjusting agent and a viscosity adjusting agent, and sufficiently mixing β to obtain a target yt ink. By inkjet printing or dispenser coating The ink obtained in the above manner is applied to various substrates represented by glass, and the coating film formed by coating is calcined to obtain a target conductive film. The gas atmosphere for calcination is not particularly limited. Sintering can be carried out in an atmospheric environment. In addition, depending on the situation, satin burning can be carried out in an inert gas atmosphere such as a nitrogen atmosphere, an argon atmosphere or a hydrogen-nitrogen mixed gas atmosphere or a reducing gas atmosphere. In any gas environment, the calcination time is preferably about 0.5 to 2 hours. One of the characteristics of the ink of the present invention is that, in the production process of the conductive crucible, even if the calcination temperature of the coating film is lowered, the yield can be improved. The surface hardness of the conductive crucible. Specifically, the calcination temperature is preferably 136688.doc 14 200938598 100 to 350 ° C, more preferably 100 to 15 (TC. Since calcination can be carried out at such a low temperature, Therefore, it is advantageous in that a conductive film can be formed on a substrate including a transparent substrate other than glass, for example, a thermoplastic resin having a heat-resistant temperature of about 130 to 160 ° C, such as a polycarbonate resin. EXAMPLES Hereinafter, the present invention will be described by way of examples. The scope of the present invention is not limited to this embodiment. [Example 1] Ο (1) Preparation of slurry to make ITO powder (Mitsui Metals Mining Co., Ltd. Manufactured, the average particle size of primary particles is 20 nm) 50 g dispersed in 200 g of ethylene glycol as a solvent, and 250 g of mother ITO slurry is prepared. (2) Dispersing treatment is used to oxidize yttrium beads (NIKKATO shares limited) The company manufactures 〇. 1 ηιιηφ) as a medium paint shaker (manufactured by Asada Iron and Steel Co., Ltd.), and disperses the mother mash aggregate for 3 hours. (3) The coarse granule removes the coarse powder contained in the obtained slurry. The particles were passed through a membrane filter (manufactured by Advantec Toyo Co., Ltd., pore size: 0.2 μm) and removed to obtain a mash slurry containing no coarse particles. (4) Preparation of Conductive Ink The acrylic resin 4_〇g (manufactured by Sakamoto Catalyst Co., Ltd., EPOCROS (registered trademark) WS500 (3D cross-linking with carbazole lyophilized base) was added to the ΙΤΟ slurry. Acrylic resin)), and titanium coupling agent 4. 〇g (Matsum〇t〇136688.doc 15 200938598
