TW293005B

TW293005B -

Info

Publication number: TW293005B
Application number: TW083112249A
Authority: TW
Original assignee: Nippon Sheet Glass Co Ltd
Priority date: 1993-12-28
Filing date: 1994-12-28
Publication date: 1996-12-11
Also published as: GB9426370D0; CN1101354C; GB2285634A; KR950017792A; CN1111216A; SG81880A1

Description

Λ7 經濟部中央標準局員工消费合作社印製五、發明説明（ 1 峰 ) 1 I I 本發明係關於一種用於建築物汽車及其他交通工具之 1 1 1 熱線反射玻璃〇 1 | 具有可見光及太陽輻射之低透明性之熱線反射玻璃近來請先 1 閱 1 已延伸用作建築物及汽車之窗玻璃 Μ 減少直射陽光之熱讀背 1 1 度減輕空調之負荷保護隱私權及改良外觀 0 熱線反之注 1 I 意 I 射玻璃係藉物理方式如噴鍍在玻璃底材上形成金觴膜或金事項 1 I 屬氮化物或藉噴射含金膈化合物之薄膜形成之溶液在加熱再填 1 寫本木至金靥化合物之熱分解溫度 Μ 上之玻璃底材表面上形成金頁 1 I 鼷氧化物膜而被製成 0 自生產成本、塗膜之耐久性等之觀 1 1 點而後者優於 Λ *· 月IJ 者〇然而由此法所得熱線反射玻璃 1 I 幾乎無法將可見光透射及太陽輻射降在某些位準 (端視塗 1 訂 1 I 膜之組成物而定 )以下< ) 在此等情況下含有鈷及 II 之金膈氧化物之塗膜已知為 1 1 一種可相對減少可見光透射等之塗膜如 JP -B - 6 3 - 3 2 7 36 1 ! 所述〇 (此處所用之” JP -Β ” -詞意指已審査之日本專利公 1« 告案 ) ) 1 I 然而 JP -B -63- 32736所示之用於導電物品之塗膜具有 1 1 小的表面電阻率及高電磁波反射率當用作建築物内之熱 1 1 線反射窗玻璃時會造成鄰近房屋之 TV影像上之複影其 1 在實用上有缺點特別在城鎮内〇 1 I 鑒於此等情況本發明之 g 的為提供一種熱線反射玻璃 1 I t 其塗膜具有電磁波反射率降至在使用時不會有間題之 1 1 位準同時保持含氧化鈷及氧化鎳之塗膜所具有之某種光 1 1 學特徵之範圍又顯示優異耐久性〇 1 1 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） 4 修正頁 ^93005 , a A7Λ7 Printed by the Employee Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (1 peak) 1 II The present invention relates to a 1 1 1 hot-line reflective glass used in buildings, automobiles and other vehicles | with visible light and solar radiation The low-transparency hot-line reflective glass has recently been first read. 1 It has been extended to be used as the window glass of buildings and cars. M. Reducing the direct sunlight reading. 1 1 degree. Reducing the load of air conditioning. Protecting privacy and improving the appearance. 0 Hotline. 1 I Italian I shot glass is formed by a physical method such as spraying on a glass substrate to form a gold film or a gold matter 1 I is a nitride or a solution formed by spraying a film containing a gold diaphragm compound is heated and then filled 1 write this book to The thermal decomposition temperature of the gold compound is on the surface of the glass substrate Formed into a gold sheet 1 I. The oxide film was made into 0. From the viewpoint of production cost, durability of the coating film, etc. 1 1 and the latter is better than Λ * · month IJ. However, the hot-line reflective glass 1 I obtained by this method is almost Unable to reduce visible light transmission and solar radiation at certain levels (depending on the composition of the coating 1 order 1 I film) below <) In these cases, the coating film of gold diaphragm oxide containing cobalt and II has Known as 1 1 A coating film that can relatively reduce visible light transmission, etc. as in JP -B-6 3-3 2 7 36 1! The 〇 (as used herein "JP -B"-the word means a Japanese patent examined Public 1 «Report)) 1 I However, the coating film for conductive articles shown in JP-B-63-32736 has 1 1 small surface resistivity and high electromagnetic wave reflectivity when used as heat in buildings 1 1 Line reflection window glass will cause double images on TV images of neighboring houses. It has disadvantages especially in towns. In view of these circumstances, the g of the present invention is to provide a hot-line reflective glass 1 I t whose coating film has an electromagnetic wave reflectivity that is reduced to 1 1 without problems during use. At the same time, it maintains a certain range of light characteristics of the coating film containing cobalt oxide and nickel oxide and also shows excellent durability. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 4 Correction page ^ 93005, a A7

經濟部中央標準局員工消費合作杜印策五、發明説明（2 ) 本發明係關於一種熱線反射玻璃，包含一玻璃底材，其表面上具有一包含氧化鈷及氧化鎳之塗膜。塗膜具有下列特激： (1) 在本發明之第一態樣中，塗膜之表面電阻率不低於 ΙΟ4 Ω /平方及厚度不低於lOnm，鈷於塗膜内之含量為每單位面積全部金牖含量之60〜90 重量3!，及鎳於塗膜内之含量為每單位面積全部金屬含量之10〜40 重最3!。 (2) 在本發明之第二態樣中，塗膜更包含一金屬氧化物，包含至少一選自鈦、釩、鉻、錳、銅及踏之金屬，且其表面電阻率不低於104 Ω/平方及厚度不低於10nm，鈷於塗膜内之含量為每單位面積全部金臑含量之60〜89 重最！>；，及練於塗膜内之含量，為每單位面積全部金属含虽之10〜 39重量S；，及至少一選自钛、釩、铬、錳、銅及皓之金属於塗膜内之含量為每單位面積全部金靥含量之1〜30重量。 (3) 在本發明之第三態樣中，塗膜更包含氧化锇，且其表面電阻率不低於104 Ω/平方及厚度不低於10nm，及鐵於塗膜内之含最為每單位面積全部金屬含虽之1.0〜 4 . 5重量S!。 (4) 本發明之第四態樣中，塗膜之表面電阻率不低於 104 Ώ/平方及厚度為10〜70nm，主要由具有尖晶石结構本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公嫠） 5修正頁 ---------(裝------訂------iiK (請先閲讀背面之注意事項δ寫本頁) -^3005 A7 B7 經濟部中央標準局員工消費合作社印製五、發明説明（3) 1 | 之氧化物 (包含氧化鈷及氧化_)所組成及 | 一反射色調白該塗 m 之熱線反射玻璃之反俩觀察為綠 1 色糸列之顔色 0 請 1 1 I 圓 1顬示在酎酸性試驗之前 ‘後鈷之含置（M 每單位面先閲讀 1 1 I 樓塗膜之全部金屬含 ft 之百分率表示 )與可見光透視改變背之 1 1 間之闞係。圓2顬示- -依照本發明之熱線反射玻璃之概略剖面圔注意事項再 1 其中號數1為玻璃底材 2為塗膜〇本 1 ά 依照本發明之熱線反射玻璃可藉一方法製成該法包含頁、， 1 1 將含有鈷化合物鎳化合物及構成塗膜組份之其他化合物 1 1 之塗 m 形成溶液施加至玻璃底材保持溫度不低於此等金 1 | 羼化合物之熱分解溫度下以形成一金羼氧化物膜 0 更明訂 I 確而 •dbr a 該方法可藉將塗膜形成溶液啧在熔化後藉溧浮法 1 1 1 形成在玻璃製造媒上之保持高溫下之玻璃上而完成〇 1 1 1 施加塗膜形成溶液之玻璃底材之溫度較佳為350〜800它。鈷化合物之例包括乙鼸丙 m 酸鈷 (I I)或 (III) 乙酸鈷線 I m 化轱 m 酸鈷 > 硫酸鈷苯甲酸鈷 > 携化鈷硝酸鈷 1 I 氟化鈷、碘化姑草酸姑磷酸鈷亞 m 酸鈷、及硬脂 1 1 I 酸姑 0 1 鎳化合物之例包括二丙 m 甲烷鎳 Λ 二丙醢丙嗣 m Λ 乙釀 1 丙酮酸嫌乙酸鍊溴化鎳氯化嫌氟化鎳 Λ 顛矽酸鎳 1 I 硝酸練甲酸 m 氫氧化嫌 > m 化嫌硬 m 酸辣 % 胺基 1 | 磺酸鎳及硫酸鎳〇 I 1 1 在此等鍊化合物中較佳者為二丙醣甲烷辣及/或二丙 1 1 _ 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 醢丙嗣鎳，其可提供具有滿意外觀並在有櫬溶劑如酵、甲苯及二甲苯内具有滿意溶解度之塗膜。乙醣丙酮酸_形成具有進一步改良外観之塗膜，亦可較佳地用於本發明。由於乙醢丙嗣酸辣在有機溶W如酵、甲笨及二甲苯内具有低溶解度•在有櫬溶劑内較好K懸浮液形式使用之。鈦化合物之例包括四氣化钛、四乙氧化呔、乙釀丙嗣酸氣钛、硫酸钛（III)、硫酸钛（IV)、四丁氧化鈦、異丙氣化钛、甲氧化钛、二異丙氧雙辛烯甘酵氧化鈦、二正丙氧雙辛烯甘酵氧化钛、二異丙氣單辛烯甘酵氣乙醮丙嗣酸钛、二正丁氧單立烯甘酵氧乙酺丙釅酸钛、四辛烯甘酵氧化钛及二正丙氧雙乙醢丙_酸钛。釩化合物之例包括乙鼸丙國酸釩、乙醣丙酮酸氧釩、三氯化釩、二氯化釩、三氣化氧釩、硝酸氧釩、草酸氧釩、及硫酸氧釩。鉻化合物之例包括乙釀丙嗣酸鉻、乙酸格（III)、氣化鉻（III)、氣化鉻（III)、甲酸鉻（III)、氟化鉻（III)、硫酸銨鉻、氫氧化鉻（III)、硝酸鉻（III)、磷酸鉻（III)、磙酸鉀鉻及磙酸鉻（III)。錳化合物之例包括乙釀丙嗣酸錳（I)、乙醜丙嗣酸錳 (II)、乙酸锰、硫酸銨錳、碥酸錳、溴化錳、碳酸錳、氱化錳、氟化錳、氟矽酸錳、甲酸錳、碘化錳、乳酸錳、确酸錳、草酸錳、二氫磷酸錳、氫磷酸錳、疏酸錳及酒石酸錳。 -=_2_二- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------襄— (請先閱讀背面之注意事項再填寫本頁) 、vaDu Yince, Employee Consumption Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (2) The present invention relates to a hot-line reflective glass, which includes a glass substrate with a coating film containing cobalt oxide and nickel oxide on its surface. The coating film has the following special features: (1) In the first aspect of the invention, the surface resistivity of the coating film is not less than 10 4 Ω / square and the thickness is not less than 10 nm, and the content of cobalt in the coating film is per unit 60 ~ 90 weight 3! Of the total gold content of the area, and the content of nickel in the coating film is 10 ~ 40 of the total metal content per unit area, and the most weight 3! (2) In the second aspect of the present invention, the coating film further includes a metal oxide, including at least one metal selected from titanium, vanadium, chromium, manganese, copper and tread, and its surface resistivity is not less than 104 Ω / square and thickness not less than 10nm, the content of cobalt in the coating film is 60 ~ 89 of the total content of gold per unit area. >; and the content in the coating film is 10 ~ 39 weight S per unit area of all metals, and at least one metal selected from titanium, vanadium, chromium, manganese, copper and hao in the coating film The content is 1 to 30 weights per unit