200301490 A7 B7 五、發明説明（1) 【發明所屬之技術領域】 (請先閲讀背面之注意事項再填寫本頁) 本發明係關於於電漿顯示器面板（以下簡稱爲PDP)之 前面基板之精細電極電路，形成黑底有用之黑色膏組成物 ，尤以鹼顯像型且光硬化型之黑色膏組成物，及具備使用 此具有白黑兩層結構之匯流電極之黑層（下層），形成黑底 ’之前面基板之PDP。 【先前技術】 經濟部智惡財產苟貨工消費合作社印災 PDP係利用經由電漿放電發光進行影像資訊顯示之平 面顯示器，依面板結構、驅動方法分類爲DC型與AC型 。經由PDP彩色顯示之原理，係經由肋條（隔牆）隔開形成 相對之前面玻璃基板與背面玻璃基板之兩電極間之單元空 間（放電空間）內產生電漿放電，經由各單元空間內被封入 之氦、氙等氣體放電產生之紫外線激勵形成於背面玻璃基 板之螢光體，以產生3原色之可見光。各單元空間’於 DC型PDP經由格子狀之肋條被間隔，另方面於AC型 PDP經由平行列設基板面之肋條被間隔，兩者單元空間之 間隔皆經由肋條所成。以下參照圖式簡單說明。 第1圖係部份表示全色顯示3電極結構之面放電方式 PDP之結構例。前面玻璃基板1之下面’以預定間矩列設 多數由用於放電之透明電極3a或3b，與用於降低該透明 電極路線電阻之匯流電極4a或4b所成一對顯示電極2a 、2b。此顯示電極2a、2b之上經由印刷、焙燒形成用以 蓄積電荷之透明介電體層5(低熔點玻璃），其上蒸鍍保護 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 -5- 200301490 A7 B7 五、發明説明（2) (請先閲讀背面之注意事項再填寫本頁) 層（M g 0) 6。保護層6具有保護顯示電極、維持放電狀態 等功能。另方面，於背面玻璃基板11，以預定間矩列設 多數區隔放電空間之條狀肋條（間牆）1 2與配設於各放電空 間內位址電極（資料電極）1 3。各放電空間之內面，規則性 配設紅（1 4 a)、藍（1 4 b)、綠（1 4 c) 3色螢光體膜。全色顯示 係以紅、藍、綠3原色之螢光體膜14a、14b、14c之一個 晝素所構成。 於形成放電空間之一對顯示電極2a、2b之兩側部， 形成用以提高畫値反差同爲條狀之黒條1〇 ° 該結構之PDP，於一對顯示電極2a ' 2b之間施加交 .流脈衝電壓^因於问一*基板上之電極間放電’故稱爲「面 放電方式」。 該結構之PDP，經由放電產生之紫外線激勵背面基板 11之螢光體膜14a、14b、14c，將產生之可見光透過前面 基板1之透明電極3a或3b成爲可見結構。 該結構之PDP，形成該匯流電極4a、4b，以往係蒸 鍍鉻-銅-鉻3層或經由濺射法成膜後，用光蝕法形成圖案 〇 經濟部智慧財產局員工消費合作社印製 但因步驟多致成本高，最近，係用將銀膏等導電性膏 網版印刷後，焙燒之方法，或用以作成1 50μιη以下之線 ‘寬，塗佈感光性導電性膏，通過圖案膜曝光後，顯像，再 焙燒之方法。 於形成此匯流電極4a、4b之PDP之前面基板，近年 用以提昇晝面反差，形成匯流電極時，於作爲顯示側之下 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -6- 200301490 Α7 Β7 五、發明説明（3) (請先閱讀背面之注意事項再填寫本頁) 層（與透明電極3a、3b接觸之層），印刷含黑色顏料與導 電性粉末之黑色膏，其上使用銀膏形成白層，形成白黑兩 層結構電極之方法，揭示日本特開平4-272634號公報。 此情況之該黑色膏，係使用摻合釕化合物之樹脂組成物。 但，釕化合物係電阻値低之黑色顏料，且材料非常昂 .貴，作爲黑色顏料之用時，有成本面之問題。 另方面，自導電性、加工性、價格面以銀粉最有效廣 泛作爲導電性粉末之用。但含銀粉之黑色膏，於ITO形 成白黑兩層結構之匯流電極時，焙燒後自畫面側視之焙燒 部份之黑色度降低，或與基材接觸部份之層擴散自IT〇 層剝落有玻璃基板變黃之問題。 含銀粉之黑色膏，亦作爲黑底之材料之用。但黑底並 非易變黃之ΙΤΟ，用以製作易變黃之玻璃基板，黑色膏中 即使存在些許銀成分易變黃之玻璃基板或介電體經由銀之 擴散，有畫面整體之黃色度大幅變高之傾向。爲此，含銀 *粉之黑色膏，無法滿足作爲黑底材料之特性。 經濟部智慈財產^Μ工消費合作社印災 【內容】 〔發明所欲解決之課題〕 因此本發明爲解決以往技術所存之課題，其主要目的 係提供可形成於焙燒後白黑兩層結構之匯流電極之白層部 份與透明電極（ΙΤΟ層）之接觸電阻低，並面板之黑色度高 ，且不變黃之焙燒皮膜，且經濟性優之黑色膏組成物。 本發明之另一目的，係提供自該黑色膏組成物所成之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） ~ ' 200301490 A7 B7 五、發明説明（4) 高精細之黑色圖案，具體言之於前面基板所形成之白黑兩 層結構之匯流電極，具備接觸電阻低，並具有充足黑色度 之黑層（下層）電極電路，並形成具有充足黑色之黑底之前 面基板之PDP。 〔用以解決發明之課題〕 本發明者們爲解決該課題銳意硏究之結果，將焙燒後 .色調優之耐熱性黑色顏料，與對玻璃基材及介電體之著色 性少，且電阻値低之導電性粉末選擇性組合解決課題，以 達成本發明。 即，本發明黑色膏組成物，係提供其特徵爲含有（A) 耐熱性黑色顏料，（B)不含銀之導電性粉末，及（C)有機黏 結劑，第2態樣之特徵爲於該成分加上含有（D)光聚合性 單體，及（E)光聚合引發劑，第3態樣之特徵爲於該成分 加上含有（F)無機微粒子之黑色膏組成物。 〔發明之實施形態〕 •本發明黑色膏組成物之耐熱性黑色顏料（A)，係用於 PDP基板製作步驟隨著500〜600°C之高溫焙燒，使用具有 高溫之色調穩定之無機顏料。 具體例有鉻、鈷、銅、鎳、鐵、錳等氧化物及複合氧 化物等，但非限定於此，可單獨或2種以上組合使用。 本發明尤以銅-鉻系黑色複合氧化物、銅-鐵系黑色複 合氧化物、四三氧化鈷等，因其焙燒後形成之黑色皮膜緻 本紙張尺度適用中國國家標率（CNS ) A4規格（210X 297公釐） f請先閱讀背面之注意事if再填寫本頁} .裝· -訂 經濟部智慧財產局員工消費合作社印製 -8- 經濟部智慧財產局®工消費合作社印製 200301490 A7 B7 五、發明説明（5) 密且色調優，故適於使用。 該耐熱性黑色顏料（A)之平均粒徑爲5μιη以下，以使 用0.05μιη以上之微粒子爲宜。平均粒徑若大於5μηι，焙 燒皮膜之黑色度降低故不宜。 尤以將最大粒徑5μηι以下且平均粒徑.〇· 1〜2μιη之四 三氧化鈷等耐熱性黑色顏料均勻分散於溶劑之獎，無二次 •凝聚物之漿適於使用。 此漿’可根據以往公知之方法，將四三氧化鈷等耐熱 性黑色顏料均句分散於溶劑所調製。例如使用球磨機等混 合機將溶劑與分散劑與四三氧化鈷完全混合分散調製之。 用於該漿之溶劑可隨意選擇，但用於防止溶劑相衝突 漿中所用之溶劑與種類相同爲宜。漿之濃度可隨意選擇， 但若考量作業性等以50〜80%爲宜。 用於該漿之分散劑，可均勻分散耐熱性黑色顏料者並 無特別限定，例如日本油脂製之Mariarim系列等高分子 分散劑。 該耐熱性黑色顏料之摻合量，以漿形態之固體成分， 有機黏結劑（C)每100質量份0.5〜100質量份，以5〜50 質量份之範圍爲宜。其理由爲耐熱性黑色顏料之摻合量若 少於該範圍，焙燒後無法製得充足黑色，反之，若超過該 範圍之摻合量，因透光性劣化而降低解相性。 本發明黑色膏組成物，不含銀之導電性粉末（B)，可 使用導電性粉末本身之變色性或對玻璃基板、介電體無著 色性之導電性粉末，例如使用至少1種選自、金、銅、鎮 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)200301490 A7 B7 V. Description of the invention (1) [Technical field to which the invention belongs] (Please read the precautions on the back before filling out this page) This invention relates to the fineness of the front substrate of the plasma display panel (hereinafter referred to as PDP) The electrode circuit forms a black paste composition useful on a black background, especially an alkali developing type and a light-curing black paste composition, and a black layer (lower layer) provided with the bus electrode having the white and black two-layer structure. Black background 'PDP of front substrate. [Previous technology] The Ministry of Economic Affairs ’intellectual property and consumer goods cooperatives printed disasters. PDP is a flat-panel display that displays image information through plasma discharge light emission. It is classified into DC type and AC type according to the panel structure and driving method. Through the principle of PDP color display, a plasma discharge is generated in the cell space (discharge space) formed between the two electrodes facing the front glass substrate and the back glass substrate by ribs (partition walls), which are sealed in each cell space. Ultraviolet rays generated by gas discharges such as helium and xenon excite phosphors formed on the back glass substrate to generate visible light of 3 primary colors. Each unit space is separated by grid-shaped ribs in the DC-type PDP, and is separated by ribs in which the substrate surface is arranged in parallel in the AC-type PDP. The space between the two unit spaces is formed by the ribs. A brief description is given below with reference to the drawings. The first figure is an example of the structure of a surface discharge PDP with a three-electrode structure for full-color display. The lower surface of the front glass substrate 1 is arranged at a predetermined interval. Most of the display electrodes 2a and 2b are formed by a transparent electrode 3a or 3b for discharging and a bus electrode 4a or 4b for reducing the resistance of the transparent electrode. A transparent dielectric layer 5 (low melting point glass) for accumulating electric charges is formed on the display electrodes 2a and 2b by printing and firing. The transparent dielectric layer 5 is deposited on this paper to protect the paper. The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm). 〉 -5- 200301490 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) Layer (M g 0) 6. The protective layer 6 has the functions of protecting the display electrode and maintaining the discharge state. In terms of the rear glass substrate 11, a plurality of strip-shaped ribs (partition walls) 12 for partitioning the discharge space are arranged at predetermined intervals, and an address electrode (data electrode) 13 is arranged in each discharge space. Each discharge space The inner surface is regularly equipped with red (1 4 a), blue (1 4 b), and green (1 4 c) three-color phosphor films. The full-color display uses three primary colors of red, blue, and green. One of the body films 14a, 14b, and 14c is composed of a daylight strip. On both sides of a pair of display electrodes 2a, 2b forming a discharge space, a stripe 10 ° is formed to enhance the contrast of the picture. In the PDP, an alternating current is applied between a pair of display electrodes 2a '2b. The discharge between the electrodes' is called the "surface discharge method." The PDP of this structure excites the phosphor films 14a, 14b, and 14c of the back substrate 11 through the ultraviolet rays generated by the discharge, and transmits the generated visible light through the transparency of the front substrate 1. The electrode 3a or 3b becomes a visible structure. The PDP of this structure forms the bus electrodes 4a and 4b. In the past, three layers of chromium-copper-chromium were vapor-deposited or a film was formed by a sputtering method, and then a pattern was formed by a photo-etching method. Printed by the Consumer Cooperative of the Property Bureau, but the cost is high due to the many steps. Recently, the conductive paste such as silver paste is screen-printed and then baked, or it is used to make a line 'width less than 150 μm, which is coated with light. The conductive conductive paste is exposed by a pattern film, developed, and then fired. The PDP front substrate on which the bus electrodes 4a and 4b are formed is used to improve the day-to-day contrast and is used as a display side when the bus electrode is formed. Below