TWI280256B - Inorganic material film, inorganic material film structure, the process of manufacture them and a transfer film - Google Patents
Inorganic material film, inorganic material film structure, the process of manufacture them and a transfer film Download PDFInfo
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- TWI280256B TWI280256B TW094140013A TW94140013A TWI280256B TW I280256 B TWI280256 B TW I280256B TW 094140013 A TW094140013 A TW 094140013A TW 94140013 A TW94140013 A TW 94140013A TW I280256 B TWI280256 B TW I280256B
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Description
1280256 度高等。但是，須使噴砂時介電體形成層和隔壁形成層的噴 砂性具有差異，在進行噴砂加工時，希望只去除光阻圖案的 開口部的隔壁形成層，而殘餘其下層的介電體形成層，但是 欲賦與噴砂性的差異並不容易。 又，對介電體層使用感光性的乾膜和噴砂法（sand-blast method)來形成圖案時，因隔壁形成層與感光性光阻劑的黏 附差’顯像中或噴砂中有剝離的問題存在。 又，當介電體層的介電常數下降時，玻璃組成有軟化點 2增高的問題存在。 而且，在煅燒步驟，有收縮的位置性不均、因收縮大而 容易產生裂痕、噴砂後的煅燒時隔壁容易鬆弛、變形之問題 存在。又，有煅燒完成後之隔壁的介電常數變高、發熱、電 力消耗等問題存在。 希望有一種不會損害噴砂性、與感光性噴吵用光阻劑的 黏附性良好、煅燒時較不會產生鬆弛、變形、裂痕，可以使 用於低介電常數的隔壁形成層之材料。 φ 專利文獻3揭示一種方法，對於無機組成物塗布時之缺 _ 陷及噴砂時之圖案缺損、進而煅燒時之裂痕等問題，係使用 鼇 混合具有2種類平均粒子大小的無機粒子而成之糊料，藉由 ^ 網版印刷來形成圖案。 但是，煅燒後無法形成高解像度的微細圖案，又，因爲 係使用印刷，就均勻性等之點而言，並非可以充分滿足之物。 專利文獻4揭示一種介電體糊料，係使用粒度分布具有 2個尖鋒的玻璃。但是，未含有本發明所使用的塡料，無法 J280256 提供來形成隔壁。又，未記載使用轉印薄膜的形成方法。 又’專利文獻5〜1 3揭示使用模具的隔壁形成法。但是， 即便使用此等方法’亦不容易得到膜厚度較厚且不產生裂 痕、局度均句的膜。 又，專利文獻14揭示一種PDP的製造方法，係在將螢 光體糊料擠入像素內面時，爲了充分使像素面內的空氣脫離 而使用多孔質的隔壁。但是，並未記載使用何種材質較佳， 亦未記載形成多孔性空隙大小、空隙率等多孔性程度。 而且’專利文獻1 5揭示，藉由在隔壁的表面形成比隔 壁更多孔質的層’在面板發光時不純氣體不容易混入放電空 間內’可以保持放電空間內的鈍氣純度、提高發光亮度。但 是’完全未揭示成爲低介電常數的方針，亦未記載隔壁表面 的層之空隙大小、空隙率等多孔性程度。亦完全未記載煅燒 時的裂痕。 [專利文獻1]特開平10-144206號公報 [專利文獻2]特開平ι〇-172424號公報 [專利文獻3]特開平1 1 - 1 3 43號公報 [專利文獻4]特開2002-15664號公報 [專利文獻5]特開2003-123637號公報 [專利文獻6]特開2000-185938號公報 [專利文獻7]特開2001-167698號公報 [專利文獻8]特開2002-75175號公報 [專利文獻9 ]特開2 0 0 2 - 9 3 3 1 3號公報 [專利文獻10]特開2002-134005號公報 1280256 [專利文獻11]特開2000-173456號公報 [專利文獻12]特開200 1 -5 83 5 2號公報 [專利文獻1 3特開2 0 0 1 - 1 4 3 6 1 2 8號公報 [專利文獻14]特開平5-47303號公報 [專利文獻15]特開2002-324491號公報 【發明內容】 本發明係提供一種無機材料膜、無機材料膜構造物、及 其製造方法及其製造使所使用的轉印薄膜，該無機材料膜、 2 無機材料膜構造物具有低介電常數，可以提供使用於能夠抑 制發熱之省電力的PDP等。 又，本發明提供一種具有高精確度、微細構造的無機材 料膜、無機材料膜構造物、及其製造方法及其製造使所使用 的轉印薄膜，該無機材料膜、無機材料膜構造物在煅燒後， 隔壁或介電體的各種圖案的線寬或膜厚度幾乎沒有變化。 又，本發明可以提供一種轉印薄膜，與網版印刷等塗布 方式比較時，可以簡單地在基板上形成隔壁或介電體的各種 圖案，以及提供使用該轉印薄膜之無機材料膜構造物的製造 方法。 m 而且，本發明提供一種轉印薄膜，其形成隔壁、介電體 ' 的各種圖案用之非感光性組成物對基板的黏附良好、且與感 光性光阻劑的黏附亦良好，及提供使用該轉印薄膜之無機材 料膜構造物的製造方法。 本發明係如以下記載，藉此可以解決上述問題。 (1 ) 一種無機材料膜，其特徵爲煅燒至少含有無機粉末 1280256 之非感光性組成物而得到的多孔性無機材料膜，其中該無機 材料膜係空隙面積率爲2 0〜6 5 %、空隙大小爲5〜2 0微米。 (2) 如（1)之無機材料膜，其中該無機粉末係由平均粒 徑及軟化點各自不同之至少2種類所構成、且平均粒徑較大 的種類具有較高的軟化點。 (3) 如（2)之無機材料膜，其中該無機粉末係由無機粉 末a、以及軟化點比其高、且平均粒徑比其大的無機粉末b 所構成。 (4) 如（1)〜（3)中任一項之無機材料膜，其中該無機粉 末係由平均粒徑0 · 9〜1 · 5微米的無機粉末A、以及平均粒徑 比其大、且平均粒徑爲1 · 5〜2 · 5微米之無機粉末B所構成。 (5) —種無機材料膜構造物，係在基板上設置如（1)〜 (4)中任一項之無機材料膜而成。 (6) —種無機材料膜構造物的製造方法，其步驟如下， 在基板上設置如（1 )〜（4)中任一項之非感光性組成物，在該 非感光性組成物上設置感光性組成物，曝光、顯像處理後， 在非感光性組成物形成圖案，隨後煅燒而得到上述（5)所記 載的無機材料膜構造物。 (7) 如上述（6)之無機材料膜構造物的製造方法，其中 在上述（6)之基板上所設置之非感光性組成物，係從在可撓 曲性暫時支撐體上形成有塗布層之轉印薄膜，轉印該塗布層 至基板上而成之物。 (8) —種轉印薄膜，其特徵爲在可撓曲性暫時支撐體上 具有由上述（6)記載的非感光性組成物所構成的塗布層。 1280256 [發明效果] 本發明藉由使用非感光性組成物，該非感光性組成物含 有平均粒徑及軟化點各自不同之至少2種類以上的無機粉 末，可以得到低介電常數的多孔性無機材料膜及含有該多孔 性無機材料膜之無材料膜構造物。 又，本發明藉由在可撓曲性暫時支撐體具有上述非感光 ^ 性組成物的塗布層作爲轉印薄膜，可以提供PDP等精確電子 裝置，具有轉印塗布層與基板的黏附性良好、及感光性乾膜 ^ 與轉印塗布層的黏附性良好，且藉由顯像，未煅燒的圖案精 確度高、並且可以容易地製造，煅燒後線寬度、膜厚度的變 化小、高精確度且省電力之圖案。 【實施方式】 本發明的無機材料膜、以及在基板上設置該無機材料膜 而成之無機材料膜構造物的無機材料膜，係具有多孔性的特 徵、且將空隙面積率和空隙大小規定在特別範圍而成之物。 該無機材料膜藉由上述構成，將非感光性組成物形成隔 ^ 壁或介電體的各種圖案後，煅燒所得到的各種圖案，因爲在 其中存在有適當空隙而成爲多孔性，在改善耐收縮率之同 # 時，可以得到降低介電常數的效果。降低介電常數具有抑制 " PDP等的發熱且具有降低電力消耗的效果。 又，本發明藉由轉印薄膜形態，因爲能夠使非感光性組 成物的塗布層轉印至支撐體而得到轉印塗布層的表面性平 滑，可以在希望的支撐體上形成具有良好精確度輪廓之優良 的圖案。 1280256 面 剖 膜 料 材 機 無 從 以 可 積 面 隙 空 及 小 大 隙 α 空得 之求 明面 發剖 本的 孔 之 空隙大小係意指該剖面的最長直徑（2點之間的距離）， 本發明爲5〜20微米，以5.2〜18微米爲更佳。 空隙面積係意指孔的剖面總和，各自剖面的面積，可以 將S E Μ剖面照片之孔的部分’描繪在描圖紙上面，將宜剪 下稱量質量而求得。 孔的剖面形狀沒有特別限制’可以是不定形，亦可以是 圓形。 又’相對於無機材料膜的剖面積，本發明之空隙面積的 比率係定義爲空隙面積率。在此，所謂空隙面積率，係指將 無機材料膜的剖面拍攝成SEM照片，從3個大小爲〗00微 米χ 1〇〇微米大的剖面，求取測定値的平均。本發明之無機 材料膜的空隙面積率爲2 0〜6 5 %，以2 5〜6 0 %爲更佳。 在本發明，將無機材料膜的多孔性控制在上述範圍的手 段’係採用以下的手段。 無機粉末係使用由平均粒徑及軟化點各自不同之至少2 種類所構成、且平均粒徑較大的種類具有較高的軟化點之 物，可以舉出以下之較佳手段。又，在此，將平均粒徑及軟 化點互相不同的無機粉末，從平均粒徑及軟化點較小的一方 起之順序，以小寫之羅馬字母的順序記載成無機粉末a、b、 C、（J、 · · · 〇 (1)使用無機粉末a與無機粉末b所構成的混合物作爲 無機粉末。 -12- 1280256 (2)使平均粒徑爲〇·9〜1.5微米無機粉末a與平均粒 徑比其大、且平均粒徑爲1 . 5〜2 · 5微米的無機粉末b所構 成的混合物作爲無機粉末。 在上述（1)的手段’較佳是選定無機粉末b的軟化點比 無機粉末a的軟化點高出50°C以上，更佳是高出loot：以 一· 上。該較高一方的軟化點以6 0 0〜1 5 0 0 °C爲佳，以7 0 0〜 ’ 1 400°c爲更佳。又’無機粉末a與無機粉末b之元素組成及 /或結晶結構不同，但是兩者的平均粒徑之具體上的大小， ^ 不必在上述（2)的範圍，然而，以在該範圍爲佳。 上述（2)的手段，特定無機粉末A與無機粉末B的粒徑 如上述係重要的。亦即，無機粉末A的平均粒徑爲〇. 9〜1 .5 微米，較佳是0.9〜1.4微米，無機粉末B的平均粒徑爲1.5 〜2.5微米，較佳是1.4〜2.4微米，且無機粉末B —方的平 均粒徑必須較無機粉末A的平均粒徑大。無機粉末A與無 機粉末B之元素組成及/或結晶結構亦可以相同，兩者的軟 化點的關係，不必在上述（1 )的範圍，然而，以在該範圍爲 •佳。 又，本發明所使用的無機粉末，其粒子大小分布曲線以 ^ 具有至少二個極大尖鋒爲佳。該無機粉末可以舉出的有無機 ^ 粉末a或無機粉末b及其等之混合物、無機粉末A或無機粉 末B及其等之混合物。該粒子大小分布曲線係藉由雷射繞射 散射法，以粒徑爲橫軸、以頻率（體積）爲縱軸而繪出之物。 又，在本發明，平均粒徑係指該頻率的累積體積的總和爲 100%時之累積體積爲50%之粒徑（D50)(但是，粒子大小分布 1280256 曲線不一定要有極大尖鋒，然而在D50附近有極大尖鋒爲 佳）。 欲使無機粉末具有至少二個極大尖鋒，可以調配賦予其 極大尖鋒之粉末成分的調配比率，使各自粉末的平均粒徑在 本發明的範圍。 因而，此時，賦予極大尖鋒的粉末成分的粒子大小分布 / 曲線，可以進行各種選定。 而且，在本發明，使粒子大小分布曲線的總和爲1 〇〇% ^ 時之累積體積爲10°/。之粒徑（D 10)，無機粉末a或是無機粉 ❿ 末A時以0·1〜1.5微米爲佳，無機粉末b或是無機粉末B 時以0 · 5〜2 · 3微米爲佳。 又，在本發明，使粒子大小分布曲線的總和爲1 00%時 之累積體積爲90%之粒徑（D90)，無機粉末a或是無機粉末A 時以1.0〜6·0微米爲佳，無機粉末b或是無機粉末B時以 1 · 5〜7微米爲佳。 可以認爲，在如上述進行特定無機粉末時，非感光性組 φ 成物的塗布層成爲在無機粉末b或是無機粉末B的間隙塡充 _ 有無機粉末a或是無機粉末A之結構，且藉由煅燒後大小與 軟化點的不同之助，可以生成如上述的空隙。 ~ 而且，爲了有助於在特定上述大小或軟化點之同時調整 空隙面積率，非感光性組成物的組成係重要因素，例如，可 以舉出的有適當地選定黏合劑、溶劑、可塑劑等、以及煅燒 條件等。 又，本發明的非感光性組成物，亦可以含有上述特定粉 1280256 末成分以外的無機成分。該無機成分例如可以使用大小、軟 化點不同的無機粉末。例如，亦可以使用平均粒徑爲5 0奈 米以下的膠體狀二氧化矽等。 本發明之無機材料膜的高度爲50〜800微米，作爲隔壁 使用時，長寬比（aspect ratio)以1〜10爲佳。 又，本發明的無機材料膜的介電常數以3 . 5〜1 2爲佳。 本發明之非感光性組成物可以直接塗布在基板上，亦可 以塗布在薄膜上，然後轉印至基板上形成膜。1280256 degrees high. However, it is necessary to make the blasting property of the dielectric layer forming layer and the partition forming layer different during blasting, and it is desirable to remove only the partition forming layer of the opening portion of the photoresist pattern while leaving the lower dielectric layer in the blasting process. Layer, but the difference between sandblasting is not easy. Further, when a pattern is formed by using a photosensitive dry film and a sand-blast method for a dielectric layer, the adhesion between the barrier layer forming layer and the photosensitive photoresist is poor, and there is a problem of peeling during development or sand blasting. presence. Further, when the dielectric constant of the dielectric layer is lowered, there is a problem that the glass composition has an increased softening point 2. Further, in the calcination step, there is a problem that the positionality of the shrinkage is uneven, the crack is likely to be generated due to the large shrinkage, and the partition wall is easily slackened and deformed during the calcination after the blasting. Further, there are problems such as high dielectric constant of the partition wall after completion of firing, heat generation, and power consumption. It is desirable to have a material which does not impair the blasting property, has good adhesion to the photosensitive irritating photoresist, and does not cause slack, deformation or cracking during firing, and can be used as a barrier layer forming layer having a low dielectric constant. φ Patent Document 3 discloses a method in which, when the inorganic composition is coated, the pattern defect at the time of sand blasting, and the crack at the time of firing are used, the mash is mixed with inorganic particles having two kinds of average particle sizes. The pattern is formed by screen printing. However, a fine pattern having a high resolution cannot be formed after the calcination, and since printing is used, the uniformity and the like are not sufficiently satisfied. Patent Document 4 discloses a dielectric paste using a glass having a particle size distribution of two sharp points. However, the tanning material used in the present invention is not contained, and J280256 cannot be provided to form the partition wall. Further, a method of forming a transfer film is not described. Further, Patent Documents 5 to 13 disclose a partition wall forming method using a mold. However, even if such methods are used, it is not easy to obtain a film having a thick film thickness and which does not cause cracks or localized sentences. Further, Patent Document 14 discloses a method for producing a PDP in which a porous partition wall is used in order to sufficiently detach the air in the pixel surface when the phosphor paste is extruded into the inner surface of the pixel. However, it is not described which material is used, and the degree of porosity such as the size of the porous void and the porosity is not described. Further, Patent Document 15 discloses that by forming a layer having more pores than the partition wall on the surface of the partition wall, the impure gas is not easily mixed into the discharge space when the panel emits light, and the indulgence purity in the discharge space can be maintained, and the luminance can be improved. . However, the principle of low dielectric constant is not disclosed at all, and the degree of porosity such as the void size and void ratio of the layer on the surface of the partition wall is not described. Cracks at the time of calcination were also not described at all. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. 