Fine Chemical公司製造之TC_1〇〇(乙醯丙嗣酸鈦）），藉由塗 料振盪器（淺田鐵鋼股份有限公司製造）進行混合，而獲得 導電性墨水。 (5)電極製作 使用旋轉塗布機（MIKASA公司製造），於無鹼玻璃基板 (曰本電氣硝子股份有限公司製造之OA-io)上，以150〇 rpm、1〇秒鐘之條件，將導電性墨水成膜。於大氣、 下將所得塗膜加熱煅燒2小時而獲得透明導電膜。 [實施例2] 於實施例1之「（5)電極製作」中，將煅燒溫度設為 120 C ’將時間設為1小時’除此以外，以與實施例1相同 之方式獲得透明導電膜。 [比較例1 ] 使用作為丙稀酸系樹脂之P〇lyacrylie Acid 5000(和光純 藥公司製造）代替實施例2之丙烯酸系樹脂WS500，除此以 外’以與實施例2相同之方式製備導電性墨水，並獲得透 明導電膜。Polyacrylic Acid 5000不具有噚唑啉基。 [比較例2] 使用作為乙烯系樹脂之polyvinylpyrrolidone K30(和光純藥公司製造）代替實施例2之丙烯酸系樹脂 WS500 ’除此以外，以與實施例2相同之方式製備導電性 墨水，並獲得透明導電膜。 [比較例3] 使用作為氧化锆偶合劑之ZB125(Matsumoto Fine Chemical 136688.doc -16- 200938598 公司製造）代替實施例2之鈦偶合劑TC100，除此以外，以 與實施例2相同之方式製備導電性墨水，並獲得透明導電 膜。 [比較例4] 使用作為矽烷偶合劑之KBM403(信越有機矽（Shin-Etsu Silicones)公司製造）代替實施例2之鈦偶合劑TC100，除此 * 以外，以與實施例2相同之方式製備導電性墨水，並獲得 透明導電膜。 e [比較例5 ] 除了不添加實施例2之丙烯酸系樹脂WS500以外，以與 實施例2相同之方式製備導電性墨水，並獲得透明導電 膜。 [比較例6] 除了不添加實施例2之鈦偶合劑TC100以外，以與實施 例2相同之方式製備導電性墨水，並獲得透明導電膜。 [比較例7] 使用作為乙烯系樹脂之POLYVINYLPYRROLIDONE K3 0(和光純藥公司製造）代替實施例2之丙烯酸系樹脂 WS500，且不添加鈦偶合劑TC100，除此以外，以與實施 例2相同之方式製備導電性墨水，並獲得透明導電膜。 [比較例8] 使用作為氧化錯偶合劑之ZB125(Matsumoto Fine Chemical公司製造）代替實施例2之鈦偶合劑TC1 〇〇，且不 添加丙烯酸系樹脂WS500 ’除此以外，以與實施例2相同 136688.doc -17- 200938598 之方式製備導電性墨水，並獲得透明導電膜。 [比較例9] 實施例2之鈦偶合劑TC100及丙烯酸系樹脂冒“⑽均不添 加，除此以外，以與實施例2相同之方式製備導電性墨 水’並獲得透明導電膜。 [評價] 藉由以下方法對實施例及比較例中所得之墨水的分散穩 定性進行評價。又，藉由以下方法對實施例及比較例中所 得之導電膜的導電性、與基板之密接性、透明性、表面硬 度、耐酸性進行平價。其等之結果示於以下之表丨中。 [墨水之分散穩定性] 將墨水於5C下冷藏保存5日後，目視觀察IT〇粒子之分 散性程度’按以下基準進行評價。 〇：未產生沈殿物 X :產生沈殿物 [導電膜之導電性] 使用四探針電阻測定機（三菱化學股份有限公司製造之 LORESTA GP) ’測定導電膜之電阻率。 [導電膜與基板之密接性] 依據JIS Κ 5600第5-6段，藉由交又切割（er〇sscut)法進行 評價。又，於水中將導電膜進行1〇分鐘之超音波清洗，繼 而於丙酮中進行10分鐘之超音波清洗，然後，使用顯微鏡 (KEYENCE公司製造之VH-8000)觀察導電膜有無剝離。將 未觀察到剝離之情形設為「〇」，將觀察到剝離之情形設 136688.doc -18- 200938598 為「X」° [導電膜之透明性] 使用分光光度計（曰立計測器公司製造之U-4000)測定波 長為450 nm之透射率。 [導電膜之表面硬度] 依據JIS K 5600，藉由劃痕硬度試驗器（COTEC公司製造 '之KT-VF2391)進行評價。 [導電膜之耐酸性] 〇 將導電膜於5重量％之草酸水溶液中浸潰1〇分鐘，在水 洗及乾燥後使用顯微鏡（KEYENCE公司製造之VH-8000)觀 察導電膜有無剝離。又，使用掃描型電子顯微鏡（FEI COMPANY公司製造之FE-SEM)觀察膜質。將未觀察到剝 離之情形設為「〇」，將觀察到剝離之情形設為「X」。 [表1] 136688.doc -19- 200938598 ON 〇 >1000 X X 97.8 6Β以下 X X 00 〇 j 0.18 1 X X 94.5 | | 6Β以下| X X 卜 〇 1 >1000 1 X X 96.6 | 6Β以下 X X v〇 〇 >1000 1_ X X 97.1 6Β以下 X X t匕較例 〇 <N 〇 〇 96.5 〇 X 寸 〇 500 〇 〇 96.8 | 6Β以下| X X 〇 〇 〇 85.3 [6Β以下J X X CN 〇 cs ϊ> 〇 〇 97.1 I 6Β以下j X X 〇 00 00 〇 〇 1 95.7 I | 6B以下| X X 實施例 cs 〇 — 〇 〇 96-9 P3 〇 〇 〇 cn cs 〇 〇 97-5 ffl 〇 〇 分散穩定性 導電性(Ωχιη) 交又切割法 超音波清洗 透明性(％) 表面硬度 顯微鏡觀察 SEM觀察 密接性 耐酸性 墨水 導電膜 136688.doc -20- 200938598 根據表1所示之結果可明顯判斷，實施例中所得之墨水 與比較例中所得之墨水相比，分散穩定性高，又，滿足導 電性、透明性、表面硬度及财酸性之全部特性。特別是根 據實施例2之結果可明顯判斷，即便將塗膜之鍛燒溫度設 定成120°C之較低溫度，所得導電膜之鉛筆硬度仍達到b， « 獲得實用上可令人滿意的表面硬度。 '[產業上之可利用性] 以上’如詳細所述’根據本發明，可提供一種ΙΤ〇墨 〇 水，其藉由喷墨法可容易形成透明性高、又電阻低、並且 表面硬度高、耐酸性優異之透明導電膜。 ❹ 136688.doc -21·TC_1 〇〇 (titanium bismuth citrate) manufactured by Fine Chemical Co., Ltd. was mixed by a coating shaker (manufactured by Asada Iron and Steel Co., Ltd.) to obtain a conductive ink. (5) Electrode production was carried out by using a spin coater (manufactured by MIKASA Co., Ltd.) on an alkali-free glass substrate (OA-io manufactured by Sakamoto Electric Glass Co., Ltd.) at 150 rpm for 1 〇 second. The ink is formed into a film. The obtained coating film was heated and calcined in the atmosphere for 2 hours to obtain a transparent conductive film. [Example 2] A transparent conductive film was obtained in the same manner as in Example 1 except that in the "(5) Electrode fabrication" of the first embodiment, the calcination temperature was changed to 120 C' and the time was set to 1 hour. . [Comparative Example 1] Conductivity was prepared in the same manner as in Example 2 except that P〇lyacrylie Acid 5000 (manufactured by Wako Pure Chemical