area of the total gold content. (3) In the third aspect of the present invention, the coating film further includes osmium oxide, and its surface resistivity is not less than 104 Ω / square and the thickness is not less than 10 nm, and the content of iron in the coating film is most per unit The area of all metals contains 1.0 ~ 4.5 weight S !. (4) In the fourth aspect of the present invention, the surface resistivity of the coating film is not less than 104 Ώ / square and the thickness is 10 ~ 70nm, which is mainly composed of spinel structure. The paper size is applicable to the Chinese National Standard (CNS) Α4 Specifications (210 X 297 gong mai) 5 correction pages --------- (installed ------ ordered ---- iiK (please read the notes on the back δ to write this page)- ^ 3005 A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (3) 1 | composed of oxides (including cobalt oxide and oxidized _) and | On the contrary, it is observed as green 1 color of the color column 0 please 1 1 I round 1 塬 shows before the acid test of the 'acid cobalt content (M per unit surface first read 1 1 I floor coating all metals containing ft (Percentage) and the visible light perspective change between the front and back of the 1 1. Circle 2 顬 shows--according to the present invention is a schematic cross-section of the hot-line reflective glass 圔 Notices Note 1 where the number 1 is the glass substrate 2 is the coating film.This 1 ά hot ray reflective glass according to the present invention can be made by a method that contains pages, 1 1 a coating solution containing a cobalt compound nickel compound and other compounds constituting the coating film component 1 1 is applied to the glass bottom The temperature of the material is not lower than these gold 1 | The thermal decomposition temperature of the compound is to form a gold oxide film. 0 It is more accurate and accurate. Dbr a This method can be used by applying the coating film forming solution after melting The Li float method 1 1 1 is formed on a glass maintained at a high temperature on a glass manufacturing medium to complete. 1 1 1 The temperature of the glass substrate to which the coating film forming solution is applied is preferably 350 to 800 ° C. Examples of cobalt compounds include B Cobalt (II) or (III) Cobalt Acetate Cobalt Acetate Line I m Cobalt Oxide Cobalt Oxide & Cobalt Sulfate Cobalt Benzoate & Cobalt Cobalt Nitrate 1 I Cobalt Fluoride, Cobalt Iodide and Cobalt Phosphate m Cobalt acid, and stearin 1 1 I Suan 0 1 Examples of nickel compounds include dipropylene m methane nickel Λ dipropylene propylene diamine m Λ ethyl alcohol 1 pyruvic acid acetic acid chain nickel bromide chloride chloride nickel chloride fluoride nickel tandem silicate 1 I nitric acid formic acid m hydroxide > m is too hard m hot and sour% amine group 1 | nickel sulfonate and nickel sulfate 〇I 1 1 Of these chain compounds, the preferred ones are dipropyl sugar methane hot and / or dipropylene 1 1 _ 1 paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The A7 B7 is printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (4) Nickel propylene, which can provide a satisfactory appearance and in the presence of solvents Such as the coating film with satisfactory solubility in yeast, toluene and xylene. Glycopyruvate_ forms a coating film with further improved external appearance, which can also be preferably used in the present invention. Due to its low solubility in organic solvents such as yeast, methylbenzine and xylene, it is used in the form of a good K suspension in a solvent. Examples of titanium compounds include tetra-gasified titanium, tetra-ethoxylated titanium, ethyl propionic acid gas titanium, titanium (III) sulfate, titanium (III) sulfate, titanium tetrabutoxide, isopropylated titanium vapor, titanium formate, Diisopropoxybisoctene Glycolytic Titanium Dioxide, Di-n-Propoxybisoctene Glycolytic Titanium Dioxide, Diisopropane Monooctene Glyoxylate Gas, Titanium Acetyl Propionate, Di-n-Butoxymonoricene Glyceryl Titanium oxyethyl hydrapropionate, titanium octoglycolate and di-n-propoxy bisacetoxypropionate titanium. Examples of vanadium compounds include vanadium propionate, vanadyl ethyl pyruvate, vanadium trichloride, vanadium dichloride, vanadium trioxide, vanadyl nitrate, vanadyl oxalate, and vanadyl sulfate. Examples of chromium compounds include chromium propionate, acetate (III), vaporized chromium (III), vaporized chromium (III), chromium (III) formate, chromium (III) fluoride, chromium ammonium sulfate, hydrogen Chromium (III) oxide, chromium (III) nitrate, chromium (III) phosphate, potassium chromate and chromate (III). Examples of manganese compounds include manganese (I) ethyl propionate, manganese (II) ethyl propionate, manganese acetate, manganese ammonium sulfate, manganese oxalate, manganese bromide, manganese carbonate, manganese trichloride, manganese fluoride , Manganese fluorosilicate, manganese formate, manganese iodide, manganese lactate, manganese oxalate, manganese oxalate, manganese dihydrogen phosphate, manganese hydrophosphate, manganese sulphate and manganese tartrate. -= _ 2_ 二-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) --------- Xiang— (Please read the precautions on the back before filling this page), va

T A7 B7 經濟部中央標準局員工消費合作社印製五、發明説明（5 ) 網化合物之例包括乙醣丙嗣酸鋦、溴化鋦（I)、溴化網 (II)、氛化飼（I)、氣化鑭（II)、氯化銨嗣（II)、檸懞酸銅（II)、氰化網（II)、氟礓酸鋦、氟化鋦（II)、氟矽酸鋦、甲酸綢（II)、氫氧化鋦（II)、磺化钃（I)、硝酸鋦、油酸鋦、草酸鋦（II)、磷酸鋦（II)及疏酸網。綹化合物之例包括乙釀丙_酸鍤、氫氧化結、硝酸維、亞硝酸結、氧氣化皓、氧磷酸皓、疏酸皓、四氣化结及乙酸锆。鐵化合物之例包括乙睡丙嗣酸嫌、氛化級（II)、氣化嫌、撺懞酸嫌、草酸銨嫌、磙酸銨嫌、氟<91酸嫌、氟化鐵、氟矽酸鐵、乳酸嫌（II)、硝酸嫌、草酸嫌（II)、磷酸鐵 (II)、磷酸鐵、磙酸嫌（II)、硫酸嫌及酒石酸嫌（II)。闞於溶解或分散上述金屬化合物之溶劑，通常可使用有櫬溶劑如芳香溶劑、_溶劑、酮溶劑、酵溶爾、醚溶劑。玻璃底材之例通常包括一無色透明之納鈣玻璃底材，但不受其所限制。為了調整可見光透射或透射光之色調，亦可使用包含撤畺著色劑之著色納鈣玻璃。為了減少反射率•塗膜可藉一步包含矽或鋁。為了諝整色調，塗膜可進一步包含鋅、錫、銻、絪等。用來減少反射率或調整色讕之此等金靨之含量，較好為每單位面積全部金臛含量之3重量S!或以下。在依照本發明第一態樣之塗膜中，自塗膜之附久性之觀點而言，鈷於塗膜内之含量較好為每單位面積全部金靨含量之68〜87重量X，鎳於塗膜内之含量較好為毎單位面積 (請先閱讀背面之注意事項再填寫本頁) 裝-T A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Descriptions of inventions (5) Examples of net compounds include glycopyrrolate, bromide (I), brominated nets (II), and aerated feed ( I), Vaporized Lanthanum (II), Ammonium Chloride (II), Copper Citrate (II), Cyanide Net (II), Fluorinated Manganese Oxide, Fluorinated Manganese (II), Fluorinated Silicate Manganese, Formic acid silk (II), hydroxide (II), sulfonated metal (I), nitrate, oleate, oxalate (II), phosphate (II) and acid-repellent net. Examples of lock compounds include ethyl propane sulfonate, hydroxide, nitrate, nitrite, oxygenated oxonate, oxyphosphate, sulfuric acid sulfonate, tetragasification, and zirconium acetate. Examples of iron compounds include acetylpyridinium chloride, chlorination grade (II), gasification sulfonate, chlorinate sulfonate, ammonium oxalate, ammonium oxalate, fluorine < 91 acid, iron fluoride, fluorosilicone Ferric acid, lactic acid (II), nitric acid, oxalic acid (II), ferric phosphate (II), ferric phosphate, aspartic acid (II), sulfuric