2000-185. [Patent Document 9] JP-A-2002-134005 (Patent Document 11) JP-A-2000-173456 (Patent Document 12) Japanese Laid-Open Patent Publication No. JP-A No. 5-47303 (Patent Document 15) JP-A-2002-324491 SUMMARY OF THE INVENTION The present invention provides an inorganic material film, an inorganic material film structure, a method for producing the same, and a transfer film used for the production thereof, the inorganic material film, and the inorganic material film structure. It has a low dielectric constant and can provide a PDP or the like for power saving that can suppress heat generation. Further, the present invention provides an inorganic material film having a high precision and a fine structure, an inorganic material film structure, a method for producing the same, and a transfer film used for the production thereof, the inorganic material film and the inorganic material film structure being After the calcination, the line width or film thickness of the various patterns of the partition walls or the dielectric body hardly changed. Moreover, the present invention can provide a transfer film which can form various patterns of partition walls or dielectrics on a substrate as compared with a coating method such as screen printing, and provide an inorganic material film structure using the transfer film. Manufacturing method. Further, the present invention provides a transfer film which is excellent in adhesion to a substrate by a non-photosensitive composition for forming various patterns of a partition wall and a dielectric body, and which is also excellent in adhesion to a photosensitive photoresist, and is provided for use. A method of producing an inorganic material film structure of the transfer film. The present invention is as described below, whereby the above problems can be solved. (1) An inorganic material film characterized by calcining a porous inorganic material film obtained by containing at least a non-photosensitive composition of inorganic powder 1280256, wherein the inorganic material film has a void area ratio of 20 to 65%, and a void The size is 5~2 0 microns. (2) The inorganic material film according to (1), wherein the inorganic powder is composed of at least two types having different average particle diameters and softening points, and a type having a larger average particle diameter has a higher softening point. (3) The inorganic material film according to (2), wherein the inorganic powder is composed of an inorganic powder a and an inorganic powder b having a softening point higher than that and having an average particle diameter larger than that. (4) The inorganic material film according to any one of (1) to (3), wherein the inorganic powder is an inorganic powder A having an average particle diameter of from 0. 9 to 1 · 5 μm, and an average particle diameter is larger than The inorganic powder B having an average particle diameter of 1 · 5 to 2 · 5 μm is composed. (5) An inorganic material film structure obtained by providing an inorganic material film according to any one of (1) to (4) on a substrate. (6) A method for producing an inorganic material film structure, comprising the steps of: providing a non-photosensitive composition according to any one of (1) to (4) on a substrate, and providing a photosensitive film on the non-photosensitive composition After the exposure and development treatment, the non-photosensitive composition is patterned, and then calcined to obtain the inorganic material film structure described in the above (5). (7) The method for producing an inorganic material film structure according to the above (6), wherein the non-photosensitive composition provided on the substrate of the above (6) is formed by coating on a flexible temporary support. The transfer film of the layer is transferred to the substrate by transferring the coating layer. (8) A transfer film comprising a coating layer comprising the non-photosensitive composition according to (6) above, in a flexible temporary support. 1280256 [Effect of the Invention] The non-photosensitive composition of the present invention contains at least two types of inorganic powders having different average particle diameters and softening points, and a porous dielectric material having a low dielectric constant can be obtained. A film and a materialless film structure containing the porous inorganic material film. Further, according to the present invention, a coating layer having the non-photosensitive composition in the flexible temporary support can be used as a transfer film, and an accurate electronic device such as a PDP can be provided, and the adhesion between the transfer coating layer and the substrate is good. And the photosensitive dry film has good adhesion to the transfer coating layer, and the uncalcined pattern has high precision by development, and can be easily manufactured, and has small variation in line width and film thickness after calcination, and high precision. And save the power of the pattern. [Embodiment] The inorganic material film of the present invention and the inorganic material film of the inorganic material film structure in which the inorganic material film is provided on the substrate have a porous property and define a void area ratio and a void size. Special range of things. According to the above-described configuration, the non-photosensitive composition is formed into various patterns of the separator or the dielectric, and then the various patterns obtained are fired, and the porous layer is formed by having appropriate voids therein, thereby improving resistance. When the shrinkage rate is the same as #, the effect of lowering the dielectric constant can be obtained. Reducing the dielectric constant has the effect of suppressing heat generation such as PDP and reducing power consumption. Further, according to the form of the transfer film, the coating layer of the non-photosensitive composition can be transferred to the support to obtain a smooth surface texture of the transfer coating layer, and can be formed with good precision on a desired support. An excellent pattern of contours. 1280256 The face slitting material machine does not have the gap size of the hole in the face gap and the small gap α, which means the longest diameter of the section (the distance between 2 points), The present invention is preferably 5 to 20 μm, more preferably 5.2 to 18 μm. The void area means the sum of the cross-sections of the holes, and the area of each cross-section can be drawn on the tracing paper by the portion of the hole in the S E Μ cross-sectional photograph, which is determined by cutting the weighing quality. The cross-sectional shape of the hole is not particularly limited 'may be amorphous or circular. Further, the ratio of the void area of the present invention is defined as the void area ratio with respect to the sectional area of the inorganic material film. Here, the void area ratio means that a cross section of the inorganic material film is taken as an SEM photograph, and the average of the measured enthalpy is obtained from three cross sections having a size of 00 μm χ 1 μm. The void ratio of the inorganic material film of the present invention is from 20 to 65 %, more preferably from 2 5 to 60%. In the present invention, the means for controlling the porosity of the inorganic material film to the above range is as follows. The inorganic powder is a material having a high softening point which is composed of at least two types having different average particle diameters and softening points and having a large average particle diameter, and the following preferable means can be mentioned. Here, the inorganic powder having different average particle diameters and softening points from each other is described as the inorganic powders a, b, and C in the order of the lowercase Roman alphabet from the smaller average particle diameter and the softening point. (J, · · · 〇 (1) A mixture of inorganic powder a and inorganic powder b is used as the inorganic powder. -12- 1280256 (2) An average particle diameter of 〇·9 to 1.5 μm of inorganic powder a and an average particle A mixture of inorganic powders b having a larger diameter and an average particle diameter of 1.5 to 2 μm is used as the inorganic powder. The means (1) above preferably optimizes the softening point of the inorganic powder b to be inorganic. The softening point of the powder a is higher than 50 ° C, more preferably higher than the loot: one. The softening point of the higher side is preferably 600 to 150 ° C, to 7 0 0 '1 400 °c is more preferable. 'The inorganic powder a and the inorganic powder b have different elemental compositions and/or crystal structures, but the specific size of the average particle diameter of the two, ^ does not have to be in the range of the above (2) However, it is preferable in the range. The means (2) above, the specific inorganic powder A and the inorganic powder B The diameter is as important as the above. That is, the inorganic powder A has an average particle diameter of 〜. 9 to 1.5 μm, preferably 0.9 to 1.4 μm, and the inorganic powder B has an average particle diameter of 1.5 to 2.5 μm, preferably It is 1.4 to 2.4 μm, and the average particle diameter of the inorganic powder B is larger than the average particle diameter of the inorganic powder A. The elemental composition and/or the crystal structure of the inorganic powder A and the inorganic powder B may be the same, and the softening of the two The relationship of the points is not necessarily in the range of the above (1), however, it is preferable in the range. Further, the inorganic powder used in the present invention preferably has a particle size distribution curve having at least two extreme sharp points. The inorganic powder may be exemplified by inorganic powder a or inorganic powder b and the like, a mixture of inorganic powder A or inorganic powder B, and the like. The particle size distribution curve is by laser diffraction scattering method. The particle diameter is the horizontal axis and the frequency (volume) is plotted on the vertical axis. Further, in the present invention, the average particle diameter means that the cumulative volume of the cumulative volume of the frequency is 100%, and the cumulative volume is 50%. Particle size (D50) (however, particle size distribution 1280256 The curve does not have to have a sharp spike, but there is a great spike near D50.) To make the inorganic powder have at least two extreme sharps, you can mix the blending ratio of the powder components that give it a great spike. The average particle diameter of the powder is within the scope of the present invention. Therefore, at this time, the particle size distribution/curve of the powder component which gives a sharp spike can be variously selected. Further, in the present invention, the sum of the particle size distribution curves is 1 The cumulative volume of 〇〇% ^ is 10 ° /. The particle size (D 10), inorganic powder a or inorganic powder A is preferably 0.1 to 1.5 μm, inorganic powder b or inorganic powder B. It is preferably 0. 