this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -6- 200301490 Α7 Β7 V. Description of invention (3) (Please read the precautions on the back before filling this page) Layer ( The layer where the transparent electrodes 3a and 3b are in contact), a black paste containing black pigment and conductive powder is printed, and a silver paste is used to form a white layer to form a white-black two-layer structure electrode. Japanese Unexamined Patent Publication No. 4-272634 In this case, the black paste is a resin composition doped with a ruthenium compound. However, the ruthenium compound is a black pigment with a low electrical resistance, and the material is very expensive. When used as a black pigment, there is a cost problem. On the other hand, silver powder is the most effective and widely used conductive powder for its self-conductivity, processability, and price. However, when the black paste containing silver powder forms a white-black two-layered bus electrode with ITO, the blackness of the fired part viewed from the side of the screen after firing decreases, or the layer in contact with the substrate diffuses from the IT0 layer and peels off. There is a problem that the glass substrate turns yellow. Black paste containing silver powder is also used as a black base material. But the black background is not ITO that is yellowing easily. It is used to make glass substrates that are yellowing easily. Even if there is some silver in the black paste, the glass substrates or dielectrics are diffused by silver, and the yellowness of the whole picture is greatly increased. The tendency to get higher. For this reason, black paste containing silver * powder cannot meet the characteristics of a black matrix material. Ministry of Economic Affairs, Intellectual Property, Industrial and Commercial Cooperatives, India [Content] [Questions to be Solved by the Invention] Therefore, the present invention aims to solve the problems in the prior art, and its main purpose is to provide a white and black two-layer structure that can be formed after firing. The contact resistance between the white layer portion of the bus electrode and the transparent electrode (ITO layer) is low, and the blackness of the panel is high, the baking film does not change yellow, and the black paste composition is excellent in economy. Another object of the present invention is to provide the paper size made from the black paste composition to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ~ '200301490 A7 B7 V. Description of the invention (4) High precision The black pattern, specifically, the white and black two-layered bus electrode formed on the front substrate, has a black layer (lower layer) electrode circuit with low contact resistance and sufficient blackness, and forms a black matrix with sufficient black. PDP on the front substrate. [To solve the problem of the invention] In order to solve the problem, the present inventors determined to solve the problem, and after baking, a heat-resistant black pigment with excellent hue and low coloring property to glass substrates and dielectrics, and resistance Selective combination of low conductive powder solves the problem to achieve cost invention. That is, the black paste composition of the present invention is characterized by containing (A) a heat-resistant black pigment, (B) a conductive powder not containing silver, and (C) an organic binder, and the second aspect is characterized in that This component is added with (D) a photopolymerizable monomer and (E) a photopolymerization initiator, and a third aspect is characterized in that a black paste composition containing (F) inorganic fine particles is added to this component. [Embodiments of the invention] • The heat-resistant black pigment (A) of the black paste composition of the present invention is used in the PDP substrate manufacturing step. It is calcined at a high temperature of 500 to 600 ° C and uses a high-temperature stable color pigment. Specific examples include oxides such as chromium, cobalt, copper, nickel, iron, manganese, and composite oxides. However, the present invention is not limited thereto, and they may be used alone or in combination of two or more. The present invention is particularly copper-chromium-based black composite oxide, copper-iron-based black composite oxide, cobalt tetraoxide, etc. The black paper film formed after firing causes the paper size to be applicable to China National Standard (CNS) A4 specifications (210X 297mm) f Please read the notes on the back if you want to fill out this page}. Packing--Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives-8-Printed by the Intellectual Property Bureau of the Ministry of Economics® Industrial and Consumer Cooperatives 200301490 A7 B7 5. Description of the invention (5) It is suitable for use because it is dense and has excellent hue. The average particle diameter of the heat-resistant black pigment (A) is 5 µm or less, and fine particles of 0.05 µm or more are preferably used. If the average particle diameter is larger than 5 µm, the blackness of the fired film is reduced, so it is not suitable. In particular, the heat-resistant black pigments, such as cobalt trioxide, which have a maximum particle size of 5 μm or less and an average particle size of 0.4 to 2 μm, are evenly dispersed in the solvent. This slurry 'can be prepared by dispersing a heat-resistant black pigment such as cobalt tetraoxide in a solvent according to a conventionally known method. For example, a solvent such as a ball mill is used to disperse and disperse the solvent and dispersant with cobalt tetraoxide completely. The solvent used in the slurry can be selected at will, but it is suitable to prevent the solvent from conflicting. The concentration of the pulp can be selected at will, but it is advisable to consider 50 to 80% of workability. The dispersant used in the slurry is not particularly limited as long as it can disperse the heat-resistant black pigment uniformly. For example, a polymer dispersant such as Mariarim series made by Japan Oils and Fats. The blending amount of the heat-resistant black pigment is a solid component in the form of a slurry, and the organic binder (C) is preferably 0.5 to 100 parts by mass per 100 parts by mass, preferably in a range of 5 to 50 parts by mass. The reason is that if the blending amount of the heat-resistant black pigment is less than this range, sufficient black cannot be obtained after firing. On the other hand, if the blending amount exceeds this range, the devitrification property is degraded due to deterioration in light transmission. The black paste composition of the present invention does not contain silver-containing conductive powder (B). The color-change property of the conductive powder itself or the conductive powder having no coloring property to the glass substrate and the dielectric can be used. For example, at least one selected from the group consisting of Paper size of gold, copper, copper and paper is applicable to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)