acid and tartaric acid (II). Kan is a solvent that dissolves or disperses the above-mentioned metal compounds. Generally, solvents such as aromatic solvents, solvents, ketone solvents, yeast solvents, and ether solvents can be used. Examples of glass substrates generally include a colorless and transparent soda lime glass substrate, but are not limited thereto. In order to adjust the hue of visible light transmission or transmitted light, tinted soda lime glass containing colorants can also be used. In order to reduce the reflectivity, the coating film can contain silicon or aluminum in one step. In order to consolidate the color tone, the coating film may further contain zinc, tin, antimony, or the like. The content of these gold garnets used to reduce the reflectance or adjust the color is preferably 3% by weight or less of the total gold slab content per unit area. In the coating film according to the first aspect of the present invention, from the viewpoint of the durability of the coating film, the content of cobalt in the coating film is preferably 68 to 87 weight X per unit area of the total gold content, nickel The content in the coating film is preferably per unit area (please read the precautions on the back before filling in this page)

、1T, 1T

J —線本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X297公釐） 8 經濟部中央標準局員工消費合作社印製 A7 __^_B7_ 五、發明説明（6 ) 全部金屬含量之13〜32重量！Κ。依照本發明之第一及第二態樣之塗膜較佳為具有厚度不超過130η β，因為若厚度太大時，表面®胆率視其組成物而定可為低於104 Ω/平方。自热線反射玻璃之生產力之觀點而言，厚度較好不超過100nm，自可見光之透射率而言，更好不超過45η·。依照本發明所有態樣之塗膜之厚度較佳為20〜45η·，因為具有此範圃厚度之塗膜可提供優異外観。厚度更佳為20 〜4〇ηΒ。使用具有該厚度之塗膜之熱線反射玻璃供建築物之窗戶用，可抑制由於室内明亮物在夜晩之反射所造成之不舒癯*因為在塗膜側上之反射顔色變成單色；亦可抑制由於建築物外壁之反射光之污染，因為可減少熱線反射玻璃在塗膜之倜（及反向於塗膜之供之反射率。在依照本發明第三態樣之塗膜中，自可見光透射率之綢整及塗膜附久性之改良之観點而言，練於塗膜内之含最較好為每單位面稹全部金羼含量之5〜40簠量S：。依照本發明之热線反射玻璃較好顧示一透射色調，如依照JIS Ζ8722-1 982所界定，在下面範_内： -4.5^ 4.5 3.0^ 12.5 上述透射顔色，以热線反射玻璃之外觀之產品價而言質 *較好在下面範圈内： -0.5^ 0.5 5.0^ 8.5 ---=_9_=- 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X 297公釐） ^--裝------訂-----—線 (請先閱讀背面之注意事項再填寫本頁) B7 經濟部中央標準局員工消费合作社印製五、發明説明( 7 ) 1 1 白反向於塗膜之热嬢反射玻璃之側看到之反射可見光較 1 | 好顯示一反射色調如依照J IS Z8722- 1 982所界定在下 | 面範圃内 1 1 -7 • os a * ^ -3 .0 請先 1 1 -5 .0^ 4 . 0 閱讀背面 1 I 1 I 此廉所用之 a*及 b*為依照 J IS Z8729- 1 980所界定之之 1 注意事 1 L* a*b*比色色系統之色度指數。 1 項再依照本發明第 __. 態樣之热線反射玻璃具有表面電阻率為填 1 10 4 Ω /平方或Μ上使霣磁波反射被抑制至- -程度在寫本頁 % 1 實用時實質上不會造成任何問題〇雖然表面霣阻率随著薄 1 1 m 厚度減少而增加由於薄膜之組成物相等本發明第一 1 I 態樣之塗 _ 之下限被設定在 1 0 n a 俾可保持對热線反射玻 1 訂璃必要之光學性能特性〇另外，本發明第一態樣之热線反射 1 I 玻璃之可見光透射率及太隈輻射率藉限制氧化鈷及氣化鍊 1 1 之含量而被控制在資際有利之範園内〇即在含有氧化鈷 1 1 及氧化嫌之塗 m 内具有尖晶石结構之鎳簿鈷礦會減少表 ] 線面電阻率〇因此雖然塗 m 之電阻率可藉使鎳對鈷之比率 1 I 大大不同於鑠鐸鈷確之化學計悬比 (N i/C0 = 1/2)而壜加 1 1 1 若此增加霣阻率之方式被應用至氧化鈷之比例低於60!ί之 1 1 情況時可見光透射率有超逢50X之可能 >另— -方面當 1 此方式被應用至氧化練之比例低於10«之情況時 |玻璃之 | 太暍輻射透射率則無法如可見光透射率一般減少〇在兩種 1 I 情況下塗膜之特性並不顯著。因此在本發明之第一態 1 1 I 樣中該問題可藉將鈷及鍊對每單位面稹塗 m 之全部金屬 1 1 1 1 本紙張尺度遑用中國國家梯準（CNS ) A4規格（210X 297公釐） 10 經濟部中央標準局員工消費合作社印製 A7 __B7_ 五、發明説明（8 ) 含量之重畺！K分別界定在60〜90¾之範圃內及10〜405ί之範圍内而避免。依照本發明第二態樣之热線反射玻璃顬示上述本發明第一態樣之特性，更改良耐久性，因為本發明第二戆樣之塗膜包含至少一遘自钛、釩、络、錳、網及皓之金颺。依照本發明第三態樣之热線反射玻璃亦具有表面霣阻率為104 Ω/平方或以上，使霣磁波反射被抑制至一程度，在實用時實霣上不會造成任何問鼴。在本發明第三態樣之塗膜中，厚度之下限被設定在lOnni，俾可保持對热線反射玻璃必要之光學性能特性，厚度之上限被設定在70η·，俾可在不使用大量鐵下達到表面電阻率為ΙΟ4 Ω/平方或Μ 上。因此*依照本發明第三態樣之塗膜内嫌之含最可被減至4.5重量！ϋ或以下，俾可改良塗膜之酎久性，特別是酎酸性。依照本發明第四態樣之热線反射玻璃亦具有表面霣阻率為104 Ώ/平方或以上，使電磁波反射被抑制至一程度，即，在實用時實質上不舍造成任何問題。在本發明第四態樣之熱媒反射玻璃中*自反向於塗膜之側看到之反射色調為綠色系列之顔色。因此，其可被用作具有綠色反射色調之熱媒反射玻璃，自配合建築物及周鼷景色之色調之觀點而言，其被要求如同建築物之窗戶般。習知具有綠色反射色調之熱線反射玻璃包括具有三曆由氧化鈦及氮化钛所組成之塗膜之玻璃，如JP-A-63-1 90742所述。（此處所用之 ” JP-A” 一詞意指未審査之日本專利申請案）。由於此習知 ---=~~L4~~=- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ----------^-- (請先閲讀背面之注意事項再填寫本頁) 訂J —Standard paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) 8 Printed by the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative A7 __ ^ _ B7_ V. Description of invention (6) 13 ~ 32 of all metal content weight! Κ. The coating films according to the first and second aspects of the present invention preferably have a thickness not exceeding 130 η β, because if the thickness is too large, the surface bladder ratio may be less than 104 Ω / square depending on the composition. From the viewpoint of productivity of the heat-ray reflective glass, the thickness is preferably not more than 100 nm, and from the transmittance of visible light, it is more preferably not more than 45η ·. The thickness of the coating film according to all aspects of the present invention is preferably from 20 to 45 η ·, because the coating film having such a thickness can provide excellent appearance. The thickness is more preferably 20 to 40 nB. The use of heat-reflecting glass with a coating film of this thickness for the windows of buildings can suppress the uncomfortableness caused by the reflection of indoor bright objects at night * because the color of the reflection on the coating film side becomes monochromatic; also It can suppress the pollution of the reflected light of the outer wall of the building, because it can reduce the reflectance of the hot-line reflective glass in the coating film (and the reflectivity of the supply opposite to the coating film. For the improvement of the visible light transmittance and the improvement of the durability of the coating film, the best content in the coating film is 5 to 40 milligrams of S :. The inventive heat ray reflective glass preferably reflects a transmission hue, as defined in accordance with JIS Z8722-1 982, within the following range: -4.5 ^ 4.5 3.0 ^ 12.5 The above transmission color, the product with the appearance of heat ray reflective glass In terms of price, quality * is better within the following circle: -0.5 ^ 0.5 5.0 ^ 8.5 --- = _ 9 _ =-This paper size is applicable to China National Standard (CNS) A4 (210X 297mm) ^-installed- ----- Subscribe ------- Line (Please read the notes on the back before filling in this page) B7 Printed by the Ministry of Central Bureau of Standards and Employee's Consumer Cooperative V. Description of the invention (7) 1 1 The visible light reflected by the side of the reflective glass on the side of the thermal film of the coating film is better than 1 | It shows a reflective hue as per J IS Z8722- 1 982 is defined below | In the front of the garden 1 1 -7 • os a * ^ -3 .0 Please first 1 1 -5 .0 ^ 4. 0 Read the back 1 I 1 I a * and b * for this product It is 1 according to the definition of J IS Z8729-1 980. Note 1 The chromaticity index of the L * a * b * colorimetric color system. Item 1 according to the invention __. The form of the heat-ray reflective glass has surface resistance The rate is filled with 1 10 4 Ω / square or Μ so that the reflection of the magnetic wave is suppressed to a level of-at the time of writing this page. 1 Practicality will not cause any problems in practice. Although the surface resistance rate decreases with the thickness of 1 1 m Decrease and increase due to the film The composition is equal to the coating of the first 1 I aspect of the present invention_ The lower limit is set to 10 na so as to maintain the optical performance characteristics necessary for the heat ray reflective glass 1 glass. In addition, the hot line of the first aspect of the present invention Reflective 1 I The visible light transmittance and Okuma's emissivity of the glass are controlled within the range of favorable resources by limiting the content of cobalt oxide and gasification chain 1 1, that is, within the coating m containing cobalt oxide 1 1 and oxidation Nickel cobalt ore with a spinel structure will reduce the surface] surface resistivity. Therefore, although the m-coated resistivity can make the ratio of nickel to cobalt 1 I greatly different from the stoichiometric ratio (N i / C0 = 1/2) and increase 1 1 1 if this method of increasing the resistance is applied to the ratio of cobalt oxide is less than 60! 