5~2 · 3 microns. Further, in the present invention, the cumulative volume of the particle size distribution curve is 100% when the cumulative volume is 90% (D90), and the inorganic powder a or the inorganic powder A is preferably 1.0 to 0.6 μm. The inorganic powder b or the inorganic powder B is preferably 1 · 5 to 7 μm. When the specific inorganic powder is carried out as described above, the coating layer of the non-photosensitive group φ product is configured to be filled with inorganic powder a or inorganic powder A in the gap between the inorganic powder b or the inorganic powder B. Further, by the difference in size and softening point after calcination, voids as described above can be produced. Further, in order to contribute to the adjustment of the void area ratio at the specific size or softening point, the composition of the non-photosensitive composition is an important factor, and for example, a binder, a solvent, a plasticizer, etc. may be appropriately selected. And calcination conditions, and the like. Further, the non-photosensitive composition of the present invention may contain an inorganic component other than the final component of the specific powder 1280256. As the inorganic component, for example, an inorganic powder having a different size and softening point can be used. For example, colloidal cerium oxide having an average particle diameter of 50 nm or less can also be used. The inorganic material film of the present invention has a height of 50 to 800 μm, and when used as a partition wall, the aspect ratio is preferably 1 to 10. Further, the dielectric material of the inorganic material film of the present invention preferably has a dielectric constant of 3.5 to 12. The non-photosensitive composition of the present invention may be directly coated on a substrate, or may be coated on a film and then transferred onto a substrate to form a film.
本發明的轉印薄膜，以在非感光性組成物的塗布層與可 撓曲性暫時支撐體之間具有脫模性層爲佳。 脫模性層係設置成能夠容易且正確地將非感光性組成 物的塗布層轉印至玻璃等基板上。 脫模性層可以舉出的有將脫模劑設置在基板上而成之 物，脫模劑可以舉出的有聚矽氧系化合物（例如，高黏度聚 矽氧系化合物、低黏度聚矽氧系化合物、改質聚矽氧系化合 物）、氟系化合物、植物油脂系化合物（例如，以植物性的磷 脂體（卵磷酯）爲主要成分之物）、鱲等。 本發明之轉印薄膜，亦可以將脫模性層與塗布層一同轉 印至基板上，亦可以將脫模性層留在可撓曲性暫時支撐體上 而只轉塗布層。因而，使用本發明的轉印薄膜，在基板上轉 印非感光性組成物的塗布層所得到的轉印塗布層亦可以具 有脫模性層。 又，使用本發明的轉印薄膜時，可以使轉印塗布層的表 面平滑，其中心平均表面粗糙度（Ra)以0.5微米以下爲佳， 1280256 以0.3微米以下爲更佳。 本發明之無機材料膜構造物的製造方法之一，可以舉出 的有在基板上形成來自上述本發明的轉印薄膜之該轉印塗 布層，在該轉印塗布層上設置感光性組成物，曝光、顯像處 理後，在非感光性組成物形成圖案，隨後進行煅燒。 以下，詳述本發明之各構成要素。 " A .可撓曲性暫時支撐體 本發明的轉印薄膜所使用的可撓曲性暫時支撐體，係可 ^ 以負載來自塗布的非感光性組成物之物。由該塗設的非感光 性組成物所構成的塗布層，可以經時性保存，使用時在轉印 至玻璃基板等基板之同時，可以剝離可撓曲性暫時支撐體。 此種可撓曲性暫時支撐體，若發揮上述機能時，其材 料、形態等沒有特別限制。可撓性暫時支撐體的材料通常可 以使用樹脂薄膜，例如，可以舉出的有聚酯系（例如，聚對 苯二甲酸乙二酯、聚萘二甲酸乙二酯等）、聚烯烴系（例如， 聚乙烯、聚丙烯等）、聚醯胺系（例如耐綸、阿拉米德（Aramid) φ 等）、聚醯亞胺系、聚颯系、纖維素等，可以按照使用目的， 適當地選定其種類 '物性（例如，楊氏率、熱膨脹率、表面 粗糙度等）、厚度等。 Λ 又，可撓曲性暫時支撐體，除了樹脂成分以外，可以含 有例如無機粉末、脫模劑等。又，亦可以對可撓曲性暫時支 撐體之設置有非感光性組成物那一側的面，進行物理性及/ 或化學性處理。例如，可以舉出的上塗層處理（設置前述脫 模性層’例如蠟塗層、聚矽氧塗層等樹脂塗層等）、金屬蒸 -16- 1280256 鍍處理、濺鍍處理、鍍敷處理、除塵埃處理、鹼處理、熱處 理、電暈放電處理、電漿處理等。 B .非感光性組成物 本發明的非感光性組成物，或是塗布可撓曲性暫時支撐 體上成爲塗布層之非感光性組成物，係至少含有無機粉末、 更含有樹脂及溶劑作爲成分。非感光性組成物除了上述成分 ^ 以外’可以含有眾所周知之各種添加劑，例如可塑劑、保存 劑、界面活性劑等。 2 但是，因爲非感光性組成物係可以提高無機粉末成分的 調配率之組成，爲了有效地發揮其優點，有機成分以盡量少 添加爲佳。 B - a.無機粉末 無機粉末沒有特別限定，對經煅燒過的無機材料膜能夠 賦予不透明性爲主的機能，例如，可以舉出的有氧化鋁、氧 化鈦、氧化鉻、堇青石（cordierite)等金屬氧化物、金屬等， g 對經煅燒過的無機材料膜能夠賦予透明性爲主的機能之無 φ 機物質，例如，可以舉出的有玻璃、較佳是低熔點玻璃等。 低熔點玻璃粉末係意指軟化點爲3 90〜990 °C之物，線性 熱膨脹係數爲（45〜100)χ1(Τ7Κ— 1，以（50〜90)χ1〇-7Κ- 1之 物爲佳。 低熔點玻璃粉末的組成，氧化矽以調配在3〜8 0質量°/〇 之範圍爲佳，以1 0〜7 0質量％之範圍爲更佳。小於3質量％ 時，玻璃層的緻密性、強度或安定性降低，而且，熱膨脹係 數從希望値偏離，容易與玻璃基板產生失配（miss match)。 1280256 又，藉由小於70質量％，具有熱軟化點變低、能夠燒結在玻 璃基板上。 低熔點玻璃粉末的組成，使用含有5〜60質量％之氧化 鉍、氧化鉛、氧化鋅、氧化鋁、氧化鋰、氧化鈉、氧化鈣中 至少1種類之物，或是合計含有8〜60質量％之氧化硼、氧 化鉍或是氧化鉛且含有〇〜1 5質量％之氧化鋰、氧化鈉、氧 化鉀中至少1種類之玻璃粒子而成的玻璃，因融點較低，乃 是較佳。The transfer film of the present invention preferably has a release layer between the coating layer of the non-photosensitive composition and the flexible temporary support. The release layer is provided so that the coating layer of the non-photosensitive composition can be easily and accurately transferred onto a substrate such as glass. The release layer may be one obtained by disposing a release agent on a substrate, and the release agent may be a polyoxo-based compound (for example, a high-viscosity polyoxo compound, a low-viscosity polypene). An oxygen-based compound, a modified polyoxo-oxygen compound), a fluorine-based compound, a vegetable oil-based compound (for example, a plant-based phospholipid (lecithin) as a main component), hydrazine or the like. In the transfer film of the present invention, the release layer may be transferred onto the substrate together with the coating layer, or the release layer may be left on the flexible temporary support to be transferred only to the coating layer. Therefore, the transfer coating layer obtained by transferring the coating layer of the non-photosensitive composition on the substrate by using the transfer film of the present invention may have a release layer. Further, when the transfer film of the present invention is used, the surface of the transfer coating layer can be made smooth, and the center average surface roughness (Ra) is preferably 0.5 μm or less, and 1280256 is preferably 0.3 μm or less. One of the methods for producing the inorganic material film structure of the present invention includes the transfer coating layer formed on the substrate from the transfer film of the present invention, and a photosensitive composition is provided on the transfer coating layer. After the exposure and development treatment, a pattern is formed on the non-photosensitive composition, followed by calcination. Hereinafter, each constituent element of the present invention will be described in detail. " A. Flexible Temporary Support The flexible temporary support used in the transfer film of the present invention is capable of supporting a non-photosensitive composition from a coating. The coating layer composed of the applied non-photosensitive composition can be stored over time, and can be peeled off from the substrate such as a glass substrate during use, and the flexible temporary support can be peeled off. When such a flexible temporary support is used, the material, form, and the like are not particularly limited. As the material of the flexible temporary support, a resin film can be usually used, and examples thereof include a polyester (for example, polyethylene terephthalate or polyethylene naphthalate) and a polyolefin (for example). For example, polyethylene, polypropylene, etc., polyamines (for example, nylon, Aramid φ, etc.), polyimine, polyfluorene, cellulose, etc., may be appropriately used according to the purpose of use. The type 'physical properties (for example, Young's rate, thermal expansion rate, surface roughness, etc.), thickness, and the like are selected. Further, the flexible temporary support may contain, for example, an inorganic powder or a release agent in addition to the resin component. Further, physical and/or chemical treatment may be performed on the side of the flexible temporary support which is provided with the non-photosensitive composition. For example, an overcoat treatment (providing the above-mentioned release layer such as a resin coating such as a wax coating or a polyoxynitride coating), a metal evaporation-16-1280256 plating treatment, a sputtering treatment, and a plating may be mentioned. Treatment, dust removal treatment, alkali treatment, heat treatment, corona discharge treatment, plasma treatment, and the like. B. Non-photosensitive composition The non-photosensitive composition of the present invention or a non-photosensitive composition which is applied as a coating layer on a flexible temporary support, contains at least an inorganic powder, a resin and a solvent as components. . The non-photosensitive composition may contain various additives such as a plasticizer, a preservative, a surfactant, and the like in addition to the above components. 2 However, since the non-photosensitive composition can improve the composition of the blending ratio of the inorganic powder component, it is preferable to minimize the organic component in order to effectively exhibit its advantages. B - a. The inorganic powder inorganic powder is not particularly limited, and a function of imparting opacity to the calcined inorganic material film can be imparted, and examples thereof include alumina, titanium oxide, chromium oxide, and cordierite. For example, a metal oxide, a metal, or the like, g, which is a function of imparting transparency to the calcined inorganic material film, may be, for example, glass, preferably low-melting glass. The low-melting glass powder means a softening point of 3 90 to 990 ° C, and the linear thermal expansion coefficient is (45 to 100) χ 1 (Τ7Κ-1, preferably (50~90) χ1〇-7Κ-1) The composition of the low-melting glass powder, the cerium oxide is preferably in the range of 3 to 80% by mass/〇, preferably in the range of 10 to 70% by mass, and more preferably less than 3% by mass. The properties, strength, or stability are lowered, and the coefficient of thermal expansion deviates from the desired enthalpy, which easily causes a mismatch with the glass substrate. 1280256 Further, by having a thermal softening point of less than 70% by mass, it can be sintered in the glass. On the substrate, the composition of the low-melting glass powder is at least one of 5 to 60% by mass of cerium oxide, lead oxide, zinc oxide, aluminum oxide, lithium oxide, sodium oxide or calcium oxide, or a total of 8 ～60% by mass of boron oxide, cerium oxide or lead oxide, and glass containing at least one type of lithium oxide, sodium oxide or potassium oxide of 〇1 to 15% by mass, because of a low melting point It is better.