-9- 200301490 Α7 Β7 五、發明説明（6) 、SnCh、ITO、金屬摻雜Sn〇2、氧化銦、釕化合物、TiB2 、LaB6等鑭化合物、鑭複合氧化物、釔複合氧化物、鉍 • 複合氧化物中者。 該導電性粉末中，尤以無變色性或著色性之導電性粉 末’且本身具有黑色，電阻値低之導電性粉末爲宜。 爲滿足該導電性粉末，可例舉SnCh、ITO、金屬摻雜 SnCh、釕化合物、TiB:、LaB6等鑭化合物、鑭複合氧化物 、釔複合氧化物、鉍複合氧化物等。 使用此類導電性粉末，用於匯流電極時無惡化黑色度 ，作爲黑底之用時無變黃製得充足之黑色度。其結果不會 產生面板化後輝度降低或亮度不勻之問題，採行大的驅動 裕度，可製作畫面反差良好少變黃之面板。 該導電性粉末（B)之平均粒徑爲ΙΟμίΉ以下，以使用平 均粒徑0.05μηι〜ΙΟμιη微粒子爲宜。其理由爲導電性粉末 粒徑若大於ΙΟμιη，形成電極路線圖案時之路線的直進性 惡化，或焙燒後之路線圖案易產生膨脹而產生短或直放電 之情況。反之，平均末粒徑若低於〇.〇5 μιη，與於白黑兩 層結構之匯流電極之黑層焙燒後膜厚相較變得非常小，匯 流電極之白層部份與透明電極（ΙΤΟ層）很難通路，電阻値 變得不低之情況。 此點，導電性粉末之平均粒徑小於以下，形成 電極路線圖案時，無損路線之直進性，匯流電極之白層部 份與透明電極（ΙΤΟ層）之電路相通’可降低接觸電阻。 該導電性粉末性（Β)之摻合量，使用耐熱性黑色顏料 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨0Χ 297公釐） --------- (請先閱讀背面之注意事項再填寫本頁) 、*! Μ 經濟部智慧財產局g(工消費合作社印製 -10 - 200301490 A7 B7 五、發明説明（7) (請先閱讀背面之注意事項再填寫本頁) (A)每100質量份0.05〜300質量份，以0.1〜200質量份 之範圍爲宜。其理由爲導電性粉末性之摻合量若少於該 圍，焙燒後之接觸電阻値無法完全降低，反之，若超過該 •範圍之摻合量，對耐熱性黑色顏料之摻合量過多，致黑色 度惡化。 本發明黑色膏組成物之有機黏結劑（C)，無特別限定 ，可用具有羧基之樹脂，或其本身具有乙烯性不飽和雙鍵 含羧基感光性樹脂及不具有乙烯性不飽和雙鍵含羧基樹脂 皆可。適於使用之樹脂（低聚物及聚合物皆合）如下所例。 (1) (a)不飽和羧酸與（b)具有不飽和雙鍵之化合物共 聚製得之含羧基樹脂 (2) 於（a)不飽和羧酸與（b)具有不飽和雙鍵之化合物 之共聚物附加乙烯性不飽和基爲側基製得之含羧基感光性 樹脂 (3) 於（c)具有環氧基與不飽和雙鍵之化合物與（b)具 有不飽和雙鍵之化合物之 經濟部智慧財產局Μ工消費合作社印製 共聚物，使（a)不飽和羧酸反應生成之2級羧基使（d) 多價酸酐反應製得之含羧基感光性樹脂 (4) 於（e)具有不飽和雙鍵之酸酐與（b)具有不飽和雙 鍵之化合物之共聚物，使（f)具有羥基之化合物反應製得 之含羧基感光性樹脂 (5) 於（e)具有不飽和雙鍵之酸酐與（b)具有不飽和雙 鍵之化合物之共聚物，使（〇具有羥基與不飽和雙鍵之化 合物反應製得之含羧基感光性樹脂 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ 297公釐） -11 - 經濟部智慈財產局員工消費合作社印繁 200301490 A7 B7 五、發明説明（8) • (6)於（g)具有多官能環氧化合物與（h)不飽和一羧酸 反應生成之2級羥基，使（d)多價酸酐反應製得之含羧基 感光性樹脂 (7) 於（b)具有不飽和雙鍵之化合物與縮水甘油（甲基） 丙烯酸酯共聚物之環氧基，使（i) 1分子中具有1個羧基， 不具乙烯性不飽和鍵之有機酸反應生成之2級羥基使（d) 多價酸酐反應製得之含羧基樹脂 (8) 於（」）含羥基聚合物使（d)多價酸酐反應製得之含羧 基樹脂 (9) 於（j)含羥基聚合物使（d)多價酸酐反應製得之含羧 *基樹脂，使（c)具有環氧基與不飽和雙鍵之化合物再反應 製得之含羧基感光性樹脂 該含羧基感光性樹脂及含羧基樹脂，可單獨或混合使 用。兩者皆以合計之組成物總量之10〜80質量％之比例 摻合爲宜。此類聚合物之摻合量若少於該範圍，形成皮膜 中該樹脂之分布易不平均，很難製得充足之硬化性及光硬 化深度，很難經由選擇性曝光、顯像形成圖案。反之若多 於該範圍，焙燒時易生圖案疵點或線寬收縮故不宜。 該含羧基感光性樹脂及含羧基樹脂，各自重量平均分 ，子量爲1，000〜1 0,000，以5,000〜70,000爲宜，及酸値50 〜250mgK〇H/g，且若爲含羧基感光性樹脂，其雙鍵當量 爲3 50〜2,000，以使用400〜i，500者爲宜。該樹脂分子 量若低於1，000，使顯像時皮膜之黏附性不佳，反之若高 於i 00,000，因易產生顯像不佳故不宜。又酸値若低於 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)-9- 200301490 Α7 Β7 V. Description of the invention (6), SnCh, ITO, metal-doped Sn02, indium oxide, ruthenium compound, lanthanum compounds such as TiB2, LaB6, lanthanum composite oxide, yttrium composite oxide, bismuth • Among the complex oxides. Among the conductive powders, a conductive powder having no discoloration or coloring property, and a conductive powder having black color and low electric resistance, are particularly preferred. To satisfy this conductive powder, SnCh, ITO, metal-doped SnCh, ruthenium compounds, lanthanum compounds such as TiB :, LaB6, lanthanum composite oxides, yttrium composite oxides, and bismuth composite oxides can be exemplified. The use of such conductive powders does not deteriorate the blackness when used in a bus electrode, and does not turn yellow when used as a black matrix to obtain sufficient blackness. As a result, there is no problem of reduced brightness or uneven brightness after panelization, and a large driving margin can be used to produce a panel with good screen contrast and less yellowing. The average particle diameter of the conductive powder (B) is 10 μL or less, and it is preferable to use fine particles having an average particle diameter of 0.05 μm to 10 μm. The reason is that if the particle diameter of the conductive powder is greater than 10 μm, the straightness of the route when the electrode route pattern is formed is deteriorated, or the route pattern after firing is prone to swell and cause short or straight discharge. Conversely, if the average final particle diameter is less than 0.05 μm, the film thickness after baking the black layer of the white and black two-layer bus electrode becomes very small. The white layer portion of the bus electrode and the transparent electrode (ΙΤΟ) Layer) where the path is difficult and the resistance 不 becomes not low. At this point, the average particle diameter of the conductive powder is less than or less than that, when the electrode route pattern is formed, the straightness of the route is not impaired, and the white layer portion of the bus electrode is in communication with the circuit of the transparent electrode (ITO layer) to reduce contact resistance. The blending amount of the conductive powder (B) uses heat-resistant black pigment. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 × 297 mm) --------- (please first Read the notes on the back and fill in this page), *! Μ Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives-10-200301490 A7 B7 V. Invention Description (7) (Please read the notes on the back before filling in this (A) 0.05 to 300 parts by mass per 100 parts by mass, preferably in the range of 0.1 to 200 parts by mass. The reason is that if the blending amount of the conductive powder is less than this range, the contact resistance after firing cannot be achieved. It is completely reduced. Conversely, if the blending amount exceeds the range, the blending amount of the heat-resistant black pigment is too much, and the blackness is deteriorated. The organic binder (C) of the black paste composition of the present invention is not particularly limited and can be used Resin having a carboxyl group, or a carboxyl-containing photosensitive resin having an ethylenically unsaturated double bond and a carboxyl-containing resin having no ethylenically unsaturated double bond can be used. Suitable resins (both oligomers and polymers) The following are examples: (1) (a) unsaturated carboxylic acid and ( b) Carboxyl-containing resin prepared by copolymerization of a compound having an unsaturated double bond (2) In a copolymer of (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond, an ethylenically unsaturated group is added as a side group The obtained carboxyl group-containing photosensitive resin (3) was printed and copolymerized with (c) a compound having an epoxy group and an unsaturated double bond and (b) a compound having an unsaturated double bond by the Ministry of Economic Affairs and Intellectual Property Bureau Carboxyl group containing photosensitive resin prepared by reacting (a) a secondary carboxyl group formed by the reaction of an unsaturated carboxylic acid and (d) a polyvalent acid anhydride (4) in (e) an acid anhydride having an unsaturated double bond and (b) A copolymer of a compound having an unsaturated double bond, (f) a carboxyl group-containing photosensitive resin prepared by reacting a compound having a hydroxyl group (5) in (e) an acid anhydride having an unsaturated double bond and (b) an unsaturated double bond A copolymer of a compound having a bond and a carboxyl group containing a photosensitive resin prepared by reacting a compound having a hydroxyl group with an unsaturated double bond. The paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) -11- Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs, India 200301 490 A7 B7 V. Description of the invention (8) • (6) The second-order hydroxyl group formed by the reaction of (g) a polyfunctional epoxy compound with (h) an unsaturated monocarboxylic acid, and (d) a polyvalent acid anhydride. The carboxyl group-containing photosensitive resin (7) in (b) the epoxy group of a compound having an unsaturated double bond and a glycidyl (meth) acrylate copolymer, so that (i) there is one carboxyl group in one molecule, without ethylene (2) Carboxy-containing resin prepared by reacting a secondary hydroxyl group formed by the reaction of an organic acid with an unsaturated unsaturated bond and (d) a polyvalent acid anhydride (8) In (") a hydroxyl-containing polymer obtained by reacting (d) a polyvalent acid anhydride Carboxy resin (9) A carboxy * group-containing resin prepared by reacting (d) a polyvalent acid anhydride with (d) a hydroxyl-containing polymer, and (c) a compound having an epoxy group and an unsaturated double bond and then reacting Carboxyl-containing photosensitive resin The carboxyl-containing photosensitive resin and the carboxyl-containing resin can be used alone or in combination. Both are preferably blended in a proportion of 10 to 80% by mass of the total composition. If the blending amount of such polymers is less than this range, the distribution of the resin in the formed film tends to be uneven, it is difficult to obtain sufficient hardenability and light hardening depth, and it is difficult to form a pattern through selective exposure and development. Conversely, if it is more than this range, pattern defects or line width contraction are liable to occur during firing, which is not suitable. The carboxyl group-containing photosensitive resin and the carboxyl group-containing resin each have an average weight fraction of 1,000 to 10, 000, preferably 5,000 to 70,000, and 50 to 250 mg KOH / g of acid. The resin has a double bond equivalent of 3 50 to 2,000, and preferably 400 to i, 500. If the molecular weight of the resin is less than 1,000, the adhesion of the film during development is not good, and if it is higher than i 00,000, it is not suitable because of poor development. If the acid is lower than the paper size, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable (Please read the precautions on the back before filling this page)