1 1 1 case of visible light transmittance may exceed 50X > > On the other hand-when the ratio of this method is applied to oxidation training is less than 10 « When the case where | glass | Ye too radiation transmittance of the visible light may not be such a transmittance of generally square reduced Laid coating film of 1 I In both cases is insignificant. Therefore, in the first state 1 1 I of the present invention, this problem can be solved by applying cobalt and chain to all the metals per unit face m 1 1 1 1 This paper standard is not in accordance with the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) 10 A7 __B7_ printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (8) The weight of the content! K is defined within the range of 60 ~ 90¾ and 10 ~ 405ί to avoid. The hot-line reflective glass according to the second aspect of the present invention shows the above-mentioned characteristics of the first aspect of the present invention, and changes the good durability, because the coating film of the second aspect of the present invention contains at least one of titanium, vanadium, complex, Jin Yang of Manganese, Net and Hao. The heat ray reflecting glass according to the third aspect of the present invention also has a surface resistivity of 104 Ω / square or more, which suppresses the reflection of the magnetic wave to a certain degree, and does not cause any problems in practice. In the coating film of the third aspect of the present invention, the lower limit of the thickness is set to lOnni, so as to maintain the optical performance characteristics necessary for the hot-line reflective glass, and the upper limit of the thickness is set to 70η ·, so that a large amount of iron is not used The lower reaches the surface resistivity of 104 Ω / square or Μ above. Therefore, * the content contained in the coating film according to the third aspect of the present invention can be reduced to 4.5 weight at most! ϋ or below, to improve the durability of the coating film, especially the acidity. The heat ray reflecting glass according to the fourth aspect of the present invention also has a surface resistivity of 104 Ώ / square or more, which suppresses the reflection of electromagnetic waves to a degree, that is, practically does not cause any problems in practice. In the heat medium reflective glass of the fourth aspect of the present invention, the reflection tone viewed from the side opposite to the coating film is a green series color. Therefore, it can be used as a heat-reflecting glass with a green reflection hue. From the viewpoint of matching the hue of the building and surrounding scenery, it is required to be like a window of a building. Conventionally, hot-line reflective glass with a green reflection hue includes glass having a coating film composed of titanium oxide and titanium nitride in three calendar years, as described in JP-A-63-1 90742. (The term "JP-A" used here means an unexamined Japanese patent application). As a result of this practice --- == ~~ L4 ~~ =-This paper standard is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) ---------- ^-(please read the back first Note to fill out this page)

J -線· A7 B7 經濟部中央標準局員工消費合作社印製五、發明説明（9 ) 1 1 热線反射坡璃係賴物理蒸氣沉積形成塗 m 而製得其生產 1 f I 力劣於本發明第四態樣之热線反射玻璃其中高度射久性 1 之塗膜可以低成本製得〇具有如本發明第四態樣相同尖晶 /·—V 請异 1 I 石結 m 但由姑鉻及嫌所組成之氧化物膜可藉塗 m 形成溶閱 ik 背 1 1 液之热沉積而製得〇然而具有該組成物之塗膜無法顬不之注 1 1 綠色反射色調即使調整其厚度亦然〇在此情況雖可得意事項， 1 -VI 接近綠色區之色調惟很難在宽面積上形成均匀塗臢而得再填 1 均匀色調〇 % 本頁 1 依照本發明之第一第二及第三態搛之熱 m 反射玻璃可 1 1 藉調整塗臢 9 明確而 —w 藉使塗膜之厚度成為70nn 或 >x 下可 1 I 顯示類似於本發明第四態樣之綠色反射色調〇 1 訂本發明將參照下列實施例及比較例更詳述之惟本發明 1 I 並不受實施例所限制〇 1 1 實施例 1 1 將 150· m長、 1 5 0 οι π 寬及 4 18 厚之納鈣矽玻璃板洗滌並乾 1 1 線煉 Μ 製備一底材 0 底材用掛鈎固定於設定在650C下之 1 | 霣爐内並維持5分鐘，使用市面上可得之嘖鎗在空氣 1 1 壓力為 3 . 0kg/ c丨 2 Λ 氣流為90 1 /分鐘及噴塗之速率為 1 1 20m 1 /分鐘下將溶解於100 C C 甲苯内之由 5 . 13g乙醢丙嗣 1 酸鈷 (111)與 1 .18g 二丙酿甲垸 m (II)所組成之塗佈溶液啧 I 在白霣爐取出之底材上歷約 10秒〇 1 1 1 依照 J IS R 3 106 -1985澜定所得熱烺反射玻璃之可見光 1 1 透射率可見光反射率太陽輻射透射率及太陽輻射反射 1 1 率〇藉射頻電漿發射光譜術澜定基於塗 m 内全部金羼含量 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- A7 B7 五、發明説明（i 0) 之鈷含1。澜定塗膜之表面電阻率及厚度。所得结果被示於下表1。實施例2 除了乙醢丙_酸鈷（ II I) 之量改為4 . 27g、二丙釀甲烷嫌 (I D 改為 1 . 9 6 g ' 嘖射時間改為約15秒及啧塗之速率改為 24 η 1 /分鐮Κ外，如實施例 1相同方式製備熱媒反射玻璃〇 Κ 如實施例1相同方式檢驗所得热線反射玻璃c >所得结果被示於表 1 ° 實豳例 3 除了乙醢丙酮酸鈷（ I I I) 之量改為3 . 2 1 g、二丙釀甲烷嫌 (I I) 改為 2 . 9 4 g ' 哦射時間改為約20秒及啧塗之速率改為 28 η 1 /分鐘Κ外，如實施例 1相同方式製備热線反射玻璃〇以如實施例1相同方式檢驗所得热媒反射玻璃< >所得结果被示於表 1 0 比較例 1 為了比較起見，形成由絡- 、鐵及鈷之金鼷氧化物所組成 I-------^--^-- (請先閱讀背面之注意事項再填寫本頁) 訂J-line · A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (9) 1 1 The hot-line reflective glass is produced by physical vapor deposition to produce m 1 f I is inferior to the original The fourth aspect of the invention is a hot-line reflective glass in which a highly durable coating film 1 can be produced at low cost. It has the same spinel as the fourth aspect of the present invention. The chromium and the oxide film composed of it can be prepared by coating m to form a thermal deposit of ik back 1 1 solution. However, the coating film with this composition cannot be applied. Note 1 1 Green reflective hue even if the thickness is adjusted Also in this case, although it is a good thing in this case, the hue of 1 -VI close to the green area is difficult to form a uniform smear on a wide area and it needs to be filled with 1 even hue. 0% Page 1 According to the first and second aspects of the invention And the third state The heat m reflective glass can be 1 1 by adjusting the coating 9 clearly and -w if the thickness of the coating film becomes 70nn or > x under 1 I can display a green reflection hue similar to the fourth aspect of the invention 〇1 The invention will be described in more detail with reference to the following examples and comparative examples. However, the invention 1 I is not limited by the examples. Example 1 1 will be 150 · m long, 1 5 0 ο π wide, and 4 18 thick. Calcium silica glass plate washed and dried 1 1 line refining Μ Preparation of a substrate 0 The substrate is fixed with a hook to the 1 set at 650C | Married furnace and maintained for 5 minutes, using a commercially available gun in the air 1 1 The pressure is 3.0 kg / c 丨 2 Λ The gas flow rate is 90 1 / min and the spraying rate is 1 1 20m 1 / min. It will be dissolved in 100 CC toluene from 5.13g acetopropanol 1 cobalt acid (111) The coating solution consisting of 1.18 g of dipropylene carbamide (II) I was taken on the substrate taken out of the white furnace for about 10 seconds. 