低熔點玻璃粉末的組成，較佳的例子，可以例示的有（1) 氧化鉛、氧化硼、氧化矽（Pb0-B203-Si02系）的混合物、（2) 氧化鋅、氧化硼、氧化砂（Ζ η Ο - Β 2 Ο 3 - S i Ο 2系）的混合物、（3 ) 氧化錯、氧化硼、氧化砂、氧化銘（P b Ο - B 2 Ο 3 - S i Ο 2 - A12 Ο 3系） 的混合物、（4)氧化鉛、氧化鋅、氧化硼、氧化矽 (Pb0-Zn0-B203-Si02 系）的混合物等。 而且，可以例示的有（5)氧化錫、氧化鋅、氧化磷系 (SnO-ZnO-P2〇5系）的混合物、（6)氧化銅、氧化磷系 (CuO-P2〇5系）的混合物、（7)氧化鉍、氧化硼系（Bi2〇3-B2〇3 系）的混合物等。 特別是在上述（1)〜（7)之去除鉛成分而成的混合物，所 謂無鉛玻璃，不只是環境保全上較佳，且可以有效地降低無 機材料膜的介電常數，應用於PDP用零件時，省電力性優 良’而且’與氧化鋁等金屬氧化物粉末的混煉性亦變佳，可 以改良無機質膜的均勻性。 又’無鉛玻璃除了上述成分以外，可以含有1種以上選 -18- 1280256 自 BaO、CaO、MgO、Na20、K20、Li2〇、Al2〇3、Ti〇2、Zr〇2、 Nb205、Bi203、SrO、V2 05、CuO等，可以更調配希望的元 素。 無給玻璃’以至少含有ZnO、B2O3、SnO、Si〇2、？2〇5、 BaO及Bi203中至少1種以上爲佳。莫耳比時，該組成以 ZnO/B203/SnO/Si02/P2〇5/BaO/Bi203/其他=20 〜70/0 〜80/0 〜55/0〜45/0〜60/0〜50/0〜15/0〜15爲佳，以25〜65/0〜 75/0〜50/0〜40/0〜55/0〜45/0〜13/0〜13爲更佳。 藉由在非感光性組成物添加特定的無機粉末成分以外 的各種金屬氧化物，可以對圖案著色。例如，藉由使非感光 性組成物含有1〜1 〇質量％之黑色的金屬氧化物，可以形成 黑色的圖案。使用於該目的之黑色或是其他經著色的氧化 物，可以藉由含有Cr、Fe、Co、Mn、Cu的氧化物中至少1 種，較佳是含有3種以上而能夠黑色化。特別是藉由使Fe 與Μη的氧化物各自含有0·5質量％以上，可以形成黑色的 圖案。 參The composition of the low-melting glass powder, preferably exemplified, is (1) a mixture of lead oxide, boron oxide, cerium oxide (Pb0-B203-SiO 2 type), (2) zinc oxide, boron oxide, or oxidized sand ( Ζ η Ο - Β 2 Ο 3 - S i Ο 2 series), (3) Oxidation error, boron oxide, oxidized sand, oxidation (P b Ο - B 2 Ο 3 - S i Ο 2 - A12 Ο 3 a mixture of (4) lead oxide, zinc oxide, boron oxide, cerium oxide (Pb0-Zn0-B203-SiO2 system), and the like. Further, examples thereof include (5) a mixture of tin oxide, zinc oxide, phosphorus oxide (SnO-ZnO-P2〇5), and (6) a mixture of copper oxide and phosphorus oxide (CuO-P2〇5). And (7) a mixture of cerium oxide, boron oxide (Bi2〇3-B2〇3), and the like. In particular, in the mixture of the lead components removed in the above (1) to (7), the lead-free glass is not only environmentally safe, but also can effectively reduce the dielectric constant of the inorganic material film, and is applied to parts for PDP. In this case, the electric power is excellent, and the kneading property with the metal oxide powder such as alumina is also improved, and the uniformity of the inorganic film can be improved. In addition to the above components, the lead-free glass may contain one or more selected from 18 to 1280256 from BaO, CaO, MgO, Na20, K20, Li2〇, Al2〇3, Ti〇2, Zr〇2, Nb205, Bi203, SrO. , V2 05, CuO, etc., can be more equipped with the desired elements. The glass is not provided to contain at least ZnO, B2O3, SnO, Si〇2? At least one of 2〇5, BaO and Bi203 is preferred. In the case of Mohr ratio, the composition is ZnO/B203/SnO/SiO 2 /P 2 〇 5 / BaO / Bi 203 / Other = 20 〜 70 / 0 〜 80 / 0 〜 55 / 0 〜 45 / 0 ~ 60 / 0 ~ 50 / 0 to 15/0 to 15 is preferable, and 25 to 65/0 to 75/0 to 50/0 to 40/0 to 55/0 to 45/0 to 13/0 to 13 are more preferable. The pattern can be colored by adding various metal oxides other than the specific inorganic powder component to the non-photosensitive composition. For example, a black pattern can be formed by allowing the non-photosensitive composition to contain 1 to 1% by mass of a black metal oxide. The black or other colored oxide to be used for this purpose can be blackened by containing at least one of oxides of Cr, Fe, Co, Mn, and Cu, preferably three or more. In particular, a black pattern can be formed by containing each of Fe and 的η oxide in an amount of 0.5% by mass or more. Reference
而且，除了黑色以外，亦可以藉由使用添加紅、藍、綠 等發色顏料而成的非感光性組成物，來形成各色的隔壁、彩 色濾光片等著色圖案的無機材料膜。 Β — b ·樹脂 在非感光性組成物中所含有的樹脂，沒有特別限制，可 以使用纖維素化合物或丙烯酸化合物。 (纖維素化合物） 非感光性組成物所使用的纖維素化合物，含有甲基纖維 -19- 1280256 素及其衍生物。纖維素化合物有乙基纖維素、甲基纖維素、 乙基丙基纖維素、硝化纖維素、乙酸纖維素、丙酸纖維、乙 酸丁酸纖維素、丁酸纖維素等纖維素系樹脂。 纖維素衍生物的取代基的取代率，爲纖維素羥基的〇〜 90%，以的10〜80%爲佳。例如乙基纖維素時，以1()〜7〇% 的取代率爲佳。此等黏合劑，可以使用單獨一種，又，聚合 物之間互相混合時，亦可以與上述以外的纖維素衍生物或是 非纖維系聚合物混合使用。混合比率係若能夠混合且可以維 ^ 持黏合劑的機能時，可以是任何混合比率。 使用作爲黏合劑之纖維素衍生物，除了上述以外，亦可 以添加使用水溶性基取代的纖維素衍生物作爲次要成分，該 樹脂除了水溶性基以外，亦可以含有低碳數醇基或是低碳數 醯基作爲取代基。取代基的水溶性基爲羥基烷基（碳數1〜3 ) 及殘基甲基。 此等羥基烷基纖維素之羥基烷基的取代率係每1單位葡 春 萄糖爲I·3〜7.0當量，以1.5〜5.0當量爲佳。取代率當每i φ 單位葡萄糖大於3 · 0時，意指羥基烷基取代的該羥基烷基進 而被取代。取代率小於1 ·3當量時，溶解性、混和性變爲不 充分，大於7.0當量時，取代度不容易提升、製造成本變高。 特佳之水溶性基取代纖維衍生物有羥基丙基纖維素、羥基甲 基纖維素、羥基乙基纖維素、羧基甲基纖維素、羧基乙基纖 維素、羧基丙基甲基纖維素、羥基甲基苯二甲酸纖維素、羥 基丙基甲基苯二甲酸纖維素、羥基丙基甲基乙酸丁酸纖維 素、硫酸纖維素。 •20- 1280256 甲基纖維素可以由鹼纖維素與甲基氯或二甲基硫酸，經 由常用方法合成得到。而且，經由常用方法與環氧乙烷反應 可以得到經基乙基甲基纖維素。乙基纖維素可以使鹼纖維素 在加壓下與乙基氯反應而得到。此外的烷基纖維素亦可以藉 由同樣的方法來合成。羥基乙基纖維素可以藉由常用方法由 纖維素與環氧乙烷合成得到。羧基甲基纖維素可以在苛性鹼 — 的存在下使纖維素與一氯乙酸反應而得到。又，硫酸纖維素 可以藉由常用方法使纖維素與二甲基甲醯胺反應得到。此外 ^ 的纖維素衍生物亦可以同樣地使用眾所周知的方法合成得 到。又，市面亦有銷售。 (丙烯酸化合物） 丙烯酸化合物含有下述通式（1 )所示（甲基）丙烯酸酯化 合物（R1係氫原子時之丙烯酸酯化合物及R1係甲基時之甲基 丙燒酸酯化合物的總稱）之單獨聚合物（1 a )、2種以上下述通 式（1)所示（甲基）丙烯酸酯化合物之共聚物（1 b )、以及下述通 式（1 )所示（甲基）丙烯酸酯化合物與其他共聚合性單體之共 2聚物（lc)。 H2C = C(R1)COOR2 (1) (式中，R1係表示氫原子或甲基，R2係表示1價的有機 • 基。有機基可以舉出的有烷基、環烷基、羥基烷基、烷氧基、 芳氧基、聚伸烷二醇之半酯殘基、聚伸烷二醇單醚之酯殘基 等） 爲了生成單獨聚合物（la)及共聚物（lb)所使用之上述通 式（1)所示（甲基）丙烯酸酯化合物之具體例，可以舉出的有甲 -21 - 1.280256 基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、丙基（甲基）丙烯 酸酯、異丙基（甲基）丙烯酸酯、丁基（甲基）丙烯酸酯、異丁 基（甲基）丙烯酸酯、第三丁基（甲基）丙烯酸酯、戊基（甲基） 丙烯酸酯、正戊基（甲基）丙烯酸酯、異戊基（甲基）丙烯酸酯、 己基（甲基）丙烯酸酯、庚基（甲基）丙烯酸酯、辛基（甲基）丙 * 烯酸酯、異辛基（甲基）丙烯酸酯、乙基己基（甲基）丙烯酸酯、 / 壬基（甲基）丙烯酸酯、癸基（甲基）丙烯酸酯、異癸基（甲基） 丙烯酸酯、十一烷基（甲基）丙烯酸酯、十二烷基（甲基）丙烯 ^ 酸酯、月桂基（甲基）丙烯酸酯、硬脂基（甲基）丙烯酸酯、異 硬脂基（甲基）丙烯酸酯等烷基（甲基）丙烯酸酯；羥基乙基（甲 基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸酯、4-羥基丁基（甲 基）丙烯酸酯、3-羥基丙基（甲基）丙烯酸酯、2-羥基丁基（甲 基）丙烯酸酯、3-經基丁基（甲基）丙烯酸酯等羥基烷基（甲基） 丙烯酸酯；苯氧基乙基（甲基）丙烯酸酯、2-羥基-3-苯氧基丙 基（甲基）丙烯酸酯等苯氧基烷基（甲基）丙烯酸酯；2-甲氧基 乙基（甲基）丙烯酸酯、2-乙氧基乙基（甲基）丙烯酸酯、2-丙 φ 氧基乙基（甲基）丙烯酸酯、2 -丁氧基乙基（甲基）丙烯酸酯、 2-甲氧基丁基（甲基）丙烯酸酯等烷氧基烷基（甲基）丙烯酸 酯；聚乙二醇單（甲基）丙烯酸酯、乙氧基二伸乙甘醇（甲基） ' 丙烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯、苯氧基聚乙二 醇（甲基）丙烯酸酯、壬基苯氧基聚二醇（甲基）丙烯酸酯、聚 丙二醇單（甲基）丙烯酸酯、甲氧基聚丙二二醇單（甲基）丙烯 酸酯、乙氧基聚丙二醇單（甲基）丙烯酸酯、壬基苯氧基聚丙 二醇（甲基）丙烯酸酯等聚伸烷二醇（甲基）丙烯酸酯；環己基 -22- 1280256 (甲基）丙烯酸酯、4-丁基環己基（甲基）丙烯酸酯、二環戊烷 基（甲基）丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、二環戊二 烯基（甲基）丙烯酸酯、萡基（甲基）丙烯酸酯、異萡基（甲基） 丙烯酸酯、三環癸基（甲基）丙烯酸酯等環烷基（甲基）丙烯酸 酯；苄基（甲基）丙烯酸酯、四氫糠基（甲基）丙烯酸酯等。此 等之中，上述通式（1)中，R2所示的基，以含有烷基或是氧 " 基伸烷基爲佳，特佳之（甲基）丙烯酸酯化合物，可以舉出的 有甲基（甲基）丙烯酸酯、丁基（甲基）丙烯酸酯、乙基（甲基） ^ 丙烯酸酯、月桂基（甲基）丙烯酸酯、異癸基（甲基）丙烯酸酯 及2-甲氧基乙基（甲基）丙烯酸酯等。 爲了生成共聚物（1〇而使用、提供來與（甲基）丙烯酸酯 化合物進行共聚合之共聚合性單體，若能夠與上述（甲基）丙 烯酸酯化合物進行共聚合之化合物時，沒有特別限制，可以 舉出的有例如（甲基）丙烯酸、乙烯基苯甲酸、順丁烯二酸、 乙烯基苯二甲酸等不飽和羧酸類；乙烯基苄基甲醚、乙烯基 環氧丙醚、苯乙烯、α-甲基苯乙烯、丁二烯、異戊二烯等乙 ^ 烯基含有自由基聚合性化合物。在共聚物（1〇，來自上述通 式（1)所示（甲基）丙烯酸酯化合物的共聚合成分，通常爲40 質量％以上，以50質量％以上爲佳。 ^ 單獨聚合物（la)、共聚物（lb)或是（1C)之丙烯酸化合物 的分子量，藉由G P C所得到換算成聚苯乙燒的質量平均分 子量’以1，〇〇〇〜300,000爲佳，以2,000〜200,000爲更佳。 相對於每1 00質量份低熔點玻璃粉末成分，非感光性組 成物之樹脂含有比率以1〜2 0質量份爲佳，以1 5〜1 8質量 -23- 1280256 份爲更佳。樹脂的比率太少時，無法確實地黏著保持低熔點 玻璃粉末成分，另一方面，該比率太大時，需要長時間的煅 燒步驟、所形成的燒結體（無機材料膜）未具有充分強度的膜 厚度。 B — c ·溶劑及可塑劑 ' 構成本發明的非感光性組成物之溶劑，最好是與無機粉 ’ 末的親和性、對樹脂之溶解性良好、能夠賦予非感光性組成 物適當的黏性，同時可以容易地藉由乾燥而蒸發去除之物。 又’特佳的溶劑，可以舉出的有標準沸點（在1氣壓時之沸 φ 點）爲60〜3 00 °C之酮類、醇類及酯類等。 如此溶劑的具體例，可以例示的有二乙基酮、甲基丁基 酮、二丙基酮、庚酮、辛酮、環己酮、N-甲基吡咯啶酮等酮 類；甲醇、乙醇、丙醇、異丙醇、丁醇類、正戊醇、4-甲基 -2-戊醇、環己醇、7-溴-庚醇、辛醇、雙丙酮醇、甘油、苄 醇、松節油、葱品醇（terpineol)等醇類、乙二醇單甲醚、乙 二醇單乙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、 φ 二伸乙甘醇單乙醚、二伸乙甘醇單丁醚等醚系醇類；乙酸正 丁酯、乙酸戊酯等飽和脂肪族單羧酸烷基酯類；乳酸乙酯、 乳酸正丁酯等乳酸酯類；2-甲氧乙基乙酸酯（methyl cellosolve acetate)、2-乙氧乙基乙酸酯（ethyl cellosolve acetate)、丙二醇單甲醚乙酸酯、乙基-3-乙氧基丙酸酯、二 伸乙甘醇單乙醚乙酸酯、二伸乙甘醇單丁醚乙酸酯等醚系酯 類等，此等之中，以葱品醇、N-甲基吡咯啶酮、甲基丁基酮、 環己酮、雙丙酮醇、乙二醇單丁醚、丙二醇單甲醚、乳酸乙 -24- 1280256 性暫時支撐體上。 供塗布在非感光性組成物的黏度，以1〜3〇〇Pa · sec爲 佳。塗布機可以舉出的有輥塗布機、刮板塗布機、簾流塗布 機、線纜塗布機等，藉此可以將非感光性組成物塗布層塗布 在可撓曲性暫時支撐體上，將塗布層捲起成捲狀的狀態來保 ’ 存、供給。可撓曲性暫時支撐體的厚度可以舉出的有例如1 〇 / 〜1 00微米。構成轉印薄膜的塗布層，可以藉由將本發明的 非感光性組成物塗布在可撓曲性暫時支撐體上，使塗膜乾 ^ 燥、去除溶劑的一部分或全部來形成。將本發明的非感光性 組成物塗布在可撓曲性暫時支撐體上的塗布方法，以能夠效 率良好地在可撓曲性暫時支撐體上形成膜厚度均勻優良之 較厚（例如20微米以上）的塗膜爲佳。 又，在塗布本發明的非感光性組成物之可撓曲性暫時支 撐體的表面，以具有脫模性層爲佳。藉此，在將塗布層轉印 至基板上之步驟，可以容易地進行剝離可撓曲性暫時支撐體 的操作。又，亦可以在轉印薄膜上設置保護薄膜層。如此保 Φ 護薄膜層，可以舉出的有聚對苯二甲酸乙二酯薄膜、聚乙烯 薄膜、聚乙烯醇系薄膜等。 * 本發明的非感光性組成物，如上述，可以使用於製造轉 ^ 印薄膜的時候，亦可以使用於藉由網版印刷法將該非感光性 組成物直接塗布在玻璃基板等的表面，乾燥塗膜來形成塗布 層的方法。在此，供給藉由網版印刷法塗布於基板的步驟之 非感光性組成物的黏度以1 0〜2 0 0 0 P a · s e C爲佳。 D·無機材料膜構造物的製造方法 -26- 1280256 本發明的無機材料膜構造物的製造方法，以下述步驟的 方法爲佳，係從轉印薄膜將轉印塗布層形成在如玻璃板之基 板上，將感光性乾膜層積在該轉印塗布層的表面，使用在該 感光性乾膜上依順序進行圖案曝光、顯像而形成之光阻圖 案’藉由噴砂法在該基板上形成圖案，隨後煅燒而形成之方 • 法。Further, in addition to black, an inorganic material film of a colored pattern such as a partition wall or a color filter of each color may be formed by using a non-photosensitive composition obtained by adding a coloring pigment such as red, blue or green. Β — b · Resin The resin contained in the non-photosensitive composition is not particularly limited, and a cellulose compound or an acrylic compound can be used. (Cellulose compound) The cellulose compound used in the non-photosensitive composition contains methylcellulose-19-1280256 and its derivative. The cellulose compound may be a cellulose resin such as ethyl cellulose, methyl cellulose, ethyl propyl cellulose, nitrocellulose, cellulose acetate, propionic acid fiber, cellulose acetate butyrate or cellulose butyrate. The substitution ratio of the substituent of the cellulose derivative is 〇 to 90% of the cellulose hydroxy group, preferably 10 to 80%. For example, in the case of ethyl cellulose, a substitution ratio of 1 () to 7 % by weight is preferred. These binders may be used singly or in combination with a cellulose derivative or a non-fibrous polymer other than the above. The mixing ratio can be any mixing ratio if it can be mixed and can maintain the function of the binder. As the cellulose derivative as the binder, in addition to the above, a cellulose derivative substituted with a water-soluble group may be added as a secondary component, and the resin may contain a low carbon number alcohol group in addition to the water-soluble group or A low carbon number thiol group serves as a substituent. The water-soluble group of the substituent is a hydroxyalkyl group (carbon number 1 to 3) and a residue methyl group. The substitution ratio of the hydroxyalkyl group of the hydroxyalkylcellulose is from 1.3 to 7.0 equivalents per 1 unit of glucosinolate, preferably from 1.5 to 5.0 equivalents. The substitution ratio means that the hydroxyalkyl group substituted with the hydroxyalkyl group is substituted when the amount of glucose per i φ unit is more than 3.8. When the substitution ratio is less than 1,3-equivalent, the solubility and the miscibility are insufficient. When the substitution ratio is more than 7.0 equivalents, the degree of substitution is not easily improved, and the production cost is increased. Particularly preferred water-soluble substituted fiber derivatives are hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl methyl cellulose, hydroxyl group Cellulose phthalate, cellulose hydroxypropylmethyl phthalate, cellulose hydroxypropyl methyl acetate butyrate, cellulose sulfate. • 20-1280256 Methylcellulose can be synthesized from alkali cellulose with methyl chloride or dimethyl sulfate by conventional methods. Further, transethylethylcellulose can be obtained by a reaction with ethylene oxide by a usual method. Ethyl cellulose can be obtained by reacting alkali cellulose with ethyl chloride under pressure. Further alkyl cellulose can also be synthesized by the same method. Hydroxyethyl cellulose can be synthesized from cellulose and ethylene oxide by a usual method. Carboxymethylcellulose can be obtained by reacting cellulose with monochloroacetic acid in the presence of caustic. Further, cellulose sulfate can be obtained by reacting cellulose with dimethylformamide by a usual method. Further, the cellulose derivative can be similarly synthesized by a known method. Also, there are sales in the market. (Acrylic Compound) The acrylic compound contains a (meth) acrylate compound represented by the following formula (1) (a generic term for a methacrylate compound in the case of a hydrogen atom in the case of a hydrogen atom and a methylpropionate compound in the case of an R1 methyl group) The copolymer (1 b ) of the (meth) acrylate compound represented by the following general formula (1) and the (meth) condensed by the following formula (1) A 2-mer (lc) of a acrylate compound with other copolymerizable monomers. H2C = C(R1)COOR2 (1) (wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent organic group. The organic group may be an alkyl group, a cycloalkyl group or a hydroxyalkyl group. , alkoxy group, aryloxy group, half ester residue of polyalkylene glycol, ester residue of polyalkylene glycol monoether, etc.) used to form individual polymer (la) and copolymer (lb) Specific examples of the (meth) acrylate compound represented by the above formula (1) include methyl-21- 1.280256-based (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tbutyl butyl (meth) acrylate, pentyl (methyl) Acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (methyl) propyl * ene Acid ester, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, / mercapto (meth) acrylate, fluorenyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylate such as stearyl (meth) acrylate or isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ester, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-butyl butyl (meth) acrylate Isohydroxyalkyl (meth) acrylate; phenoxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate such as 2-hydroxy-3-phenoxypropyl (meth) acrylate Acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-prop φ oxyethyl (meth) acrylate, 2-butoxy Alkoxyalkyl (meth) acrylate such as ethyl ethyl (meth) acrylate or 2-methoxybutyl (meth) acrylate; polyethylene glycol single (Meth) acrylate, ethoxy diethylene glycol (methyl) 'acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate , nonylphenoxy polyglycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, ethoxy propylene glycol mono (methyl a polyalkylene glycol (meth) acrylate such as acrylate, nonylphenoxy polypropylene glycol (meth) acrylate; cyclohexyl-22- 1280256 (meth) acrylate, 4-butylcyclohexyl ( Methyl) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, decyl (meth) acrylate a cycloalkyl (meth) acrylate such as an ester, isodecyl (meth) acrylate or tricyclodecyl (meth) acrylate; benzyl (meth) acrylate, tetrahydro fluorenyl (methyl) Acrylate and the like. Among these, in the above formula (1), the group represented by R2 is preferably an alkyl group or an oxygen group, and a particularly preferred (meth) acrylate compound may be exemplified. Base (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-methoxy Ethyl ethyl (meth) acrylate or the like. In order to form a copolymer (a copolymerizable monomer which is used for copolymerization with a (meth) acrylate compound, if it is a compound which can copolymerize with the above (meth) acrylate compound, there is no particular The limitation includes, for example, unsaturated carboxylic acids such as (meth)acrylic acid, vinylbenzoic acid, maleic acid, and vinyl phthalic acid; vinylbenzyl methyl ether and vinyl epoxidized ether; The ethylenic group such as styrene, α-methylstyrene, butadiene or isoprene contains a radically polymerizable compound. In the copolymer (1〇, from the above formula (1) (methyl) The copolymerization component of the acrylate compound is usually 40% by mass or more, preferably 50% by mass or more. ^ The molecular weight of the acrylic compound of the polymer (la), the copolymer (lb) or (1C) alone, by GPC The mass