-12- 200301490 A7 B7 五、發明説明（9) 50mgK〇H/ g，對鹼水溶液之溶解性不足易生顯像不佳’ 反之若高於2 5 0 m g K〇H / g，顯像時使顯像之黏附性劣化 或光硬化（曝光部）之溶解故不宜。若爲含羧基感光性樹脂 ，感光性樹脂之雙鍵當量若小於3 50，焙燒時易留殘渣’ 反之若大於2,000，顯像時之作業裕度變小，因光硬化時 須高曝光量故不宜。 本發明光聚合性單體（D)係爲促進組成物之光硬化性 及提高顯像性。光聚合性單體（D)，可例舉2-羥乙基丙烯 酸酯、2-羥丙基丙烯酸酯、二甘醇二丙烯酸酯、三甘醇二 丙烯酸酯、聚乙二醇二丙烯酸酯、聚氨基甲酸酯二丙烯酸 酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季 戊四醇四丙烯酸酯、三羥甲基丙烷環氧乙烷改性三丙烯酸 酯、三羥甲基丙烷環氧丙烷改性三丙烯酸酯、一縮二季戊 四醇五丙烯酸酯、一縮二季戊四醇六丙烯酸酯及對應該丙 烯酸酯之各甲基丙烯酸酯類；苯二酸、己二酸、馬來酸、 •衣康酸、琥珀酸、偏苯三酸、對苯二酸等多價酸與羥烷基 (甲基）丙烯酸酯之一、二、三或其上之聚酯等，並無特別 限定，此類可單獨或組合2種以上使用。此類光聚合單體 中以1分子中具有2個以上的丙烯酯基或曱基丙烯酯基之 多官能單體。 此類光聚合性單體（D)之摻合量，爲該有機黏結劑（含 羧基感光性樹脂及/或含羧基樹脂（C)每100質量份20〜 1 00質量份爲宜。光聚合性單體（D)之摻合量若少於該範 圍，得難製得組成物充足之光硬化性。反之若超過該範圍 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐〉 (請先閱讀背面之注意事項再填寫本頁) -裝·-12- 200301490 A7 B7 V. Description of the invention (9) 50mgK〇H / g, insufficient solubility in alkaline aqueous solution, easy to develop poor imaging 'Conversely, if it is higher than 250 mg K〇H / g, when imaging It is not suitable to deteriorate the adhesion of the developer or dissolve the light-hardened (exposed part). If it is a carboxyl-containing photosensitive resin, if the double bond equivalent of the photosensitive resin is less than 3 50, residues are liable to remain during firing. Conversely, if it is greater than 2,000, the operating margin during imaging becomes small, and it is not suitable due to the high exposure required during light curing. . The photopolymerizable monomer (D) of the present invention is to promote the photo-hardening property of the composition and to improve the developability. Examples of the photopolymerizable monomer (D) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, Polyurethane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane epoxy Propane-modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and methacrylates corresponding to acrylates; phthalic acid, adipic acid, maleic acid, itaconic Polyvalent acids such as acids, succinic acid, trimellitic acid, terephthalic acid, and one, two, three, or polyesters of hydroxyalkyl (meth) acrylates are not particularly limited. These can be used alone or in combination. Such photopolymerizable monomers are polyfunctional monomers having two or more propylene ester groups or fluorenyl acrylate groups in one molecule. The blending amount of such photopolymerizable monomer (D) is preferably the organic binder (20 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin (C). Photopolymerization If the blending amount of the monomer (D) is less than this range, it is difficult to obtain sufficient photohardenability of the composition. Conversely, if it exceeds this range, the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) Li> (Please read the notes on the back before filling in this page)
、1T 經濟部智慧財產局肖工消費合作社印製 -13- 200301490 A7 B7 五、發明説明（ib 時變成多量時，因較之皮膜深部其表面部之光硬化提早故 • 易生硬化不勻。 (請先閲讀背面之注意事項再填寫本頁) 該光聚合引發劑（E)之具體例，有苯偶姻、苯偶姻甲 醚、苯偶姻乙醚、苯偶姻異丙醚等苯偶姻與苯偶姻烷基醚 類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2-2-二乙氧基-2-苯基苯乙酮、1-1-二氯苯乙酮等苯乙酮類；2-甲基-1-4[-甲硫基]苯]-2-嗎啉丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎 啉苯）-丁烷-1-酮等胺苯乙酮類；2-甲基蒽醌、2-乙基蒽醌 、2-叔丁基蒽醌-氯蒽醌等蔥醌類；2,4-二甲基噻噸酮、 2.4- 二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙噻噸酮等噻 噸酮類；苯乙酮二甲基縮酮、苯二甲基縮酮等縮酮類；二 苯甲酮等二苯甲酮類·，或咕噸酮類；（2,6-二甲氧基苯醯- 2.4.4- 戊膦氧化物、雙（2,4,6-三甲基苯醯）-苯基磷化氫、 經濟部智慈財產局g(工消費合作社印製 2.4- 6-三甲基苯醯二苯基磷化氫、甲基-2,4,6-三甲基苯醯 苯基膦酸酯等磷化氫類；各種過氧化物類等，此類公知慣 用之光聚合引發劑可單獨或組合2種以上使用。此類光聚 合引發劑（E)之摻合比例，適當爲該有機黏結劑（含羧基感 光性樹脂及/或含羧基樹脂）（C)每100質量份1〜30質量 份，以5〜20質量份爲宜。 該光聚合引發劑（E)，可組合1種或2種以上之N，N-. 二甲胺基苯酸乙酯、N-N-二甲胺基苯酸異戊酯、戊基-4-二甲胺基苯甲酸酯、三乙胺、三乙醇胺等三級胺基類之增 光劑加以使用。 爲因應要求更深之光硬化深度時，於可見範圍開始自 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -14· 200301490 A7 B7 五、發明説明（1) (請先閱讀背面之注意事項再填寫本頁) 由基聚合組合汽巴特殊化學（Ciba Specialty Chemicals公 司）製歐加固化（Irgacure)784之Citasan系光聚合引發劑、 隱色染料等爲助硬化劑加以使用。 再爲因應要求更深之光硬化深度時，可將熱聚合觸媒 與該光聚合引發劑倂用。此熱聚合觸媒係經數分鐘至i小 時之高溫老化以反應製得未硬化之光聚合性單體者，具體 例爲過氧化苯醯等過氧化物、偶氮二異丁腈等偶氮化合物 '。以2, 2 偶氮二異丁腈、2, 2 偶氮-2-甲基丁腈、2,2 一 -f禽氮-2、4-二戊腈、1 偶氮-1-環己酮腈、二甲基-2,2 偶氮異丁酸酯、4,4 \偶氮-4-氰戊醯酸、2-甲基-2, 2 '偶氮丙腈、2,4-二甲基-2,2,2 ' 2 —-偶氮戊腈、1，厂-偶氮（卜乙酸基-1-乙苯）、2,2,2>，2> -偶氮（2-甲基酞醯亞 胺假）二氫氯化物等，較佳爲緩和環境之非氰、非鹵素型 之1，厂-偶氮（1-乙酸基-1-乙苯）。 本發明之組成物，按實施需要得無損本發明黑色膏組 成物之特性之量的比例摻合軟化溫度400〜600°c之玻璃 粉末、二氧化矽粉末等無機微粒子（F)。 經濟部智惡財產局員工消費合作社印¾ 爲提高焙燒後與導體電路之黏附性，可以耐熱性黑色 顏料（A)每100質量份之500質量份以下，以3 00質纛份 以下爲宜之比例添加玻璃粉末。此玻璃粉末之玻璃化溫度 (Tg)爲3 00〜5 00°C，玻璃軟化溫度（Ts)爲400〜600°C者 爲宜。自解相度觀點視之，以使用平均粒徑1 〇 M m以下 ’以5 // m以下之玻璃粉末爲宜。 若將該玻璃粉末添加於黑色膏組成物，曝光、顯像後 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 200301490 A 7 B7 五、發明説明（4 (請先閱讀背面之注意事項再填寫本頁) 之皮膜以600 °C以下可易於焙燒。但本發明之組成物使用 燃燒性佳之有機黏結劑，爲成玻璃粉末熔融前結束去黏之 組成，玻璃粉末軟化溫度若低於400 °C，以低於此之溫度 熔融易包入生成之有機黏結劑，經由分解殘存之有機黏結 劑於組成物中因生成燒石膏故不宜。 玻璃粉末以使用以氧化鉛、氧化鉍、氧化鋰或氧化鋅 等爲主要成分之非晶性玻璃料。 多量之無機塡料或玻璃粉末摻合於黑色膏組成物時， 製得組成物之保存穩定性不佳，因凝膠化或流動性降低有 惡化塗佈作業性之傾向。因此，本發明之組成物，爲提高 .組成物之保存穩定性，以添加無機塡料或玻璃粉末之成分 的金屬或與氧化物粉末之配位化或鹽形成等效果之某化合 物爲穩定劑爲宜。 經濟部智慧財產局員工消費合作社印災 穩定劑，可例舉硝酸、硫酸、鹽酸、硼酸等各種無機 酸；丙二酸、己二酸、甲酸、乙酸、乙醯乙酸、檸檬酸、 硬脂酸、馬來酸、富馬酸、苯二酸、苯颯酸、氨基磺酸等 各種有機酸；磷酸、亞磷酸、次磷酸、磷酸甲酯、磷酸乙 酯、磷酸丁酯、磷酸苯、次磷酸乙酯、次磷酸二苯、一 (2-甲基丙烯羥氧乙基）酸性磷酸脂等各種磷酸化合物（無機 磷酸、有機磷酸）等酸，可單獨或組合2種以上使用。此 ’類穩定劑以該玻璃粉末或無機微粒子（F)毎100質量份以 〇· 1〜1 0質量份之比例添加爲宜。 二氧化矽粉末尤以合成阿莫芬二氧化矽微粉末爲宜， 其具體例有，日本Aerosil(股）製之AEROSIL(註冊商標）50 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） -16- 200301490 A7 B7Printed by Xiao Gong Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs, 1T-200301490 A7 B7 V. Description of the invention (When ib becomes a large amount, it is earlier than the light hardening of the surface of the film deep. • Prone to hardening unevenness. (Please read the notes on the back before filling this page) Specific examples of the photopolymerization initiator (E) include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. And benzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-2-diethoxy-2-phenylacetophenone, 1- Acetophenones such as 1-dichloroacetophenone; 2-methyl-1-4 [-methylthio] benzene] -2-morpholinpropane-1-one, 2-benzyl-2-dimethylamine Amine acetophenones such as 1- (4-morpholinobenzene) -butane-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone-chloroanthraquinone Isoquinones; 2,4-dimethylthioxanthone, 2.4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisothioxanthone and other thioxanthone; phenethyl Ketals such as ketal ketals, xylylene ketals; benzophenones such as benzophenones, or glutathiones; (2,6-dimethoxybenzophenone- 2.4. 