1 1 1 Visible light of thermoreflective glass obtained in accordance with J IS R 3 106 -1985 Landing 1 1 Transmittance visible light reflectance Solar radiation transmittance and solar radiation reflection 1 1 rate The content of all the gold in the m 1 1 The size of the paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- A7 B7 V. Description of the invention (i 0) Cobalt contains 1. The surface resistivity and thickness of Landing coating film. The results obtained are shown in Table 1 below. Example 2 Except that the amount of ethylenedipropionate-cobalt (II I) was changed to 4.27g, the dipropylene methane (ID was changed to 1.96 g 'shot time was changed to about 15 seconds and the rate of coating It was changed to 24 η 1 / min K, and the heat medium reflective glass was prepared in the same manner as in Example 1. The obtained heat ray reflective glass was examined in the same manner as in Example 1. The obtained results are shown in Table 1 °. 3 Except that the amount of cobalt (III) acetoacetate is changed to 3.2 1 g, and that of dipropyl alcohol (II) is changed to 2. 9 4 g 'The shooting time is changed to about 20 seconds and the coating rate is changed. Except for 28 η 1 / min Κ, a heat ray reflective glass was prepared in the same manner as in Example 1. The obtained heat medium reflective glass was examined in the same manner as in Example 1. The results obtained are shown in Table 10. Comparative Example 1 For the sake of comparison, the formation of gold-oxide oxides consisting of gold, iron and cobalt I ------- ^-^-(please read the precautions on the back before filling out this page)

J —線· 經濟部中央標準局員工消費合作杜印製之薄膜被形成Μ產生热線反射玻璃。除了乙醣丙嗣酸鈷 (III)之量改為6.55g、1.90g乙醸丙嗣酸嫌（III)及5.00g 乙釀丙嗣酸铬（III)被用來取代二丙釀甲烷嫌（II)、啧射時間改為約30秒及嗔塗之速率改為35ml /分鐘Μ外，以如實施例1相同方式製備热線反射玻璃。以如實施例1相同方式檢《所得熱線反射玻璃。所得结果被示於表1。 —-1-3_二本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）年月曰補充％ 2· 〇7 Α7 Β7 五、發明説明U〇£〇减詻漥一 »«詻漥2 WI® 漥 3 tb » 渣一一 η m ) 26 IZ 18 88 (vt!!(％) 007 ^1.1 7 8 私知.0 6 2 5 0.0 6 3 3 2.3 u) 23.7 2ro. 0 22.3 32.6 u) 合3 . 6 浴5 . 1 5 1.2 37.2 經濟部中央樣準局員工消費合作社印製 li爾N 醉聆凶挪法£1挪涞 Hi®譎 H13譎谢Μ® ft 闲 _ N 陈 aN-^lsiltN-燄 ιίΝ·郊固慚 0 a概J-line · The film produced by the Duo Printing Co., Ltd. of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China is formed into a hot-line reflective glass. Except that the amount of cobalt (III) ethyl propionate is changed to 6.55g, 1.90g of ethyl propionate (III) and 5.00g of chromium (III) ethyl propionate are used to replace dipropylene methane II). The injection time was changed to about 30 seconds and the coating rate was changed to 35 ml / min. M, and the hot-ray reflective glass was prepared in the same manner as in Example 1. The obtained hot-line reflective glass was examined in the same manner as in Example 1. The results obtained are shown in Table 1. —-1-3_The size of the two papers is in accordance with the Chinese National Standard (CNS) Α4 specification (210Χ297mm). The date is supplemented by 2%. 〇7 Α7 Β7 V. Description of the invention U〇 £ 〇輻漻漥一 »« 詻漥 2 WI® 漥 3 tb »slag one η m) 26 IZ 18 88 (vt !! (%) 007 ^ 1.1 7 8 private knowledge. 0 6 2 5 0.0 6 3 3 2.3 u) 23.7 2ro. 0 22.3 32.6 u) 3.6 baths 5. 1 5 1.2 37.2 Ministry of Economic Affairs Central Prospects Bureau employee consumer cooperatives printed lier N drunk listening murder law £ 1 Nor Lai Hi® X H13 X Xie M® ft idle_ N 陈 aN -^ lsiltN- 火 ιίΝ · 乡固歭 0 a

aem(ΚΩ/ u) 书时 20.3 51 19.0 2ίο 18.5 170 3 5,0 I 本紙張尺度逋用中國國家標準（CMS ) A4規格（210X 297公釐） 0 1 13 α修正頁 (請先閱讀背面之注意事項再填寫本頁) 袈 -9 2^3005 A7 B7 __ 五、發明说明Ul) (請先聞讀背面之注意事項真填寫本頁) 由表1之结果可知，實腌例1〜3之热線反射玻瑰具有表面«阻率為104 Ω/平方或以上及可見光透射率為50X或Μ 下，太»輻射透射率不超邊高於可見光射率之值2.5Χ。在比較例1之热嬢反射玻_中•可見光之适射率被抑制至50Χ 或以下，但太_轜射之透射率幾乎高於可見光透射率5Χ。因此，實豳例1〜3之热線反射玻璃在太限輻射邃蔽性能方面優於比較例1者。測定實施例2及3與比較例1所得之热鑲反射玻璃之透射光之色度指數a*及b*。其结果被示於下表2。表 2 3 ί右 b幸實 m 例 2 0. 2 8 8.29 實施例 3 -0. .13 8.41 比較例 1 -0. ,72 13.80 賁豳例4〜8及比較例2與3 除了改變塗佈溶液之組成物以外·Μ如實施例1相同方式製備热線反射玻璃。依照JIS R 31 06-1985測定所得熱嬢反射玻璃之可見光透射率、可見光反射率、太陽轜射适射率及太皤輻射反射率。另外，依照J IS R 3221-1990檢驗酎化學性，但將玻璃浸溃於化學品内之時間為3日。所得结果被示於表3及圏1。經濟部中央揉準局貝工消費合作社印製表 3 塗膜之鈷含可見光太陽轜表面霣附久性厚度量之适射射之适阻率酸 _ 率射率 (ΚΩ / (X) (X) (η·) (wtX) ⑴ ⑴ 平方）資豳例4 30 80 41.1 43.6 51 2.30.0 實施例5 30 70 42.0 43.5 48 3.60.0 14 本紙張尺度遑用中國國家標準（CNS ) A4规格（210X2.97公釐）經濟部中央樣準局貝工消费合作社印製五、發明説明（l2) A7 —_______B7 寅施例6 25 85 44.5 47.2 70 3.9 0.0 «豳例7 25 67 44.0 45.1 29 5.4 0.0 實施例8 25 80 43.8 46.2 63 3.4 0.0 比較例2 25 50 50.3 51.2 170 39.4 0.0 比較例3 30 100 42.5 47.3 250 8.3 0.0 備註：*射久性：在化學品内浸潰前後之遒射率之改變。由圖1可知》塗膜之射酸性在鈷含悬為68〜87重量：(之區内特別優異。由表3之结果可知，具有鈷含量為50簠量X之金羼氧化物塗Μ具有可見光透射率超遘5 0X，但具有鈷含量為100重量 X之金鼷氧化物塗_具有太矚輻射透射率高於可見光透射率約5Χ·因此無法達到充分透射能量控制性能。有所有實施例1〜8中，可得具有均勻外観之塗膜。在資施例1〜8中，無色逋明納鈣玻璃醮被用作玻璃底材，所得熱線反射玻璃之可見光透射率、太隈辐射透射率及适明色調可使用著色納鈣玻璃作為底材而被壤笛鯛整。比較例4 除了乙釀丙酮酸鈷（III)之量改為7.12g、二丙釀甲烷鎳 (II)改為3.13g，甲烷之量改為2 00cc、嗔射時間改為約50 秒及啧塗之速率改為100·1/分鐘以外* Μ如實施例1相同方式製備热媒反射玻璃。所得熱媒反射玻璃具有厚度為 150η·之塗膜•且可見光之透射率為8.5«·但表面電阻率為1100 Ω /平方。賞施例9 將150·長、150·寘及4··厚之納鈣矽玻璃板洙滌並乾燥，Μ製備一底材。底材用掛鈎固定於設定在650 t：下之 «爐內*並維持5分鐘。使用市面上可得之嗔鎗·在空氣本紙張纽逋用中ΒΒΙ家橾準（CNS > A4«US· ( 210x297公釐) " ~ 15 -------^-I裝------訂-----『‘線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央梂準局貝工消费合作杜印製 A7 B7 五、發明説明（13) 颳力為3.0kg/cB2 、氣流為901/分鏟及噴塗之速率為 20屋1/分鐘下，將溶解於100<：(；甲苯内之由5.138乙醸丙酮酸鈷（III)與1.18g二丙》甲烷嫌（II)及〇.65g乙醢丙酮酸釩所組成之塗佈溶液嗔在自電《取出之底材上，歷約1〇秒。依照JIS R 3106-1 985測定所得熱媒反射玻璃之可見光透射率。藉射頻霣漿發射光譜術测定基於塗膜内全部金羼含量之鈷含量。測定塗膜之表面電阻率及厚度。所得結果被示於下表4。實_例10 除了 0.66 g乙釀丙酮酸鉻被用來取代乙釀丙酮酸釩以外，Μ如實施例9相同方式製備热線反射玻璃’並Μ如實施例9相同方式檢驗之。所得结果被示於表4。實施例11 除了 0.66g乙醮丙酮酸錳被用來取代乙釀丙_酸釩以外，以如實施例9相同方式製備热線反射玻璃，並以如霣施例9相同方式檢驗之。所得结果被示於表4。賨施例12 除了 0.66g乙醢丙_酸络被用來取代乙釀丙_酸釩以外，以如實腌例9相同方式製備热線反射玻璃’並Μ如實腌例9相同方式檢驗之。所得结果被示於表4。實施例13 除了 0.66s乙醢丙酮酸皓被用來取代乙醢丙_酸釩以外，以如資施例9相同方式製備熱線反射玻璃，並Μ如實施例9相同方式檢驗之。所得结果被示於表4。本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） I------叫—裝------訂-----『.線 (請先閱讀背面之注意事項再填寫本頁) 16 經濟部中央標準局員工消費合作社印製 A7 _____B7_ 五、發明説明（1 4 ) 比較例5 除了未使用乙釀丙酮酸皓Μ，Μ如實腌例9相同方式製備熱線反射玻璃，並Κ如實施例9相同方式檢驗之。所得結果被示於表4。表 4 加入之塗膜之可見光姑含表面電元素厚度之透射量阻率射率 (k Ω / (n m) (% ) ⑴ ^ % ) 實施例 9 釩 35 40.8 85 2,350 實施施 10 鉻 29 44.5 82 216 實施例 11 錳 36 40.6 83 1,420 實施例 12 鋦 37 37.0 89 30 實施例 13 锆 22 49.8 86 790 比較例 5 - 26 41.1 87 51 由表 4所示之結果可知1 1實施例 9〜13之熱線反射玻璃具有表面電阻為 104 Ω /平方及可見光透射率為50S!或下，當釩絡、鐳或結之金屬氧化物被加入塗膜時，表面電阻率大為增加〇實施例 14 Μ 莫耳比為 78 . 4/19.6/2混合乙醣丙嗣酸鈷（II)、乙釀丙嗣酸嫌 (I D 及乙釀丙嗣酸呔，將15g所得混合物加入 lOOcc含有聚乙二酵與聚二甲基矽氧烷之甲苯作為分散劑内。使用塗料搖動器（Eishin公司製造）將混合物攪拌10秒 =—ί-7—~ 本紙張尺度逋用中國國家標準（CNS ) Α4規格（210Χ297公釐） -------^--裝------訂-----<線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（1 5 ) 鐘，Μ得一塗佈溶液。將300··長、300··寬及4bid厚之納鈣矽玻璃板洗滌並乾煉，Μ製備一底材。底材用掛鈎固定於設定在65〇υ下之電《内，並維持5分鐘。使用市面上可得之嗔鎗，在空氣壓力為4kg/ca2 、氣流為1401/分鐘下，將15g上述塗佈溶液嗔在自轚爐取出之底材上，以形成具有厚度為50nm之金屬氧化物塗膜。依照JIS R 3 1 06-1 985測定所得熱線反射玻璃之可見光透射率及太陽輻射透射率。測定塗膜之表面電阻率。所得結果被示於下表5。實施例15〜19 除了乙醢丙_酸鈦Μ相同最之乙醯丙嗣酸釩、乙醢丙嗣酸鉻、乙釀丙嗣酸錳、乙醮丙酮酸鋦或乙騸丙國酸維取代 Μ外* Κ如霣施例14相同方式可得熱媒反射玻璃。Μ如實施例14相同方式檢驗所得熱媒反射玻璃。所得結果被示於表5。比較例6 除了未使用乙醣丙酮酸钛Μ外，Κ如賁施例14相同方式可得熱線反射玻璃。