average molecular weight obtained in the conversion to polystyrene is preferably from 1, 〇〇〇 to 300,000, more preferably from 2,000 to 200,000. Non-photosensitive composition per 100 parts by mass of the low-melting glass powder component Resin The ratio is preferably from 1 to 20 parts by mass, more preferably from 1 5 to 18 parts -23 to 1280256 parts. When the ratio of the resin is too small, the low-melting glass powder component cannot be surely adhered. On the other hand, When the ratio is too large, a long-time calcination step is required, and the formed sintered body (inorganic material film) does not have a film thickness of sufficient strength. B - c · Solvent and plasticizer' constitute the non-photosensitive composition of the present invention The solvent preferably has an affinity with the inorganic powder and a good solubility to the resin, and can impart a suitable viscosity to the non-photosensitive composition, and can be easily evaporated and removed by drying. Examples of the solvent include ketones, alcohols, and esters having a normal boiling point (boiling point at 1 atmosphere) of 60 to 300 ° C. Specific examples of such a solvent are exemplified by two. Ketones such as ketone, methyl butyl ketone, dipropyl ketone, heptanone, octanone, cyclohexanone, N-methylpyrrolidone; methanol, ethanol, propanol, isopropanol, butanol, N-pentanol, 4-methyl-2-pentanol, cyclohexanol, 7-bromo-heptanol, octanol, Alcohols such as diacetone alcohol, glycerin, benzyl alcohol, turpentine, terpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,醚 Diethylglycol monoethyl ether, diethylene glycol monobutyl ether and other ether alcohols; n-butyl acetate, amyl acetate and other saturated aliphatic monocarboxylic acid alkyl esters; ethyl lactate, lactate Lactic acid esters such as esters; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl-3-B An ether ester such as oxypropionate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate, among which, onion alcohol, N-methylpyrrole Iridone, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, lactate B-24- 1280256 temporary support. The viscosity to be applied to the non-photosensitive composition is preferably 1 to 3 Å Pa · sec. The coater may be a roll coater, a blade coater, a curtain coater, a cable coater or the like, whereby the non-photosensitive composition coating layer may be applied onto the flexible temporary support. The coating layer is wound up in a roll shape to keep it in storage. The thickness of the flexible temporary support may be, for example, 1 〇 / 〜1 00 μm. The coating layer constituting the transfer film can be formed by applying the non-photosensitive composition of the present invention onto a flexible temporary support, drying the coating film, and removing a part or all of the solvent. The coating method of applying the non-photosensitive composition of the present invention to a flexible temporary support can efficiently form a thick film having a uniform thickness on the flexible temporary support (for example, 20 μm or more) The coating film is preferred. Further, it is preferable to have a release layer on the surface of the flexible temporary support to which the non-photosensitive composition of the present invention is applied. Thereby, the operation of peeling off the flexible temporary support can be easily performed in the step of transferring the coating layer onto the substrate. Further, a protective film layer may be provided on the transfer film. Examples of the protective film layer include a polyethylene terephthalate film, a polyethylene film, and a polyvinyl alcohol film. * The non-photosensitive composition of the present invention can be used for the production of a transfer film as described above, or can be applied to a surface of a glass substrate or the like by a screen printing method, and dried. A method of coating a film to form a coating layer. Here, the viscosity of the non-photosensitive composition to be applied to the substrate by the screen printing method is preferably 10 to 2 0 0 P a · s e C . D. Method for Producing Inorganic Material Film Structure -26 - 1280256 The method for producing an inorganic material film structure of the present invention is preferably a method of forming a transfer coating layer from a transfer film such as a glass plate. On the substrate, a photosensitive dry film is laminated on the surface of the transfer coating layer, and a photoresist pattern formed by pattern exposure and development on the photosensitive dry film is sequentially used on the substrate by sand blasting. A pattern formed by subsequent calcination.
' 層積在該轉印塗布層的表面之感光性乾膜，係在如PET 薄膜的暫時支撐體上設置有感光性樹脂組成物層（亦稱爲光 ^ 阻劑層）而成之物，可以是正型的光阻材料亦可以是負型的 光阻材料，其中以負型爲佳。正型時，特別是以由鹼可溶性 酚樹脂和萘醌二疊氮所構成的正型光阻劑爲佳。其中以甲酚 甲階酚醛樹脂和鄰萘醌二疊氮磺酸衍生物所構成之物爲 佳。負型可以舉出的有組合具有脂環之鏈狀聚合物等環化橡 膠和芳香族雙疊氮化合物等雙疊氮化合物而成的環化橡膠-雙疊氮系光阻劑、組合間甲酚甲階酚醛樹脂和1 -疊氮芘而成 的甲階酚醛樹脂-疊氮系光阻劑、組合丙烯酸系單體和光聚 ^ 合引發劑而成的丙烯酸系光阻液等。此等可以購買自市售 品。 形成有轉印塗布層的基板係稱爲玻璃等的單體基板、具 ^ 有電極或電路等之基板，基板面可以是基板的表面或是背 面。 將感光性乾膜層積在轉印塗布層後，在感光性乾膜上使 用曝光裝置進行圖案曝光。上述轉印塗布層的形成、及該層 積，可以使用熱輥。轉印塗布層的形成係通過熱輥使轉印薄 -27- 1280256 膜的塗布層黏附在基板上，隨後，剝離暫時支撐體，得到轉 印塗布層。感光性乾膜的層積，係使感光性乾膜黏附在該轉 印塗布層上，和上述同樣地通過熱輥，隨後，剝離感光性乾 膜的暫時支撐體。該感光性乾膜的暫時支撐體的剝離可以在 曝光步驟之前進行、亦可以在之後進行。The photosensitive dry film laminated on the surface of the transfer coating layer is formed by providing a photosensitive resin composition layer (also referred to as a photoresist layer) on a temporary support of a PET film. The photoresist material which may be a positive type may also be a negative type photoresist material, of which a negative type is preferred. In the case of a positive type, a positive type resist composed of an alkali-soluble phenol resin and naphthoquinonediazide is particularly preferred. Among them, a composition composed of a cresol resol resin and an o-naphthoquinonediazidesulfonic acid derivative is preferred. The negative type may be a cyclized rubber-dual azide photoresist composed of a cyclized rubber such as a chain polymer having an alicyclic ring or a bi-azide compound such as an aromatic diazide compound, and a combination of A resole phenolic resin obtained by a phenol resol resin and a la- azide, an azide-based photoresist, an acrylic-based photoreceptor obtained by combining an acrylic monomer and a photopolymerization initiator. These can be purchased from commercial products. The substrate on which the transfer coating layer is formed is referred to as a single substrate such as glass, or a substrate having an electrode or a circuit, and the substrate surface may be the surface or the back surface of the substrate. After the photosensitive dry film was laminated on the transfer coating layer, pattern exposure was performed on the photosensitive dry film using an exposure apparatus. A heat roller can be used for the formation of the transfer coating layer and the layer. The transfer coating layer was formed by adhering a coating layer of a transfer thin film -27 to 1280256 to a substrate by a heat roller, and then, the temporary support was peeled off to obtain a transfer coating layer. The lamination of the photosensitive dry film is such that the photosensitive dry film adheres to the transfer coating layer, passes through a heat roller in the same manner as described above, and then the temporary support of the photosensitive dry film is peeled off. The peeling of the temporary support of the photosensitive dry film may be performed before or after the exposure step.