4-pentylphosphine Compounds, bis (2,4,6-trimethylphenylphosphonium) -phenylphosphine, Intellectual Property Office of the Ministry of Economic Affairs (printed by Industry and Consumer Cooperatives 2.4-6-trimethylphenylphosphonium diphenylphosphine) Phosphines such as hydrogen, methyl-2,4,6-trimethylphenylphosphonium phenylphosphonate; various peroxides, etc. Such well-known and commonly used photopolymerization initiators can be used alone or in combination of two or more Use. The blending ratio of such photopolymerization initiator (E) is suitably the organic binder (carboxyl-containing photosensitive resin and / or carboxyl-containing resin) (C) 1 to 30 parts by mass per 100 parts by mass, in a range of 5 to 5 parts. The content is preferably ~ 20 parts by mass. The photopolymerization initiator (E) can be used in combination of one or two or more kinds of N, N-. Dimethylaminobenzoic acid ethyl ester, NN-dimethylaminobenzoic acid isoamyl ester , Pentyl-4-dimethylamino benzoate, triethylamine, triethanolamine and other tertiary amine-based brighteners are used. In response to the requirements of deeper light hardening depth, in the visible range from the paper The dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -14 · 200301490 A7 B7 V. Description of the invention (1) (Please read the precautions on the back before filling this page) Polymerization combination Ciba Specialty Chemicals (Igacure) 784 Citasan-based photopolymerization initiator, leuco dye, etc. are used as hardening aids. When the deeper light hardening depth is required, A thermal polymerization catalyst can be used in combination with the photopolymerization initiator. The thermal polymerization catalyst is obtained by aging at a high temperature for several minutes to i hours to obtain an unhardened photopolymerizable monomer, and a specific example is benzene peroxide.醯 and other peroxides, azobisisobutyronitrile and other azo compounds'. With 2, 2 azobisisobutyronitrile, 2, 2 azo-2-methylbutyronitrile, 2, 2-mono-f birds nitrogen-2, 4-divaleronitrile, 1 azo-1-cyclohexanone Nitrile, dimethyl-2,2 azoisobutyrate, 4,4 \ azo-4-cyanovaleric acid, 2-methyl-2,2'azopropionitrile, 2,4-dimethyl -2,2,2 '2 —-Azovaleronitrile, 1,2-Azo (diacetoxy-1-ethylbenzene), 2,2,2 >, 2 > -Azo (2-methyl Phthalophthalmine imine pseudo) dihydrochloride, etc., preferably non-cyanide, non-halogen type 1, plant-azo (1-acetoxy-1-ethylbenzene) that relaxes the environment. The composition of the present invention is blended with inorganic fine particles (F) such as glass powder and silicon dioxide powder having a softening temperature of 400 to 600 ° C in such a proportion that the characteristics of the black paste composition of the present invention are not impaired. Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs ¾ In order to improve the adhesion to the conductor circuit after firing, heat-resistant black pigment (A) may be 500 parts by mass or less per 100 parts by mass, and 300 parts by mass or less may be appropriate. Glass powder is added in proportion. The glass powder has a glass transition temperature (Tg) of 300 ~ 500 ° C, and a glass softening temperature (Ts) of 400 ~ 600 ° C. From the viewpoint of self-dissolving degree, it is preferable to use glass powder having an average particle size of 10 M m or less ′ and 5 // m or less. If the glass powder is added to the black paste composition, the paper size after exposure and development is subject to the Chinese National Standard (CNS) A4 (210X297 mm) -15- 200301490 A 7 B7 V. Description of the invention (4 (please first Read the notes on the back side and fill in this page) The film can be easily fired below 600 ° C. However, the composition of the present invention uses an organic binder with good flammability. If the temperature is lower than 400 ° C, the generated organic binder will be easily melted and melted at a temperature lower than this temperature, and the remaining organic binder will be decomposed in the composition due to the formation of calcined gypsum. It is not suitable to use glass powder with lead oxide, Amorphous glass frit whose main component is bismuth oxide, lithium oxide or zinc oxide, etc. When a large amount of inorganic frit or glass powder is blended with the black paste composition, the storage stability of the prepared composition is not good due to the gel The coating composition tends to be deteriorated due to chemical or fluidity reduction. Therefore, in order to improve the storage stability of the composition, the composition of the present invention is made by adding an inorganic filler or glass powder. It is advisable that the metal or a compound that has effects such as coordination with an oxide powder or salt formation is a stabilizer. The employee of the Intellectual Property Bureau of the Ministry of Economic Affairs, a consumer cooperative cooperative disaster stabilizer, may include various types of nitric acid, sulfuric acid, hydrochloric acid, boric acid, etc. Inorganic acids; malonic acid, adipic acid, formic acid, acetic acid, acetic acid, citric acid, stearic acid, maleic acid, fumaric acid, phthalic acid, phenylarsonic acid, sulfamic acid and other organic acids; Phosphoric acid, phosphorous acid, hypophosphorous acid, methyl phosphate, ethyl phosphate, butyl phosphate, benzene phosphate, ethyl hypophosphite, diphenyl hypophosphite, mono (2-methacryloxyoxyethyl) acid phosphate, etc. Acids such as phosphoric acid compounds (inorganic phosphoric acid and organic phosphoric acid) can be used alone or in combination of two or more. This type of stabilizer is based on 100 parts by mass of the glass powder or inorganic fine particles (F) and 0.1 to 10 parts by mass. It is advisable to add in proportion. Silicon dioxide powder is particularly suitable for the synthesis of amofen silicon dioxide fine powder. Specific examples are: AEROSIL (registered trademark) 50 made by Japan Aerosil (stock). CNS) A4 specifications 210X297 mm) -16- 200301490 A7 B7
五、發明説明（A (請先閲讀背面之注意事項再填寫本頁) 、130、200、200V、200CF、200FAD、300、300CF、380 、〇X50、TT600、M〇X80、MOX170、COK84，日本 Nipgel Silica 工業（股）製之 Nipsil ((註冊商標）AQ、AQ-S、VN3 .、LP、L300、N-300A、ER-R、ER、RW-150、ES、RW-150 、ES、NS、NS-T、NS-P、NS-KR、NS-K，KA、KQ、KM、 DS等，此類可單獨或組合2種以上使用。其中一次粒子 徑5〜50nm，比表面積50〜500m2/g者爲宜。 若將該合成阿莫芬二氧化矽微粉末添加於該光硬性樹 脂組成物，可抑制焙燒步驟時骨材作用焙燒時之變形。 經濟部智慧財產局貸工消費合作社印災 本發明中用於調整塗佈步驟膏之黏度，並可經由乾燥 造膜與接觸曝光，可摻合作爲稀釋劑之有機溶劑。具體例 丁酮、環己酮等酮類；甲苯、二甲苯、四甲基苯等芳族烴 類；溶纖劑、甲基溶纖劑、卡必醇、甲基卡必醇、丁基卡 '必醇、丙二醇一甲基醚、二丙二醇一甲基醚、二丙二醇一 乙基醚、三甘醇一乙基醚等乙二醇醚類；乙酸乙酯、乙酸 丁酯、溶纖劑乙酸酯、甲基溶纖劑乙酸酯、卡必醇乙酸酯 、丁基卡必醇乙酸酯、丙二醇一甲基醚乙酸酯等乙酸酯類 ;乙醇、丙醇、乙二醇、丙二醇、萜晶醇等醇類；辛烷、 癸烷等脂肪族烴；石油醚、石腦油、加氫石腦油、溶劑石 腦油等石油系溶劑，此類可單獨或組合2種以上使用。 本發明黑色膏組成物，按實施需要，亦可摻合聚氧院 基系、丙烯系等消泡、塗平劑，用以提高皮膜黏附性之有 機矽烷偶合劑，等其他添加劑。再按實施需要，亦可添力口 公知慣用之防氧化劑，或用於提高保存時之熱性穩定性之 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X 297公釐） -17- 200301490 A7 B7 五、發明説明（ 熱聚合抑制劑，焙燒時作爲與基板鍵合成分之金屬氧化物 ，矽氧化物，硼氧化物等微粒子。 (請先閱讀背面之注意事項再填寫本頁) 本發明黑色膏組成物，可爲膏狀形態或於P E T等合 成樹脂薄膜上製膜之薄膜狀形態。亦可預先於薄膜狀成膜 時於基板上層壓’若爲膏狀組成物狀態，用網版印刷法、 條紋塗料器、刮板塗料器等適當的塗佈方法塗佈於基板， 例如塗佈於爲PDP前面基板之玻璃基板，爲得指觸乾燥 性再用熱風循環式乾燥、遠紅外線乾燥爐等以約60〜 120□乾燥5〜40分鐘左右以蒸發有機溶劑，製得無皴折 之塗膜。之後進行選擇性曝光、顯像、焙燒，形成預定圖 、 案之電極電路、黑底。 曝光步驟’可使用具有預定圖案之複製膜接觸曝光及 非接觸曝光。曝光光源可使用鹵素燈、高壓水銀燈、雷射 光、金屬鹵化燈、紅外線燈、無電極燈等。曝光量以50 〜1000 m J/cm2左右爲宜。 經濟部智慈財產局貞工消費合作社印製 顯像步驟可用噴霧法、浸漬法等。顯像液以氫氧化鈉 、氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉等金屬鹼性水溶液 ，或乙醇胺、二乙醇胺、三乙醇胺等胺水溶液，尤適合使 用約1.5質量％以下濃度之稀鹼水溶液，但以除去組成物 中含羧基樹脂之羧基經皂化、未硬化部（未曝光）爲宜，非 ^限定該顯像液。爲除去顯像後不須之顯像液，以水洗或酸 中和爲宜。 將顯像後之基板以空氣中或氮環境下進行約4 0 0〜 600°C加熱處理之焙燒步驟，形成所期之圖案。此時昇溫 本紙張尺度適用中國國家標準（CNS ) A4規格（210x 297公楚） -18- 200301490 A7 _ B7 五、發明説明（4 速度設定於20 °C /分以下爲宜。 本發明黑色膏組成物，不含光聚合單體（D)與光聚合 引發劑（E)之非感光性組成物，可經由設有蝕刻光阻蝕刻 形成黑色圖案。尤以白黑兩層結構之匯流電極時，可採用 •白層曝光、顯像時同時顯像黑層之方法。 【實施方式】 〔實施例〕 以下根據實施例具體說明本發，但本發明非限定該實 施。又’以下之「部」，除特別限定外皆爲重量者。 合成例1 將甲基丙烯酸酯與甲基丙烯酸以〇 . 8 7 : 〇. 1 3之莫耳 比裝入備有溫度計、攪拌機、滴漏斗 '及回流冷卻器之燒 瓶’放入二丙二醇一甲基醚爲溶劑，偶氮二異丁腈爲觸媒 ’於氮環境下8 0 °C攪拌2〜6小時，製得爲樹脂溶液之有 機黏結劑A。此有機黏結劑A中之共聚樹脂之重量平均分 子量約1 0,000，酸値爲74mgKOH/g。 測量製得共聚樹脂重量平均分子量，係根據附有島津 製作所製泵浦LLC-6AD與昭和電工製柱Shodex(註冊商 標）KG-8(M、KGS〇2三支之高速液相色譜法測量。 使用製得之有機黏結劑A，以下示之組成比摻合，用 攪拌機攪拌後，用三支輕式硏磨機磨碎成膏化。磨碎條件 .爲以試料1公克於室溫30分鐘。 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX 297公釐） ^-- (請先閱讀背面之注意事項再填寫本頁) 訂 線 經濟部智慧財產局員工消f合作社印災 -19- 200301490 A7 B7 五、發明説明（ιέ 本實施例之四三氧化鈷漿，係使用最大徑粒爲5 # m 以下平均粒徑〇·2 // m之四三氧化鈷黑色微粒子摻合5%之 高分子系分散劑（日本油脂製，AKM-053 1 )之TPM(三丙二 醇一甲基醚）中均勻分散濃度70%之四三氧化鈷漿。 又，低熔點玻璃粉末，係使用粉碎Bn〇3 50 %、B2〇3 15%、Zn〇 15%、Si2〇h 6%、Ba〇 17%，熱膨脹係數 , 3 0 0 = 850 x 1 ，玻璃化溫度46(TC，平均粒徑1.6 • m 者。