Co., Ltd.) as an acrylic resin was used instead of the acrylic resin WS500 of Example 2. Ink and obtain a transparent conductive film. Polyacrylic Acid 5000 does not have an oxazoline group. [Comparative Example 2] A conductive ink was prepared in the same manner as in Example 2 except that polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Co., Ltd.) as a vinyl resin was used instead of the acrylic resin WS500' of Example 2. Conductive film. [Comparative Example 3] The same procedure as in Example 2 was carried out except that ZB125 (manufactured by Matsumoto Fine Chemical 136688.doc -16-200938598), which is a zirconia coupling agent, was used instead of the titanium coupling agent TC100 of Example 2. A conductive ink is obtained, and a transparent conductive film is obtained. [Comparative Example 4] Conductive was prepared in the same manner as in Example 2 except that KBM403 (manufactured by Shin-Etsu Silicones Co., Ltd.) as a decane coupling agent was used instead of the titanium coupling agent TC100 of Example 2. The ink is obtained and a transparent conductive film is obtained. [Comparative Example 5] A conductive ink was prepared in the same manner as in Example 2 except that the acrylic resin WS500 of Example 2 was not added, and a transparent conductive film was obtained. [Comparative Example 6] A conductive ink was prepared in the same manner as in Example 2 except that the titanium coupling agent TC100 of Example 2 was not added, and a transparent conductive film was obtained. [Comparative Example 7] The same procedure as in Example 2 was carried out except that the acrylic resin WS500 of Example 2 was used instead of the acrylic resin WS500 of Example 2, and the titanium coupling agent TC100 was not added. A conductive ink was prepared in a manner, and a transparent conductive film was obtained. [Comparative Example 8] The same procedure as in Example 2 was carried out except that ZB125 (manufactured by Matsumoto Fine Chemical Co., Ltd.) as an oxidative coupling agent was used instead of the titanium coupling agent TC1 实施 of Example 2, and the acrylic resin WS500' was not added. A conductive ink was prepared in the manner of 136688.doc -17- 200938598, and a transparent conductive film was obtained. [Comparative Example 9] A conductive ink was prepared in the same manner as in Example 2 except that the titanium coupling agent TC100 of the second embodiment and the acrylic resin were not added ("10), and a transparent conductive film was obtained. [Evaluation] The dispersion stability of the inks obtained in the examples and the comparative examples was evaluated by the following methods. Further, the conductivity of the conductive film obtained in the examples and the comparative examples, the adhesion to the substrate, and the transparency were evaluated by the following methods. Surface hardness and acid resistance were used for the price. The results are shown in the following table. [Dispersion stability of ink] After the ink was stored in 5 C for 5 days, the degree of dispersibility of the IT 〇 particles was visually observed. The evaluation was carried out. 