Μ如賨施例14相同方式檢驗所得熱線反射玻璃。所得结果被示於表5。本紙張尺度適用中國國家橾準（CNS ) Α4規格（210X 297公嫠） -------「--裝------訂-----「線 (請先閱讀背面之注意事項再填寫本頁) ^ ^ 〇 0Q5 A7 B7 五、發明説明（丨5α) πιε ΙΕΠε BICSI0 48·担《 s s m®«aem (ΚΩ / u) Book time 20.3 51 19.0 2ί 18.5 170 3 5,0 I This paper scale uses the Chinese National Standard (CMS) A4 specification (210X 297 mm) 0 1 13 α correction page (please read the back page first (Notes and then fill out this page) 袈 -9 2 ^ 3005 A7 B7 __ V. Description of the invention Ul) (please read the notes on the back to fill in this page) From the results of Table 1, we can see that the actual examples 1 ~ 3 The hot-line reflective glass has a surface resistance of 104 Ω / square or more and a visible light transmittance of 50X or Μ, and the radiation transmittance does not exceed 2.5X which is higher than the visible light transmittance. In Comparative Example 1, the thermal transmittance glass_middle • Visible light transmittance was suppressed to 50X or less, but the transmittance of Tai_Yang was almost higher than the visible light transmittance of 5X. Therefore, the heat ray reflecting glasses of Examples 1 to 3 are superior to those of Comparative Example 1 in terms of too limited radiation shielding performance. The chromaticity indexes a * and b * of the transmitted light of the hot-set reflective glass obtained in Examples 2 and 3 and Comparative Example 1 were measured. The results are shown in Table 2 below. Table 2 3 Right b Xingshi m Example 2 0. 2 8 8.29 Example 3 -0. .13 8.41 Comparative Example 1 -0., 72 13.80 Benxi Examples 4 to 8 and Comparative Examples 2 and 3 Except for changing the coating solution Except for the composition, M was prepared in the same manner as in Example 1 for heat-ray reflective glass. According to JIS R 31 06-1985, the visible light transmittance, visible light reflectance, solar reflectance and solar radiation reflectance of the obtained thermally reflective glass were measured. In addition, according to J IS R 3221-1990, the chemistry of the hydrazone was checked, but the time for immersing the glass in the chemical was 3 days. The results obtained are shown in Table 3 and 圏 1. Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Central Bureau of Industry and Technology Co., Ltd. Printed Table 3 Cobalt of the coating film contains visible light, the surface of the sun, and the thickness of the surface is suitable for the appropriate resistivity of the radiance. The rate of radiance (KΩ / (X) (X ) (η ·) (wtX) ⑴ ⑴ squared) Example 4 30 80 41.1 43.6 51 2.30.0 Example 5 30 70 42.0 43.5 48 3.60.0 14 The size of this paper uses the Chinese National Standard (CNS) A4 specification ( 210X2.97mm) Printed by the Central Sample Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative V. Invention Description (l2) A7 —_______ B7 Example 6 25 85 44.5 47.2 70 3.9 0.0 «Example 7 25 67 44.0 45.1 29 5.4 0.0 Example 8 25 80 43.8 46.2 63 3.4 0.0 Comparative Example 2 25 50 50.3 51.2 170 39.4 0.0 Comparative Example 3 30 100 42.5 47.3 250 8.3 0.0 Remarks: * Permanence: the change of the shot rate before and after immersion in the chemical . It can be seen from FIG. 1 that the acidity of the coating film is 68 to 87 weight in the cobalt suspension: (the area is particularly excellent. From the results in Table 3, it can be seen that the gold oxide coating with a cobalt content of 50% X has Visible light transmittance exceeds 50X, but has a gold oxide coating with a cobalt content of 100% by weight X. It has too much radiation transmittance about 5X higher than visible light transmittance. Therefore, it cannot achieve sufficient transmission energy control performance. There are all examples In 1 ~ 8, a coating film with a uniform appearance can be obtained. In Zi Shi 1 ~ 8, colorless calcium silicate glass was used as the glass substrate, and the visible light transmittance and Taiko radiation transmission of the obtained hot-line reflective glass The rate and appropriate color can be adjusted by using colored soda lime glass as the substrate. The comparative example 4 is changed to 7.12g except for the amount of cobalt (III) pyruvate and dipropylene nickel (II). 3.13g, the amount of methane was changed to 200cc, the shooting time was changed to about 50 seconds, and the coating rate was changed to other than 100 · 1 / min * Μ Heat medium reflective glass was prepared in the same manner as in Example 1. The resulting heat medium reflection The glass has a coating film with a thickness of 150η · and the transmittance of visible light is 8.5 «· But the surface resistivity is 1100 Ω / square. Appreciation Example 9 The 150 · long, 150 · set and 4 ·· thick sodium calcium silicate glass plates are soaked and dried, and a substrate is prepared by M. The substrate is hooked Fixed at 650 t: «in the furnace * at the next time and hold for 5 minutes. Use a commercially available gun. In the use of air-based paper, the BBI family standard (CNS > A4« US · (210x297 )) &Quot; ~ 15 ------- ^-I installed ------ ordered ----- "'line (please read the precautions on the back before filling in this page) Ministry of Economic Affairs Central Accreditation A7 B7 produced by the bureau cooperating with consumers. V. Description of the invention (13) The scraping force is 3.0kg / cB2, the airflow is 901 / min shovel and the spraying rate is 20 houses / minute, it will be dissolved in 100 <:(; The coating solution consisting of 5.138 cobalt (III) ethylpyruvate pyruvate and 1.18 g dipropylene methane (II) and 0.65 g vanadium acetate pyruvate in toluene is on the substrate removed from the electricity It takes about 10 seconds. The visible light transmittance of the obtained heat-medium reflective glass is measured in accordance with JIS R 3106-1 985. The cobalt content based on the total gold content in the coating film is measured by radio frequency flare emission spectroscopy. The surface of the coating film is measured The resistivity and thickness. The results obtained are shown in Table 4. Actual Example 10 Except that 0.66 g of chromium ethyl pyruvate was used to replace vanadium pyruvate, M was prepared in the same manner as in Example 9 The M was tested in the same manner as in Example 9. The results obtained are shown in Table 4. Example 11 was prepared in the same manner as in Example 9, except that 0.66 g of manganese acetonate pyruvate was used instead of vanadium propionate. The hot wire reflects the glass and examines it in the same way as in Example 9. The results obtained are shown in Table 4. Example 12 Except that 0.66 g of acetopropionate was used to replace acetopropionate vanadium, hot-line reflective glass was prepared in the same manner as in Example 9 and tested in the same manner as in Example 9. The results obtained are shown in Table 4. Example 13 Except that 0.66s of acetoxypyruvate was used to replace acetopropionate vanadium, hot-line reflective glass was prepared in the same manner as in Example 9 and tested in