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慈財產局貨工消費合作社印製 上層（白層）用導電性膏： 有機黏結劑A 100.0 份 季戊四醇三丙烯酸酯 50.0 份 2-苄基-2-二甲胺基-Ι Ο - 嗎啉苯 ） 丁烷 -1 - 酮 5.0份 二丙二醇一甲基醚 8 0.0 份 銀粉 450.0 份 低熔點玻璃粉末 22.0 份 次磷酸 1.0份 下層（黑層）用膏： 組成物例1 有機黏結劑A 100.0 份 季戊四醇三丙烯酸酯 50.0 份 2-苄基-2-二甲胺基-1- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX297公釐） -20- 200301490 A7 B7 五、發明説明（ (4-嗎啉苯）丁烷-1-酮 15.0份 •二丙二醇一甲基醚 70.0份 四三氧化鈷 35.0份 低熔點玻璃粉末 70.0份 丙二酸 1.0份 IT〇玻璃料 3.0份 組成物例2 有機黏結劑A 100.0份 季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-Ια-嗎啉苯 ）丁烷 -1-酮 15.0 份 二丙二醇一甲基醚 70.0份 四三氧化鈷 35.0份 低熔點玻璃粉末 70.0份 丙二酸 1.0份 ΙΤ〇玻璃料 7.0份 組成物例3 有機黏結劑A 100.0份 . 季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-1- (4-嗎啉苯）丁烷-1-酮 15.0份 二丙二醇一甲基醚 70.0份 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 、11 經濟部智慈財產苟員工消費合作社印製 -21 - 200301490 A7 B7 經濟部智慈財產局3(工消骨合作社印製 五、發明説明（ 四三氧化鈷 低熔點玻璃粉末 丙二酸 Sn〇2玻璃料 組成物例4 有機黏結劑A 季戊四醇三丙烯酸酯 2-苄基-2-二甲胺基-1-(4-嗎啉苯）丁烷-1-酮 二丙二醇一甲基醚 銅-鉻-錳系黑色複合氧化物 (C u 0 - C r 2 0 3 - Μ η 2 0 3) 低熔點玻璃粉末 '丙二酸 ιτ〇玻璃料 組成物例5 有機黏結劑A 季戊四醇三丙烯酸酯 2-苄基-2-二甲胺基-1-(4-嗎啉苯）丁烷-卜酮 二丙二醇一甲基醚 四三氧化鈷漿 3 5.0 份 70.0 份 1.0份 7.0份 100.0 份 50·0 份 1 5.0 份 70.0 份 35.0 份 70·0 份 1.0份 7·0份 100.0 份 50.0 份 7.5份 5 5.0 份 5 0.0 份 批衣 訂 線 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -22- 200301490 A7 B7 經濟部智慈財產局肖工消费合作社印製 五、發明説明（1¾ 低熔點玻璃粉末 70.0份 丙二酸 1.0份 ITO玻璃料 7.0份 組成物例6 有機黏結劑A 100.0份 季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-1- (4-嗎啉苯）丁烷-1-酮 7.5份 二丙二醇一甲基醚 55.0份 四三氧化鈷漿 50.0份 低熔點玻璃粉末 70.0份 丙二酸 1.0份 Sn〇2玻璃料 7.0份 比較組成物例1 有機黏結劑A 100.0份 、季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-1- (4-嗎啉苯）丁烷-1-酮 15.0份 二丙二醇一甲基醚 70.0份 四三氧化鈷 3 5.0份 低熔點玻璃粉末 70.0份 丙二酸 1 . 0份 (請先閱讀背面之注意事項再填寫本頁) •裝. 、v" 線 本纸張尺度適用中國國家標率（CNS ) A4規格（210>< 297公釐） -23- 200301490 A7 B7 五、發明説明（2¾ 比較組成物例2 (請先閲讀背面之注意事項再填寫本頁) 有機黏結劑A 100.0份 季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-1- (4-嗎啉苯）丁烷-1-酮 15.0份 二丙二醇一甲基醚 70.0份 四三氧化鈷 3 5.0份 低熔點玻璃 70.0份 丙二酸 1.0份 銀粉 7.0份 比較組成物例3 有機黏結劑A 100.0份 季戊四醇三丙烯酸酯 50.0份 2-苄基-2-二甲胺基-1- (4-嗎啉苯）丁烷-1-酮 7.5份 經濟部智E財產局員工消贤合作社印製 二丙二醇一甲基醚 5 5.0份 四三氧化鈷漿 50.0份 低熔點玻璃 70.0份 丙二酸 1.0份 銀粉 7.0份 接觸電阻値： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -24- 200301490 A7 B7 五、發明説明（2) (請先閱讀背面之注意事項再填寫本頁) 於附ITO膜之PD200(旭硝子公司製，高變應點玻璃） 之ITO面，使用200篩孔之聚酯網版將評估用黑色膏進行 全面Θ印刷，再用熱風循環式乾燥爐以90°C乾燥40分鐘 形成指觸乾燥性良好之皮膜。 其後，以金屬鹵素燈爲光源，組成物上之累積光量爲 600mJ/ cm2將印刷部份之一半/3印刷曝光後，用液溫30 °C0.4wt%之Na2C〇3水溶液進行顯像，水洗。 再使用3 2 5舖孔之不绣銅網版全面塗佈上層（白層）用 導電性層膏，再用熱風循環式乾燥爐以90°C乾燥30分鐘 形成指觸乾燥性良好之白黒兩層與白單層皮膜。其後，使 用圖案尺寸300 // m X 3cm之複製膜使白黑兩層部份之 組成物上之累積光量爲4 0 0 m / c m2圖案曝光後，用液溫 3 0 °C 0.4 w t %之N a 2 C〇3水溶液進行顯像，水洗。 最後，於空氣環境下以5°C /分昇溫，以600°C 30分 ,焙燒製作基板。將製得白黑兩層路線上之任意點與ITO 上之任意點之間之電阻値（用測試機測量）與距離測量數點 作成圖表，自此求出接觸電阻値。 經濟部智M財產苟員工消費合作社印製 L *，a *，b * 値： 白黑兩層： 於附ITO膜之PD200之ITO面，使用200篩孔之聚 酯網版進行全面固體印刷，再用熱風循環式乾燥爐以90 °C乾燥40分鐘形成指觸乾燥性良好之皮膜。 再使用325篩孔之不銹銅網版全面塗佈上層（白層）用 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐1 " -25- 200301490 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（2) 導電性層膏，再用熱風循環式乾燥爐以9CTC乾燥30分鐘 形成指觸乾燥性良好之白黒兩層與白單層皮膜。 最後，於空氣環境下以5°C /分昇溫，以600°C 30分 焙燒製作基板。 將製得之焙燒皮膜，用色調色彩色計（MINLOTA CAMERA公司製，CR-2U)根據JIS-Z-8729自非塗佈面測 測量L * ’ a *，b *表色系之値，以a *値爲紅色度指標， 以b値爲頁色度指標評估。此l *愈小黑色度優，a *値愈 低紅色度低，b *値愈低黃色度小。 黑單層 於PD2 00之TOP面，使用200篩孔之聚酯網版進行 全面固體印刷，再用熱風循環式乾燥爐以90°C乾燥40分 鐘形成指觸乾燥性良好之皮膜。 再於空氣環境下以5°C /分昇溫，以600°C 30分焙燒 製作基板。 測量製得之焙燒皮膜之L *，a *，b *値。 其結果示於表1、表2。自表所示結果淸楚得知，根 據本發明黑色膏組成物，不會惡化接觸電阻値，可得優異 之L * ’ a * ’ b *値。即根據本發明黑色膏組成物，可形成 於焙燒後白黑兩層結構之匯流電極之白層部份與透明電極 (IT〇層）之接觸電阻低，並面板之黑色度高，且不變黃之 焙燒皮膜。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公趁） (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (A (please read the precautions on the back before filling this page), 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, OX50, TT600, MOX80, MOX170, COK84, Japan Nipsil (registered trademark) AQ, AQ-S, VN3., LP, L300, N-300A, ER-R, ER, RW-150, ES, RW-150, ES, NS , NS-T, NS-P, NS-KR, NS-K, KA, KQ, KM, DS, etc. These can be used alone or in combination of two or more. Among them, the primary particle diameter is 5 ~ 50nm, and the specific surface area is 50 ~ 500m2. If this synthetic amofen fine silica powder is added to the light-hardening resin composition, it can suppress the deformation of the aggregate during the firing step during firing. In the present invention, it is used to adjust the viscosity of the paste in the coating step and can be used as an organic solvent as a diluent through dry film formation and contact exposure. Specific examples include ketones such as methyl ethyl ketone and cyclohexanone; toluene and xylene , Tetramethylbenzene and other aromatic hydrocarbons; cellosolve, methylcellosolve, carbitol, methylcarbitol, butylcarbitol Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, methyl ester Cellulose based acetates, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and other acetates; ethanol, propanol, ethylene glycol, propylene glycol, terpene crystals Alcohols such as alcohols; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha, which can be used alone or in combination of two or more. The black paste composition can also be blended with polyoxygen-based, acrylic-based defoaming and leveling agents as required for implementation, organic silane coupling agents used to improve film adhesion, and other additives. According to implementation needs, You can also add the well-known and commonly used antioxidants, or the paper size used to improve the thermal stability during storage. Applicable to China National Standard (CNS) A4 (210X 297 mm) -17- 200301490 A7 B7 V. Invention Explanation (Thermal polymerization inhibitor, used as a component of the bond with the substrate during firing It is oxide, silicon oxide, boron oxide and other fine particles. (Please read the precautions on the back before filling this page) The black paste composition of the present invention can be in the form of a paste or a film formed on a synthetic resin film such as PET. It can also be laminated on the substrate during film formation. If it is in the state of a paste composition, it can be applied to the substrate by a suitable coating method such as screen printing, a stripe coater, and a blade coater. For example, it is coated on the glass substrate which is the front substrate of the PDP. In order to achieve dryness, it can be dried by hot air circulation type drying, far-infrared drying furnace, etc. at 60 ~ 120 □ for 5 ~ 40 minutes to evaporate the organic solvent. Premature coating. After that, selective exposure, development, and firing are performed to form a predetermined pattern, an electrode circuit, and a black matrix. The exposure step 'can use a contact and non-contact exposure of a replication film having a predetermined pattern. The exposure light source may be a halogen lamp, a high-pressure mercury lamp, a laser light, a metal halide lamp, an infrared lamp, or an electrodeless lamp. The exposure amount is preferably about 50 to 1000 m J / cm2. Printed by the Zhengong Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The imaging steps can be sprayed or impregnated. The developing solution is an alkali metal aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, or an amine aqueous solution such as ethanolamine, diethanolamine, and triethanolamine. It is particularly suitable to use a dilute solution with a concentration of about 1.5% by mass or less. Aqueous alkaline solution, but it is preferable to remove the carboxyl group of the carboxyl group-containing resin in the composition from the saponified, uncured portion (unexposed), and the developing solution is not limited. In order to remove unnecessary developing solution after development, washing with water or acid neutralization is suitable. The developed substrate is subjected to a baking step of about 400 to 600 ° C in the air or a nitrogen environment to form a desired pattern. At this time, the paper size is subject to the Chinese National Standard (CNS) A4 specification (210x 297 Gongchu) -18- 200301490 A7 _ B7 V. Description of the invention (4 It is better to set the speed below 20 ° C / min. The black paste of the present invention Composition, non-photosensitive composition