〇: The shovel was not produced. X: The shoal was produced. [The conductivity of the conductive film] The conductivity of the conductive film was measured using a four-probe resistance measuring machine (LORESTA GP manufactured by Mitsubishi Chemical Corporation). Adhesion between film and substrate] According to JIS Κ 5600, paragraphs 5-6, by er〇sscut method, the conductive film is subjected to ultrasonic cleaning for 1 minute in water. Then, ultrasonic cleaning was performed for 10 minutes in acetone, and then the presence or absence of peeling of the conductive film was observed using a microscope (VH-8000 manufactured by KEYENCE Co., Ltd.), and the case where no peeling was observed was set to "〇", and peeling was observed. 136688.doc -18- 200938598 is "X" ° [Transparency of Conductive Film] The transmittance at a wavelength of 450 nm was measured using a spectrophotometer (U-4000 manufactured by Sigma Instruments). [Surface Hardness of Conductive Film] Evaluation was carried out by a scratch hardness tester (KT-VF2391 manufactured by COTEC Corporation) in accordance with JIS K 5600. [Acid resistance of the conductive film] 导电 The conductive film was immersed in a 5% by weight aqueous solution of oxalic acid for 1 minute, and after washing with water and dried, the conductive film was observed for peeling using a microscope (VH-8000 manufactured by Keyence Corporation). Further, the film quality was observed using a scanning electron microscope (FE-SEM manufactured by FEI COMPANY). The case where no peeling was observed was set to "〇", and the case where peeling was observed was set to "X". [Table 1] 136688.doc -19- 200938598 ON 〇>1000 XX 97.8 6Β以下XX 00 〇j 0.18 1 XX 94.5 | | 6Β以下| XX 〇1 >1000 1 XX 96.6 | 6Β以下XX 〇〇 >1000 1_ XX 97.1 6Β The following XX t匕 comparison example <N 〇〇96.5 〇X inch 〇500 〇〇96.8 | 6Β以下| XX 〇〇〇85.3 [6ΒJJ CN 〇cs ϊ> 〇〇97.1 I 6Β以下 j XX 〇00 00 〇〇1 95.7 I | 6B or less | XX Example cs 〇—〇〇96-9 P3 〇〇〇cn cs 〇〇97-5 ffl 〇〇Dispersion stability Conductivity (Ωχιη) Cutting method Ultrasonic cleaning transparency (%) Surface hardness Microscopic observation SEM observation of adhesive acid-resistant ink conductive film 136688.doc -20- 200938598 According to the results shown in Table 1, it can be clearly judged that the ink obtained in the examples is compared with In the case of the ink obtained in the example, the dispersion stability is high, and all the properties of conductivity, transparency, surface hardness and acidity are satisfied. In particular, it can be clearly judged from the results of Example 2 that even if the calcination temperature of the coating film is set to a lower temperature of 120 ° C, the pencil hardness of the obtained electroconductive film reaches b, « obtaining a practically satisfactory surface hardness. '[Industrial Applicability] The above 'As described in detail', according to the present invention, it is possible to provide an ink-repellent water which can easily form a high transparency, a low electrical resistance, and a high surface hardness by an inkjet method. A transparent conductive film excellent in acid resistance. ❹ 136688.doc -21·