the same manner as in Example 9. The results obtained are shown in Table 4. The size of this paper is applicable to China National Standard (CNS) Α4 specification (210X297mm) I ------ called-installed ------ order ----- ". Line (please read the notes on the back first (Fill in this page again) 16 Printed A7 _____B7_ by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (1 4) Comparative Example 5 Except for the fact that ethyl pyruvate Hao M is not used, M is prepared in the same way as in Example 9 , And K were tested in the same manner as in Example 9. The results obtained are shown in Table 4. Table 4 Transmittance and emissivity (k Ω / (nm) (%) ⑴ ^%) of visible light and surface electrical element thickness of the added coating film Example 9 Vanadium 35 40.8 85 2,350 Implementation 10 Cr 29 44.5 82 216 Example 11 Manganese 36 40.6 83 1,420 Example 12 Manganese 37 37.0 89 30 Example 13 Zirconium 22 49.8 86 790 Comparative Examples 5-26 41.1 87 51 According to the results shown in Table 4, 1 1 Hotline for Examples 9 to 13 Reflective glass has a surface resistance of 104 Ω / square and a visible light transmittance of 50S! Or below. When vanadium, radium or junction metal oxides are added to the coating film, the surface resistivity is greatly increased. Example 14 M Mo The ratio is 78. 4 / 19.6 / 2 mixed ethyl sugar propionate cobalt (II), ethyl alcohol propionate acid (ID and ethyl alcohol propionate acid, add 15g of the resulting mixture to 100cc containing polyethylene fermentation and poly two Methylsiloxane toluene is used as a dispersant. Use a paint shaker (manufactured by Eishin) to stir the mixture for 10 seconds = —ί-7— ~ This paper Degrees use the Chinese National Standard (CNS) Α4 specification (210Χ297mm) ------- ^-installed ------ order ----- < line (please read the notes on the back first (Fill in this page again) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (1 5) minutes, M gets a coating solution. Put 300 ·· long, 300 ·· wide and 4bid thick sodium calcium The silicon glass plate is washed and dried, and M prepares a substrate. The substrate is fixed with a hook in the electric set at 65 ° and maintained for 5 minutes. Use a commercially available gun, with an air pressure of 4kg / ca2, under the airflow of 1401 / min, 15g of the above coating solution was applied to the substrate taken out from the furnace to form a metal oxide coating film with a thickness of 50nm. Measured according to JIS R 3 1 06-1 985 The visible light transmittance and solar radiation transmittance of the obtained heat ray reflective glass. The surface resistivity of the coating film was measured. The results obtained are shown in Table 5. Examples 15 to 19 The most of the acetanilides except acetopropionate_titanate M Vanadium oxalate, chromium acetopropionate, manganese acetoacetate, manganese acetonate, or acetopropionate replace Μ 外 * Κ 如霣施In Example 14, heat medium reflective glass can be obtained in the same manner. Μ The obtained heat medium reflective glass was examined in the same manner as in Example 14. The results obtained are shown in Table 5. Comparative Example 6 A hot-line reflective glass can be obtained in the same manner as in Example 14 except that titanium M in ethyl pyruvate is not used. In the same manner as in Example 14, the obtained hot-line reflective glass was examined. The results obtained are shown in Table 5. This paper scale is applicable to China National Standard (CNS) Α4 specification (210X 297 male daughter) ------- "-installed ------ order -----" line (please read the back side first (Notes and fill in this page again) ^ ^ 〇0Q5 A7 B7 Fifth, the invention description (丨 5α) πιε ΙΕΠε BICSI0 48 · Dan "ssm®«

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εε 9COε8ζε ΙΛεζε 9CO οειεοε 63ιε 6CNJ ι ε 规 0 a 雄 9筚轚d3 61 匡MM 001 签進» U军暹» 9Ϊ医里贓 91—1軍進 Μ 寸 τ5εΜκ ίδίΒΜοί 迪» :9ί» «嵌：V* ffl掣 T線本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） W,+Vi - 經濟部中央標準局員工消費合作社印製挪〇〇5 A7 B7 五、發明説明（1 β) 由表5所示之結果可知，具有鈷及鎳氧化物之塗膜之熱線反射玻璃之耐酸性可藉將钛、釩、鉻、錳、嗣或皓之金藤氧化物加入塗祺内而改良。在釩、鉻、錳、鋦或鍤之情況下，附酸性之改良效果相亀大〇由加入有呔等氧化物之實施例15〜19與未加入有金羼氣化物之比較例6間之比較更可知，實施例15〜19之热線反射玻璃在塗膜之射久性方面，特別是附酸性方面有改良，同時保持可見光透射率及太陽輻射透射率在特定範圃内。在所有實施例9〜19内，皆可得具有均勻外觀之塗膜。在實施例9〜19中，當無色透明納鈣玻璃被用作玻璃底材，所得熱線反射玻璃之可見光透射率、太隈輻射透射率、透明色調可藉使用著色納鈣玻璃作為底材而被缠當調整。實施例20 將150mB長、150mm寬及6mm厚之納鈣矽玻璃板洗滌並乾煉，K製備一底材。底材用掛鈎固定於設定在650Ό下之甯爐内，並維持5分鐘。使用市面上可得之噴艙，在空氣壓力為1.5kg/cn2 、氣流為501/分鏟及唄塗之速率為 100ml/分鐘下，將溶解於200cc甲苯內之由5, 3g乙醸丙鬭酸鈷（III)與1.2g二丙醣甲烷鎳（II)及0.3g乙鼸丙酮酸嫌 (III)所組成之塗佈溶液喷在自霣爐取出之底材上，歷約5 秒。依照JIS R 3 1 06- 1 985測定所得熱線反射玻璃之可見光透射率。藉射頻電漿發射光譜術測定基於塗臢内全部金靨含量之鈷含量。藉X射媒衍射光繒術测定塗膜之结晶结構本紙張尺度適用中國國家標準（CNS〉A4規格（210X 297公釐） --------^--裝------訂----一I線 (請先閱讀背面之注意事項再填寫本頁) —______B7_ 五、發明説明（H 7 ) 。以熱線反射玻璃被切成5x 4cm之方式澜定塗_之表面霣阻率，將銀色膏狀物施加在5cm之較長緣上至宽度為0.5cm ，以形成一電極，並Μ數位萬用錶測定電阻率。依照JIS R 322卜1990Μ200轉數旋轉Taber·卡車車輪之方式測定耐磨性，並測定處理前後灞度值之差異。Μ在401C下將熱線反射玻璃浸入1Ν硫酸或1Ν氫氧化納之水溶液内歷24小時之方式測定耐化學性，評估塗膜之變質，等級A，其中實質上未看到變質，等級B，其中看到明顯的變質。所得结果被示於下表6。實施例21 除了作為底材之納鈣矽玻璃之厚度改為12mmM外，Μ如實施例20相同方式製備熱線反射玻璃。Μ如實施例20相同方式檢驗所得热線反射玻璃。所得结果被示於表6。實施例22 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 除了乙醢丙嗣酸鈷（III)之ft改為8.2g、二丙醢甲烷鎳 (II)改為1.2g、及乙釀丙酮酸嫌（111)之量改為0.4gM外 * Μ如實施例20相同方式製備热線反射玻璃。Μ如實施例 20相同方式檢驗所得热線反射玻璃。所得結果被示於表6。實施例23 除了乙醢丙酮酸鈷（III)之悬改為4.5g、二丙醢甲烷鎳 (II)改為1.2g、及乙釀丙_酸鐵（III)之量改為0.3gK外，以如實施例20相同方式製備热線反射玻璃。以如實施例 20相同方式檢驗所得熱線反射玻璃。所得結果被示於表6。比較例7 ---=_2-0—— 本紙張尺度逋用中國囷家樣準（CNS ) A4規格（210X297公釐） A7 __B7 _ 五、發明説明（18) 除了乙釀丙酮酸鈷（III)之Μ改為5.3g、二丙醮甲烷鍊 (II)改為1.2g、及乙醢丙嗣酸嫌（111)之量改為〇.7gM外 *以如竇施例20相同方式製備热線反射玻璃。以如實施例 20相同方式檢驗所得熱線反射玻璃。所得结果被示於表6。比較例8 除了乙醣丙酮酸鈷（III)之量改為5.3g、二丙醣甲烷鎳 (II)改為1.2g、乙釀丙嗣酸鐵（III) 改為0.7g及噴 ^--y 射時間改為實施例20之兩倍Μ外，Μ如實施例20相同方式製備热線反射玻璃。Μ如實施例20相同方式檢驗所得熱線反射玻璃。所得结果被示於表6。比較例9 除了乙釀丙嗣酸鈷（III)之量改為3.3g、二丙醢甲烷嫌 (II)改為2.9g、及乙釀丙嗣酸嫌（III)之量改為O.lgM外，以如實腌例20相同方式製備热線反射玻璃。Μ如實施例 20相同方式檢驗所得熱镍反射玻璃。所得结果被示於表6。 I 1 裝訂 ( ' 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製本紙張尺度逋用中國國家標準（CNS ) Α4規格（2丨0Χ297公釐） =~~24~— 298005 A7 B7 五、發明説明（/扣）减薄滢20 W謙鸢21 W薪鸢22 W諶漥23 tb» 鸢 7 tCT-» 戔 8 tb» 渔 9 睇彌N-棚 0 (ηB) 25 30 22 33 27 75 20 B踟m BSIIIm 沿踟m 泊齣m )Θ鉀άί 泊踟m ^smm sssnl m 0 嫌a« 5 35.7 33.6 3IV5. 1 45.8 3Γ«ο to5 · 3 50.3 10. 