that does not contain photopolymerizable monomer (D) and photopolymerization initiator (E), can be formed with a black pattern by etching photoresist. Especially for white and black bus electrodes A method of simultaneously developing a black layer while exposing a white layer and developing it can be adopted. [Embodiments] [Examples] The following specifically describes the present invention based on examples, but the present invention is not limited to this implementation. "Unless otherwise specified, they are all by weight. Synthesis Example 1 A methacrylic acid ester and methacrylic acid were charged in a molar ratio of 0.87 to 0.13, and were equipped with a thermometer, a stirrer, a dropping funnel, and reflux. The flask of the cooler was placed with dipropylene glycol monomethyl ether as the solvent and azobisisobutyronitrile as the catalyst. The mixture was stirred at 80 ° C for 2 to 6 hours under a nitrogen environment to prepare an organic binder A as a resin solution. The weight of the copolymer resin in this organic binder A The average molecular weight is about 10,000, and the acid content is 74 mgKOH / g. The weight average molecular weight of the copolymer resin obtained by measurement is based on the pump LLC-6AD manufactured by Shimadzu Corporation and the Showa Denko column Shodex (registered trademark) KG-8 (M, KGS〇2 measured by high-speed liquid chromatography. Using the prepared organic binder A, blended with the composition ratio shown below, after mixing with a stirrer, grind it into a paste with three light honing mills. Mill Crushing conditions: 1 gram of sample at room temperature for 30 minutes. This paper size applies Chinese National Standard (CNS) A4 (2 丨 OX 297 mm) ^-(Please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China Co-operative Disaster 19-19200301490 A7 B7 V. Description of the Invention (The cobalt trioxide slurry of this embodiment uses a maximum diameter of 5 # m and an average particle diameter of less than 0. 2 // m of tetracobalt trioxide black fine particles blended with 5% polymer dispersant (made by Japan Oil, AKM-053 1) in TPM (tripropylene glycol monomethyl ether) uniformly dispersed concentration of 70% Cobalt oxide paste. Low melting point glass powder is made of pulverized Bn〇5. 0%, B203, 15%, Zn〇15%, Si2Oh 6%, Ba〇17%, thermal expansion coefficient, 3 0 = 850 x 1, glass transition temperature 46 (TC, average particle diameter 1.6 m (Please read the notes on the back before filling this page) The conductive paste for the upper layer (white layer) printed by the Goods and Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: Organic binder A 100.0 parts Pentaerythritol triacrylate 50.0 parts 2- Benzyl-2-Dimethylamino-1 I-morpholine benzene) Butane-1 -one 5.0 parts dipropylene glycol monomethyl ether 8 0.0 parts silver powder 450.0 parts low melting glass powder 22.0 parts hypophosphorous acid 1.0 part lower layer (black Layer) Paste: Composition Example 1 Organic Binder A 100.0 parts pentaerythritol triacrylate 50.0 parts 2-benzyl-2-dimethylamino-1- This paper size applies Chinese National Standard (CNS) A4 specification (2 丨OX297 mm) -20- 200301490 A7 B7 V. Description of the invention ((4-morpholinobenzene) butane-1-one 15.0 parts • Dipropylene glycol monomethyl ether 70.0 parts Cobalt trioxide 35.0 parts Low melting point glass powder 70.0 Parts malonic acid 1.0 parts IT〇 glass frit 3.0 parts composition example 2 organic binder A 100.0 parts quarter Tetraol triacrylate 50.0 parts 2-benzyl-2-dimethylamino-1α-morpholine benzene) butane-1-one 15.0 parts dipropylene glycol monomethyl ether 70.0 parts cobalt trioxide 35.0 parts low melting glass 70.0 parts of powder 1.0 part of malonic acid 7.0 parts of ITO glass frit Composition Example 3 Organic binder A 100.0 parts. Pentaerythritol triacrylate 50.0 parts of 2-benzyl-2-dimethylamino-1- (4-morpholine Benzene) butane-1-one 15.0 parts dipropylene glycol monomethyl ether 70.0 parts This paper is sized for China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page) 11 Printed by the Intellectual Property Cooperative of the Ministry of Economic Affairs and Employees' Cooperatives-21-200301490 A7 B7 Printed by the Intellectual Property Office of the Ministry of Economic Affairs 3 (Printed by the Industrial Cooperative Cooperative) 〇2 Glass frit composition example 4 Organic binder A Pentaerythritol triacrylate 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butane-1-one dipropylene glycol monomethyl ether copper -Cr-Mn black composite oxide (C u 0-C r 2 0 3-Μ η 2 0 3) Low melting point glass powder 'malonic acid ιτ〇 glass Composition Example 5 Organic Binder A Pentaerythritol triacrylate 2-benzyl-2-dimethylamino-1- (4-morpholinebenzene) butane-butanone dipropylene glycol monomethyl ether tetracobalt trioxide slurry 3 5.0 parts 70.0 parts 1.0 parts 7.0 parts 100.0 parts 500.0 parts 1 5.0 parts 70.0 parts 35.0 parts 700.0 parts 1.0 parts 7.0 parts 100.0 parts 50.0 parts 7.5 parts 5 5.0 parts 5 0.0 parts Read the notes on the reverse side and fill in this page) This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) -22- 200301490 A7 B7 Printed by Xiaogong Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs 1¾ Low melting point glass powder 70.0 parts malonate 1.0 part ITO glass frit 7.0 parts Composition Example 6 Organic binder A 100.0 parts pentaerythritol triacrylate 50.0 parts 2-benzyl-2-dimethylamino-1- (4- Morpholine benzene) butane-1-one 7.5 parts dipropylene glycol monomethyl ether 55.0 parts cobalt trioxide slurry 50.0 parts low melting glass powder 70.0 parts malonic acid 1.0 part SnO2 frit 7.0 parts comparative composition example 1 Organic binder A 100.0 parts, pentaerythritol triacrylate 50.0 parts 2-benzyl-2-dimethylamino-1- (4-morpholine benzene) butane-1-one 15.0 parts dipropylene glycol monomethyl ether 70.0 parts cobalt tetraoxide 3 5.0 parts low melting glass powder 70.0 parts malonic acid 1.0 part (please read the note on the back first Please fill in this page again for matters) • Packing., V " Paper size of paper is applicable to China National Standard (CNS) A4 specification (210 > < 297 mm) -23- 200301490 A7 B7 V. Description of invention (2¾ Comparative composition Example 2 (Please read the precautions on the back before filling out this page) Organic Binder A 100.0 parts pentaerythritol triacrylate 50.0 parts 2-benzyl-2-dimethylamino-1- (4-morpholinobenzene) butyl Alkan-1-one 15.0 parts dipropylene glycol monomethyl ether 70.0 parts cobalt tetraoxide 3 5.0 parts low melting glass 70.0 parts malonate 1.0 part silver powder 7.0 parts Comparative composition example 3 Organic binder A 100.0 parts pentaerythritol triacrylate 50.0 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butane-1-one, 7.5 parts, Dipropylene glycol monomethyl ether, printed by employees of the Intellectual Property Office of the Ministry of Economic Affairs and Intellectual Property, 5 5.0 parts of cobalt tetraoxide slurry 50.0 parts of low melting point glass 70.0 parts of malonic acid 1.0 part of silver powder 7.0 parts of contact resistance 値: This paper ruler Applicable to China National Standard (CNS) A4 specification (210X 297 mm) -24- 200301490 A7 B7 V. Description of invention (2) (Please read the precautions on the back before filling this page) For PD200 with ITO film (Asahi Glass Co., Ltd.) Manufacturing, high allergy point glass) ITO surface, using a polyester mesh screen with 200 sieve holes to conduct a comprehensive Θ printing of the black paste for evaluation, and then drying in a hot-air circulation drying oven at 90 ° C for 40 minutes to form finger touch drying Good film. After that, a metal halide lamp was used as a light source, and the cumulative light amount on the composition was 600 mJ / cm2. After one-half / 3 of the printed portion was exposed by printing, the