曝光步驟可以使用通常的光微影術進行，通常係使用光 罩進行遮罩曝光的方法。所使用的遮罩，係按照光阻劑層的 感光性有機成分的種類，來選定負型或正型其中一種。又， 亦可以使用紅色或藍色的可見光雷射光、Ar離子雷射、UV 離子雷射等直接描繪而不採用光罩之方法。 曝光裝置，可以使用步進式曝光機、接近式曝光機等。 又，進行大面積曝光時，藉由邊搬運玻璃基板等基板邊進行 曝光，可以使用較小的曝光機來進行大面積的曝光。 此時所使用的活性光源，例如，可以舉出的有可見光 線、近紫外線、紫外線、電子線、X線、雷射光等，此等之 中，以紫外線爲佳，該光源例如可以使用低壓水銀燈、高壓 水銀燈、超高壓水銀燈、鹵素燈、殺菌燈等。此等之中以超 高壓水銀燈爲佳。曝光條件因塗布厚度而異，可以使用1〜 1 0 0mW/cm2輸出功率的超高壓水銀燈，進行〇.1〜30分鐘曝光。 曝光後，利用光阻劑層的感光部分與非感光部分在顯像 液中的溶解度差異，來進行顯像，此時可以使用浸漬法或噴 霧法、刷塗法來進行。所使用的顯像液可以使用水來顯像， 亦可以使用能夠溶解光阻劑層中的有機成分之有機溶劑。光 阻劑層中存在有具有羧基等酸性基之化合物時，亦有使用鹼 -28 - 1280256 水溶液來顯像比使用水來顯像佳的情況。鹼水溶液可以使用 如氫氧化鈉或碳酸鈉、氫氧化鈣水溶液等金屬鹼水溶液，但 是因爲在煅燒時可以容易地去除鹼成分，以使用有機鹼水溶 液爲佳。又，決取於樹脂，亦可能使用水來顯像。 有機鹼可以使用通常的胺化合物。具體上，可以舉出的 有氫氧化四甲基銨、氫氧化三甲基苄基銨、單乙醇胺、二乙 醇胺等。鹼水溶液的濃度通常爲0.0 1〜1 0質量％、以0.1〜5 質量％爲更佳。鹼濃度太低時，無法去除可溶部，鹼濃度太 $ 高時，因爲有可能將圖案部剝離、有可能將非可溶部腐蝕而 不佳。又，顯像時的顯像溫度就工程管理上而言，以2 0〜4 0 °C 進行爲佳。 隨後，移至按照形成於光阻劑層的圖案，進行去除轉印 塗布層的步驟。該步驟以噴砂法爲佳。噴砂法有以高速噴射 混合壓縮氣體而成的硏磨劑微粒子，物理性地對轉印塗布層 施加蝕刻之方法。 又，轉印塗布層的蝕刻，亦可以使用日本專利特開 $ 2 0 0 0- 1 64 1 2號公報所記載的高壓噴霧顯像方法。 亦可以在對轉印塗布層鈾刻後，設置有去除轉印塗布層 上的光阻圖案的步驟，亦可以直接移至煅燒步驟。該去除該 ~ 光阻圖案的步驟，可以浸漬在剝離液，或噴霧塗布來去除。 隨後，使用煅燒進行煅燒。煅燒環境或溫度係因轉印塗 布層或基板的種類而異，其中可以在空氣中、氮氣、氫等的 環境中煅燒。煅燒爐可以使用分批式的煅燒爐或輸送帶式的 連續型煅燒爐。煅燒溫度係在400〜600 °C進行。煅燒時間爲 -29 - 1280256 1 〇〜60分鐘。就能量經濟性而言，煅燒溫度雖然是較低爲 佳，爲了去除有機成分和促進玻璃的燒結，400 °C的溫度是 必要的。又，不必高至600 °C以上的溫度。又，在以上的曝 光、顯像、煅燒的各步驟中，爲了乾燥、預備反應的目的， 亦可以導入5 0〜3 0 0 °C的加熱步驟。 本發明的無機材料膜構造物的製造方法，除了使用感光 ' 性乾膜的方法以外，可以使用以下的製造方法，係將使用本 發明的轉印薄膜所形成轉印塗布層，藉由壓模法形成在基板 ^ 上而不使用感光性乾膜。該壓模法可以舉出的有將模具直接 接觸轉印塗布層而在轉印塗布層形成圖案的方法。所使用的 模具，可以舉出的有在對應凸狀圖案的部分係凹狀、在對應 凹狀圖案的部分係凸狀之模具（旋轉模具、平面模具），將該 模具壓住轉印塗布層至預定深度，按照模具來使轉印塗布層 產生塑性變形而形成圖案之方法。 其他的壓模法，可以舉出的有將具有對應圖案凸部孔穴 之陰模，接觸轉印塗布層而只取走該凸部，然後藉由陽模或 ^ 液壓或氣壓將該被陰模取走的轉印塗布層，擠出在基板上之 對應該孔穴的位置上來形成形圖案的方法。 ^ 最好是在此等模具的表面及/或是轉印塗布層表面施加 - 有如前述脫模性層所使用的脫模劑。又，本發明可以採用例 如特開平1 0-3 26562號公報、特開2002-93 3 1 3號公報所記 載的方法。 此時之轉印塗布層可以選定其轉印塗布層的組成（特別 是溶劑、可塑劑等之種類、量），適當地調整其可塑性，而 -30- 1280256 能夠進行上述的模製成型。 [實施例] 以下，使用實施例來具體地說明本發明。但是，本發明 並不受此等之限制。 實施例1 · 1〜1 - 4、比較例1 -1〜1 - 3 (1)塗布用非感光性組成物的調製 塗布用非感光性組成物1〜7的調製 如表1，組合由70克平均粒徑各爲0.5、0.8、0.9、1.0、 1.2、1.5、1.8微米的無機粉末甲（A)(在表1記載種類及組 成）、及30克平均粒徑爲2.0微米的無機粉末乙（氧化鋁、軟 化點：1 200 °C )所構成的無機粉末成分，將其分散在葱品醇 和丁基卡必醇乙酸酯的混合溶劑中溶解2克的樹脂（乙基纖 維素）而成的溶液中，隨後，添加苯二甲酸二丁酯作爲可塑 劑，進行混煉得到塗布用非感光性組成物（糊料）1〜7。 1280256 米大小的3個剖面照片，求取描繪而成的複數孔之最長直徑 的平均値。 裂痕：經由肉眼詳細觀查。若無法觀察到時爲無，可以 觀察到時標記爲有。 介電常數：使用橫河電機製介電常數測定器（i MHz)來測 定。 解像性：變更曝光量、改變線寬度，來調查煅燒後之圖 案極限解像力。該解像力係煅燒後隔壁的寬度。 強度：使用島津製微小硬度計DUH〜W2〇l，以200gf 的負荷壓住直徑50微米的圓板3分鐘，觀察膜有無破損。 -34- 1280256The exposure step can be performed using conventional photolithography, typically using a mask for mask exposure. The mask to be used is one selected from a negative type or a positive type depending on the type of photosensitive organic component of the photoresist layer. Further, a method of directly drawing a red or blue visible light laser, an Ar ion laser, a UV ion laser, or the like without using a photomask may be used. As the exposure device, a stepper, a proximity exposure machine or the like can be used. Further, when performing large-area exposure, exposure can be performed by transporting a substrate such as a glass substrate, and a large exposure can be performed using a small exposure machine. The active light source used at this time may, for example, be visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, or laser light. Among them, ultraviolet light is preferable, and the light source may be, for example, a low-pressure mercury lamp. , high pressure mercury lamp, ultra high pressure mercury lamp, halogen lamp, germicidal lamp, etc. Among these, ultra-high pressure mercury lamps are preferred. The exposure conditions vary depending on the thickness of the coating, and an ultrahigh pressure mercury lamp having an output of 1 to 100 mW/cm 2 can be used for exposure for 1 to 30 minutes. After the exposure, development is carried out by utilizing the difference in solubility between the photosensitive portion and the non-photosensitive portion of the photoresist layer in the developing solution, and this can be carried out by a dipping method, a spray method or a brush coating method. The developing solution used can be developed using water, and an organic solvent capable of dissolving the organic component in the photoresist layer can also be used. When a compound having an acidic group such as a carboxyl group is present in the photoresist layer, it is also possible to use a base -28 - 1280256 aqueous solution for image development better than water. As the aqueous alkali solution, a metal alkali aqueous solution such as sodium hydroxide or sodium carbonate or a calcium hydroxide aqueous solution can be used, but since the alkali component can be easily removed at the time of calcination, it is preferred to use an organic alkali aqueous solution. Also, depending on the resin, it is also possible to use water for visualization. As the organic base, a usual amine compound can be used. Specific examples thereof include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethylethanolamine. The concentration of the aqueous alkali solution is usually from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass. When the alkali concentration is too low, the soluble portion cannot be removed, and when the alkali concentration is too high, the pattern portion may be peeled off, and the non-soluble portion may be corroded and may be poor. Further, the development temperature at the time of development is preferably 20 to 40 ° C in terms of engineering management. Subsequently, the step of removing the transfer coating layer is carried out in accordance with the pattern formed on the photoresist layer. This step is preferably a sand blasting method. The sandblasting method has a method of physically etching a transfer coating layer by pulverizing fine particles obtained by mixing a compressed gas at a high speed. Further, as the etching of the transfer coating layer, a high-pressure spray development method described in Japanese Patent Laid-Open Publication No. JP-A No. 2000-1281 can also be used. It is also possible to provide a step of removing the photoresist pattern on the transfer coating layer after engraving the transfer coating layer uranium, or directly to the calcination step. The step of removing the photoresist pattern may be performed by immersing in a stripping solution or by spray coating. Subsequently, calcination is carried out using calcination. The calcination environment or temperature varies depending on the type of the transfer coating layer or the substrate, and can be calcined in the air, nitrogen, hydrogen or the like. The calciner may use a batch type calciner or a conveyor type continuous calciner. The calcination temperature is carried out at 400 to 600 °C. The calcination time is -29 - 1280256 1 〇 ~ 60 minutes. In terms of energy economy, although the calcination temperature is preferably lower, in order to remove organic components and promote sintering of the glass, a temperature of 400 ° C is necessary. Also, it is not necessary to be as high as 600 °C or higher. Further, in each of the above steps of exposure, development, and calcination, a heating step of 50 to 300 °C may be introduced for the purpose of drying and preliminary reaction. In the method for producing an inorganic material film structure of the present invention, in addition to the method of using a photosensitive dry film, the following production method can be used, and a transfer coating layer formed by using the transfer film of the present invention can be used. The method is formed on the substrate ^ without using a photosensitive dry film. The compression molding method may be a method in which a mold is directly contacted with a transfer coating layer to form a pattern on a transfer coating layer. The mold to be used may be a mold having a concave shape in a portion corresponding to the convex pattern and a convex shape in a portion corresponding to the concave pattern (rotary mold, flat mold), and the mold is pressed against the transfer coating layer. A method of forming a pattern by plastically deforming the transfer coating layer in accordance with a mold to a predetermined depth. For other compression molding methods, there may be mentioned a female mold having a corresponding pattern convex portion hole, which is contacted with the transfer coating layer and only the convex portion is removed, and then the negative mold is pressed by a male mold or a hydraulic or pneumatic pressure. The transfer coating layer is taken out and extruded on the substrate at a position corresponding to the hole to form a pattern. It is preferable to apply a release agent as used in the above-mentioned