image was developed with a 0.4 wt% Na2CO3 aqueous solution at a liquid temperature of 30 ° C. Washed. Then use 3 2 5 perforated non-embossed copper screen to fully coat the conductive layer paste for the upper layer (white layer), and then use a hot-air circulation drying oven at 90 ° C for 30 minutes to form a white tampon with good finger-drying properties. Layer with white monolayer film. Thereafter, using a copy film with a pattern size of 300 // m X 3cm to make the cumulative light amount on the composition of the white and black layers to be 400 m / c m2, the pattern was exposed at a liquid temperature of 30 ° C 0.4 wt The development was carried out with a Na 2 CO 3 aqueous solution of% and washed with water. Finally, the substrate was heated at 5 ° C / min in an air environment and baked at 600 ° C for 30 minutes. The resistance 値 (measured with a testing machine) and the distance measurement points between any point on the white and black two-layer route and the ITO were plotted as a chart, and the contact resistance 値 was calculated from this point. Printed by L *, a *, b * on the consumer cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs: white and black: on the ITO side of PD200 with ITO film, using a polyester screen with 200 meshes for full solid printing, It was then dried in a hot-air circulation drying oven at 90 ° C for 40 minutes to form a film with good touch-drying properties. Then use the 325 mesh stainless copper screen to fully coat the upper layer (white layer). The paper size for the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm1 " -25- 200301490. Employees ’intellectual property bureau consumption Cooperative prints A7 B7 V. Description of the invention (2) Conductive layer paste, then dried in 9CTC for 30 minutes in a hot-air circulating drying oven to form two layers of white and white single-layer film with good dryness. Finally, in the air environment The substrate was fired at a temperature of 5 ° C / min, and baked at 600 ° C for 30 minutes to prepare a substrate. The obtained baked film was self-coated with a color meter (CR-2U, manufactured by MINLOTA CAMERA, Inc.) in accordance with JIS-Z-8729. The surface measurement measures L * 'a *, b * of the color system, with a * 値 as the redness index and b 値 as the page colorimetric index. The smaller the l *, the better the blackness, and the more a * 値Low redness, low b * 値, lower yellowness. Black single layer on the TOP side of PD2 00, full solid printing using a 200 mesh polyester screen, and then dried in a hot air circulation drying oven at 90 ° C Form a film with good dryness in 40 minutes. Then raise the temperature at 5 ° C / min in the air. The substrate was fired at 600 ° C for 30 minutes to measure the L *, a *, b * 测量 of the fired film obtained. The results are shown in Tables 1 and 2. From the results shown in the table, it is clear that the black color according to the present invention is black. The paste composition does not deteriorate the contact resistance 値, and can obtain excellent L * 'a *' b * 値. That is, according to the black paste composition of the present invention, it can be formed on the white layer of the bus electrode with white and black two-layer structure after firing. The contact resistance between the part and the transparent electrode (IT0 layer) is low, and the blackness of the panel is high, and the baking film does not change yellow. This paper size applies to China National Standard (CNS) A4 specification (210X 297) while (please (Read the notes on the back before filling out this page)
-26- 200301490 A7 B7 五、發明説明（ [表1] 物性 實施例 組成物例 組成物例 組成物例 組成物例 組成物例 組成物例 1 2 3 4 5 6 黑層乾燥膜厚(μ m) 7 7 7 7 7 7 白黑2層/ITO 1/ 5.35 5.76 5.21 5.80 4.95 5.13 a. 0.34 0.19 0.18 0.15 0.25 0.16 b+ 0.75 1.20 0.65 0.51 0.65 0.61 黑矩陣/PD200 5.26 5.35 5.59 5.74 4.87 4.96 ♦ a -0.26 -0.37 -0.30 -0.51 -0.24 -0.30 b* 0.36 0.97 0.69 0.28 0.43 0.55 接觸電阻値(Ω) 34 35 36 37 38 36 (請先閱讀背面之注意事項再填寫本頁) 衣 、11 經濟部智慧財產苟貨工消骨合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） -27- 200301490 五、發明説明（2i [表2] 物性 比較例 比較組成物例1 比較組成物例2 比較組成物例3 黑層乾燥膜厚(μ m) 7 7 7 白黑2層/IT〇 L* 4.66 8.01 8. 15 * a -0.07 0.43 0.39 b· 1.22 1.14 1.21 黑矩陣/PD200 L； 4.84 4.01 4.56 a" -0.56 -0.52 -0.50 b· 0. 11 3.6 4.2 接觸電阻値(Ω) 62 33 34 (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 線 〔發明效果〕 經濟部智慈財產局員工消費合作社印製-26- 200301490 A7 B7 V. Description of the invention ([Table 1] Physical properties Example composition Example composition Example composition Example composition Example composition Example composition Example 1 2 3 4 5 6 Black layer dry film thickness (μm ) 7 7 7 7 7 7 white and black 2 layers / ITO 1 / 5.35 5.76 5.21 5.80 4.95 5.13 a. 0.34 0.19 0.18 0.15 0.25 0.16 b + 0.75 1.20 0.65 0.51 0.65 0.61 black matrix / PD200 5.26 5.35 5.59 5.74 4.87 4.96 ♦ a -0.26 -0.37 -0.30 -0.51 -0.24 -0.30 b * 0.36 0.97 0.69 0.28 0.43 0.55 Contact resistance Ω (Ω) 34 35 36 37 38 36 (Please read the precautions on the back before filling this page) Clothing, 11 Intellectual Property of the Ministry of Economic Affairs The paper size printed by Gou Gong Bone Cooperative Co., Ltd. applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -27- 200301490 V. Description of the invention (2i [Table 2] Comparative Examples of Physical Properties Comparative Composition Example 1 Comparison Composition example 2 Comparative composition example 3 Black layer dry film thickness (μm) 7 7 7 White and black 2 layers / ITOL * 4.66 8.01 8. 15 * a -0.07 0.43 0.39 b · 1.22 1.14 1.21 Black matrix / PD200 L; 4.84 4.01 4.56 a " -0.56 -0.52 -0.50 b · 0. 11 3.6 4.2 Resistance Zhi (Ω) 62 33 34 (please read the Notes on the back to fill out this page) • Order line installed · Ministry of Economic Effect of the Invention Chi Chi Property Office employees consumer cooperatives printed
如上說明根據本發明，可提供於焙燒後白黑兩層結構 之匯流電極形成白層部份與透明電極（ITO層）之接觸電阻 低，並面板之黑色度高，且不變黃之焙燒皮膜之黑色膏組 成物。其結果，係提供可自該黑色膏組成物所成之高精細 之黑色圖案，具體言之於前面基板所形成之白黑兩層結構 之匯流電極，具備接觸電阻低，並具有充足黑色度之黑層 (下層）電極電路，並具有充足黑色之黑底前面基板之PDP 本:紙張尺度適用中國國家標準（CNS )八4規格（210X 297公釐） -28- 200301490 A7 B7 五、發明説明（2表 【圖式簡單說明】 第1圖係面放電方式之AC型PDP之部份分解剖面圖 (請先閱讀背面之注意事項再填寫本頁) 〇 【圖號說明】 1前面玻璃基板 2a、2b顯示電極 3a、3b透明電極 、4a、4b 匯流電極 5透明介電體層 6保護層 10黒條 11背面玻璃基板 12肋條 1 3 位址電極 14a、14b、14c螢光體膜 經濟部智惡財產局Μ工消費合作社印繁 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210X297公釐） -29-As described above, according to the present invention, it is possible to provide a firing film having a low contact resistance between the white layer portion and the transparent electrode (ITO layer) of the bus electrode forming the white and black two-layer structure after firing, and a high blackness of the panel and no yellowing. Black paste composition. As a result, it provides a high-definition black pattern that can be formed from the black paste composition, specifically, a white-black two-layered bus electrode formed on a front substrate, which has a low contact resistance and a sufficient blackness. Black layer (lower layer) electrode circuit and PDP with sufficient black and black front substrate. The paper size is applicable to China National Standard (CNS) 8-4 specifications (210X 297 mm) -28- 200301490 A7 B7 V. Description of the invention ( Table 2 [Schematic description] Figure 1 is a partial exploded cross-sectional view of AC-type PDP with surface discharge method (please read the precautions on the back before filling this page) 〇 [Illustration of the drawing number] 1 Front glass substrate 2a, 2b display electrodes 3a, 3b transparent electrodes, 4a, 4b bus electrodes 5 transparent dielectric layers 6 protective layers 10 purlins 11 back glass substrate 12 ribs 1 3 address electrodes 14a, 14b, 14c phosphor film Ministry of Economy and Intellectual Property The paper size printed by the Bureau of Industrial and Consumer Cooperatives is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) -29-