release layer to the surface of the mold and/or the surface of the transfer coating layer. Further, the present invention can be applied, for example, to the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2002-93. At this time, the transfer coating layer can be selected such that the composition of the transfer coating layer (particularly, the kind and amount of a solvent, a plasticizer, etc.) is appropriately adjusted in plasticity, and -30 - 1280256 can be molded as described above. [Examples] Hereinafter, the present invention will be specifically described using examples. However, the invention is not limited by these. Example 1 - 1 to 1 - 4, Comparative Example 1 -1 to 1 - 3 (1) Preparation of non-photosensitive compositions 1 to 7 for preparation and application of a non-photosensitive composition for coating are shown in Table 1, and the combination is 70. Inorganic powder A (A) (species and composition shown in Table 1) and 30 g of inorganic powder having an average particle diameter of 2.0 μm each having an average particle diameter of 0.5, 0.8, 0.9, 1.0, 1.2, 1.5, and 1.8 μm (Alumina, softening point: 1 200 ° C) The inorganic powder component is dispersed in a mixed solvent of onion alcohol and butyl carbitol acetate to dissolve 2 g of the resin (ethyl cellulose). In the resulting solution, dibutyl phthalate was added as a plasticizer, followed by kneading to obtain a non-photosensitive composition (paste) 1 to 7 for coating. A photograph of three sections of 1280256 meters in size, and the average diameter of the longest diameter of the plurality of holes drawn is obtained. Rift: A detailed examination through the naked eye. If it is not observed, it is marked as Yes when it is observed. Dielectric constant: measured using the Yokogawa mechanism dielectric constant measurer (i MHz). Resolution: Change the exposure amount and change the line width to investigate the ultimate resolution of the pattern after calcination. This resolution is the width of the partition wall after calcination. Strength: Using a Shimadzu microhardness tester DUH to W2〇l, the disk having a diameter of 50 μm was pressed with a load of 200 gf for 3 minutes, and the film was observed for damage. -34- 1280256
1280256 由表2，如比較例1 -1及1 -2所示，無機粉末乙（玻璃） 的平均粒徑小於〇 · 9微米時，空隙面積率及空隙大小在本發 明的下限以下，且膜的介電常數高，煅燒時會產生裂痕，又， 如比較例1 - 3所示，玻璃的平均粒徑大於1 . 5微米時，空隙 大小大於本發明的上限’有產生裂痕、在膜強度試驗時產生 * 損壞，實用上會有問題。另一方面，得知無機粉末甲（玻璃） ^ 的平均粒徑爲0.9〜1 .5微米之實施例1-1〜1-4,在符合空隙 面積率及空隙大小之同時，介電常數低、未產生裂痕、強度 亦可以符合 貫施例2 -1〜2 - 3、比較例2 - 1〜2 - 2 如表3 ’除了改變無機粉末甲（A)爲（B)的組成，使平均 粒徑爲1.0,使無機粉末乙的平均粒徑爲1·4、1·6、2.〇、2.5、 3 ·〇微米以外，和實施例1 - 1同樣地調製塗布用非感光性組 成（糊料）8〜1 2，而且，和實施例1 -1同樣地形成隔壁煅燒圖 案並評價。 -36- 1280256 [表3] 比較例 2-1 實施例 2-1 實施例 2-2 實施例 2-3 比較例 2-2 塗布用非感光性組成物 無機粉末甲 種類 平均粒徑 (微米） 8 9 11 121280256 From Table 2, as shown in Comparative Examples 1-1 and 1-2, when the average particle diameter of the inorganic powder B (glass) is less than 〇·9 μm, the void area ratio and the void size are below the lower limit of the present invention, and the film The dielectric constant is high, and cracks are generated during calcination. Further, as shown in Comparative Example 1-3, when the average particle diameter of the glass is larger than 1.5 μm, the void size is larger than the upper limit of the present invention, and cracks occur at the film strength. * Damage occurred during the test and there was a problem in practical use. On the other hand, it is known that Examples 1-1 to 1-4 of the inorganic powder of A (glass) ^ having an average particle diameter of 0.9 to 1.5 μm have a low dielectric constant while satisfying the void area ratio and the void size. No cracks, strength can also be consistent with the application of Examples 2 -1 to 2 - 3, Comparative Example 2 - 1 to 2 - 2 as shown in Table 3 'In addition to changing the composition of the inorganic powder A (A) to (B), making the average The non-photosensitive composition for coating was prepared in the same manner as in Example 1-1 except that the average particle diameter of the inorganic powder B was 1.0, 1.6, 2., 2., and 3. In the same manner as in Example 1-1, a paste pattern of the partition wall was formed and evaluated. -36- 1280256 [Table 3] Comparative Example 2-1 Example 2-1 Example 2-2 Example 2-3 Comparative Example 2-2 Non-photosensitive composition for coating Inorganic powder for coating A type average particle diameter (micrometer) 8 9 11 12
BB
BB
BB
BB
B 1.0 1.0 1.0 1.0 1.0 無機粉末乙 種類 平均粒徑 (微米） 氧化鋁 氧化鋁 氧化鋁 氧化銘 氧化鋁 1.4 1.6 2.0 2.5 3.0 塗布厚度 (微米） 隔壁高度 (微米） 長寬比 耐收縮率 (%) 200 200 200 200 200 140 160 190 190 190 1.6 2.0 3.1 1.1 3.1 70 95 95 95 評價 空隙面積率 空隙大小 (微米） 裂痕 41 44 44 44 0.1 25 有 yfnT. Μ 迦 介電常數 12.0 無B 1.0 1.0 1.0 1.0 1.0 Inorganic Powder B Species Average Particle Size (μm) Alumina Oxide Alumina Oxidation Alumina 1.4 1.6 2.0 2.5 3.0 Coating Thickness (μm) Partition Height (μm) Aspect Ratio Shrinkage Resistance (%) 200 200 200 200 200 140 160 190 190 190 1.6 2.0 3.1 1.1 3.1 70 95 95 95 Evaluation of void area ratio void size (micron) Crack 41 44 44 44 0.1 25 with yfnT. 迦 介 dielectric constant 12.0 No
由表3，如比較例24所示，無機粉末乙（玻璃）的平均 粒徑小於1 . 5微米時，空隙面積率及空隙大小在本發明的下 限以下，且膜的介電常數高，煅燒時會產生裂痕，又，如比 較例2-2所示，無機粉末乙的平均粒徑大於2·5微米時，空 -37- 1280256 隙大小大於本發明的上限，在膜強度試驗時產生損壞，實用 上會有問題。另一方面，得知無機粉末乙的平均粒徑爲5 〜2 · 5微米之實施例2 -1〜2 - 3，在符合空隙面積率及空隙大 小之同時，介電常數低、未產生裂痕、強度亦可以符合。 實施例3 -1〜3 - 5 ' 如表4，除了將平均粒徑1 ·2的無機粉末甲的種類，改 " 變爲C、D、E、F、G之平均粒徑2.0微米的無機粉末以外， 和實施例1 -1同樣地調製塗布用非感光性組成（糊料）1 3〜 Φ 1 7，而且，和實施例1 -1同樣地形成隔壁锻燒圖案並評價。 -38 - 1280256From Table 3, as shown in Comparative Example 24, when the average particle diameter of the inorganic powder B (glass) is less than 1.5 μm, the void area ratio and the void size are below the lower limit of the present invention, and the dielectric constant of the film is high, and calcination is performed. When cracks are formed, as shown in Comparative Example 2-2, when the average particle diameter of the inorganic powder B is more than 2.5 μm, the gap size of the empty -37-1280256 is larger than the upper limit of the present invention, and damage occurs during the film strength test. There will be problems in practical use. On the other hand, Example 2 -1 to 2 - 3 in which the average particle diameter of the inorganic powder B was 5 to 2 · 5 μm was observed, and the dielectric constant was low and cracks were not formed while satisfying the void area ratio and the void size. The intensity can also be met. Example 3 -1~3 - 5 ' As shown in Table 4, except for the type of inorganic powder A having an average particle diameter of 1.2, the average particle diameter of C, D, E, F, and G was changed to 2.0 μm. In the same manner as in Example 1-1 except that the inorganic powder was used, the non-photosensitive composition (paste) for coating 1 3 to Φ 1 7 was prepared in the same manner as in Example 1-1, and a fire-retardant pattern of the partition wall was formed and evaluated. -38 - 1280256
表4] 實施例 3-1 實施例 3-2 實施例 3-3 實施例 3-4 實施例 3-5 塗布用非感光性組成物 13 14 15 16 17 無機粉末甲 種類 C D E F G 平均粒徑 (微米） 1.2 1.2 1.2 1.2 1.2 無機粉末乙 種類 氧化鋁 氧化鋁 氧化鋁 氧化鋁 氧化鋁 平均粒徑 (微米） 2.0 2.0 2.0 2.0 2.0 塗布厚度 (微米） 200 200 200 200 200 評價 隔壁高度 (微米） 189 188 185 189 188 δ M t匕 1.6 2.0 3.1 3.1 3.1 耐收縮率 (%) 95 94 93 95 94 空隙面積率 45 44 44 46 47 空隙大小 (微米） 7 8 5 6 8 裂痕 Μ /\\\ 川、 Μ / \\\ >frrr 將 "、、 介電常數 6.5 6.0 7.2 8.0 7.4 解像性 61 61 61 61 61 強度 無損壞 無損壞 無損壞 無損壞 無損壞 由表4，即使變更無機粉末甲（玻璃）組成，在符合空隙 面積及空隙大小之同時，可以得到解像性高、介電常數低、 不產生裂痕、強度亦良好的膜。 -39 - 1280256 【圖式簡單說明】 Μ 〇 【元件符號說明】 4FR1 〇 J \\\Table 4] Example 3-1 Example 3-2 Example 3-3 Example 3-4 Example 3-5 Non-photosensitive composition for coating 13 14 15 16 17 Inorganic powder type A CDEFG Average particle size (micron 1.2 1.2 1.2 1.2 1.2 Inorganic powder Type A Alumina Alumina Alumina Alumina Alumina Average particle size (μm) 2.0 2.0 2.0 2.0 2.0 Coating thickness (micron) 200 200 200 200 200 Evaluation of bulkhead height (micron) 189 188 185 189 188 δ M t匕1.6 2.0 3.1 3.1 3.1 Shrinkage resistance (%) 95 94 93 95 94 Void area ratio 45 44 44 46 47 Void size (μm) 7 8 5 6 8 Fracture Μ /\\\ Sichuan, Μ / \\\ >frrr will ",, dielectric constant 6.5 6.0 7.2 8.0 7.4 resolution 61 61 61 61 61 strength no damage no damage no damage no damage no damage by table 4, even if changing inorganic powder A (glass) The composition is such that, in accordance with the void area and the void size, a film having high resolution, low dielectric constant, no cracking, and good strength can be obtained. -39 - 1280256 [Simple description of the diagram] Μ 〇 [Description of component symbols] 4FR1 〇 J \\\
-40-40
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