8 3.5 0 .Co lroo 谢Bi鵡e0 (ΚΩ / s一」經濟部中央標準局員工消費合作杜印製εε 9COε8ζε ΙΛεζε 9CO οειεοε 63ιε 6CNJ ι ε regulation 0 a male 9 譚轚 d3 61 Kuang MM 001 Sign in »U Army Siam» 9 ΪMedical stolen 91-1 military advance Μ Int τ5εΜκ ίδίΒΜοί Di »: 9V * The size of the ffl-printed T-line paper is applicable to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) W, + Vi-Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs No. 5 A7 B7 V. Description of invention ( 1 β) From the results shown in Table 5, it can be seen that the acid resistance of the hot-line reflective glass with a coating film of cobalt and nickel oxide can be added to Tu Qi by adding titanium, vanadium, chromium, manganese, heir or Hao Jinteng oxide Improve. In the case of vanadium, chromium, manganese, manganese, or lanthanum, the effect of improving the acidity is quite large. Examples 15 to 19 with the addition of oxides, etc., and Comparative Example 6 without the addition of Jinqi vapors By comparison, it can be seen that the heat-reflective glass of Examples 15 to 19 has an improvement in the durability of the coating film, especially the acidity, while keeping the visible light transmittance and solar radiation transmittance within a specific range. In all of Examples 9 to 19, a coating film with a uniform appearance can be obtained. In Examples 9 to 19, when colorless transparent soda lime glass is used as the glass substrate, the visible light transmittance, Taiko radiation transmittance, and transparent hue of the resulting hot-line reflective glass can be determined by using colored soda lime glass as the substrate Tangle up adjustments. Example 20 A nanocalcium silicate glass plate 150 mB long, 150 mm wide and 6 mm thick was washed and dried, and K prepared a substrate. The substrate was fixed in a kiln set at 650 ° with a hook and maintained for 5 minutes. Using a commercially available spray cabin, at an air pressure of 1.5 kg / cn2, an air flow of 501 / min shovel and a coating rate of 100 ml / min, dissolve 5, 3 g of Ethylene Propylol in 200 cc of toluene A coating solution composed of cobalt (III) acid, 1.2 g of dipropylosemethane nickel (II) and 0.3 g of ethyl pyruvate (III) was sprayed on the substrate taken out of the furnace for about 5 seconds. The visible light transmittance of the obtained heat ray reflecting glass was measured in accordance with JIS R 3 1 06-1 985. The cobalt content based on the total content of gold in the smear was determined by radio frequency plasma emission spectroscopy. Determination of the crystalline structure of the coating film by X-ray diffractometry. The paper size is applicable to the Chinese National Standard (CNS> A4 specification (210X 297 mm) -------- ^-installation ------ Order ---- I line (please read the precautions on the back before filling in this page) —______ B7_ V. Description of the invention (H 7). The surface of the glass is cut into 5x 4cm by means of the hot wire reflective glass cut into 5x 4cm For resistivity, apply a silver paste on the longer edge of 5cm to a width of 0.5cm to form an electrode, and measure the resistivity with a multimeter. According to the method of JIS R 322 Bu 1990 rpm 200 Taber truck wheels Measure the abrasion resistance, and determine the difference between the Ba and B values before and after the treatment. Measure the chemical resistance by immersing the hot-line reflective glass in 1N sulfuric acid or 1N sodium hydroxide aqueous solution at 401C for 24 hours, and evaluate the deterioration of the coating film. Grade A, in which substantially no deterioration is seen, Grade B, in which obvious deterioration is seen. The results are shown in the following Table 6. Example 21 Except that the thickness of the soda lime glass used as the substrate was changed to 12mmM, M Hot-wire reflective glass was prepared in the same manner as Example 20. Μ as in Example 20 The obtained hot-line reflective glass was tested in the same way. The results are shown in Table 6. Example 22 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) (III) ft is changed to 8.2g, dipropylene methane nickel (II) is changed to 1.2g, and the amount of ethyl pyruvate (111) is changed to 0.4gM. Reflective glass. Μ The obtained hot-wire reflective glass was examined in the same manner as in Example 20. The results are shown in Table 6. Example 23 Except for the suspension of cobalt (III) acetate pyruvate to 4.5 g, nickel dipropionate ( II) Change to 1.2g, and the amount of ferric propionate (III) is changed to 0.3gK, and the heat reflecting glass is prepared in the same manner as in Example 20. The obtained heat reflecting glass is inspected in the same manner as in Example 20 The results are shown in Table 6. Comparative Example 7 --- = _ 2-0—— This paper uses the Chinese standard (CNS) A4 specification (210X297 mm) A7 __B7 _ V. Description of the invention (18 ) Except that the M of cobalt (III) pyruvate is changed to 5.3g, the dipropylene methane chain (II) is changed to 1.2g, and acetophenone The amount of acid (111) was changed to 0.7 gM *. The heat-ray reflective glass was prepared in the same manner as in Sinus Example 20. The obtained heat-ray reflective glass was examined in the same manner as in Example 20. The results are shown in Table 6. Comparative Example 8 Except that the amount of cobalt (III) ethyl pyruvate is changed to 5.3g, nickel dipropylose methane (II) is changed to 1.2g, and iron ferric propionate (III) is changed to 0.7g and sprayed ^- y The shooting time was changed to twice M in Example 20, and M was prepared in the same manner as in Example 20 for hot-line reflective glass. M was examined in the same manner as in Example 20 for the obtained heat-ray reflective glass. The results obtained are shown in Table 6. Comparative Example 9 Except that the amount of cobalt (III) ethyl propionate was changed to 3.3 g, the amount of dipropionyl methane (II) was changed to 2.9 g, and the amount of ethyl propionate (III) was changed to O.lgM In addition, hot-ray reflective glass was prepared in the same manner as in Example 20. Μ The obtained hot nickel reflective glass was examined in the same manner as in Example 20. The results obtained are shown in Table 6. I 1 binding ('line (please read the notes on the back before filling in this page) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is based on the Chinese National Standard (CNS) Α4 specification (2 丨 0Χ297mm) = ~~ 24 ~ — 298005 A7 B7 V. Description of invention (/ deduction) Thinning Ying 20 W Kite 21 W Salary 22 W Chen 23 tb »Kite 7 tCT-» 戋 8 tb »Yu 9 Sumi N-shed 0 (ηB) 25 30 22 33 27 75 20 B 踟 m BSIIIm along the 舟 m 樟 m) Θκάά 樟踟 m ^ smm sssnl m 0 0 a «5 35.7 33.6 3IV5. 1 45.8 3Γ« ο to5 · 3 50.3 10. 8 3.5 0 .Co lroo Xie Bi Mue0 (ΚΩ / s 一) Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Consumer Cooperation

(¾) u) (I) 0 0 / - 1 —1 . 4.2 21.7 0.003>3> 1.9 20.70.9 A A 3.8 8.30.7 A A 1.2 36.001.1 k h 6.7 21.-4 0.8 BA 2.N5JgCJlo.g3>3» 1.1 私 6 .001 . 0 ® A 嫌時轚時 3靦aa5 _ _ 0 糨h¥ -------叫裝------訂-----(‘線 (請先閱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 ) A4規格（210X297公釐） -i /U- A7 B7 經濟部中央標準局員工消費合作杜印製五、發明説明U 9) 由表6所示之結果可知，塗臢内之嫌含量較佳為1.0重量 «或Μ上，Μ抑制塗臢之導電性，但若嫌含量太大時*塗膜之附久性，特別是耐酸性會變質，因此，嫌含量較佳為 4.5重量X或以下。若辣含量太大時，塗膜内金鼷氧化物之结晶結構不會變成尖晶石結構，導致如高度可見光透射率之問題。因此，鑒於塗膜之附久性，辣含量較佳為5〜40 重量！ϋ。實施例24 將150mm長、150mm寬及6ββ厚之納鈣矽玻璃板洗滌並乾煉，Μ製備一底材。底材用掛鈎固定於設定在650Ό下之霄爐内*並維持5分鐘。使用市面上可得之噴鎗，在空氣壓力為1.5kg/cin2 、氣流為501/分鐘及哦塗之速率為 120·1/分鐘下，將溶解於200cc甲苯内之由8.2g乙醢丙嗣酸鈷（III)與1.2g二丙醣甲烷鎳（II)所組成之塗佈溶液嗔在自電爐取出之底材上，歷約5秒。依照JIS R 3 1 06-1 985測定所得熱線反射玻璃之可見光透射率。依照JIS R 3 1 06-1 985测定依照JIS Z 8729-1 980 所界定之L*a*b*比色系統之色度指數a*及b*。箱X射媒衍射光譜術測定塗膜之結晶结構。以熱線反射玻璃被切成 5X 4cm之方式測定塗膜之表面電阻率，將銀色齋狀物施加在5cm之較長緣上至寬度為0.5cb，Μ形成一電棰，並以數位萬用錶測定電阻率。依照JIS R 3221-1990W200轉數旋轉Taber卡車車輪之方式測定附磨性*並测定處理前後獨度值之差異。K將热線反射玻瑰浸入JIS R 3221所界定之 -=_2-2~-- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) Γ •裝訂線五、發明説明（2 0) A7 B7 經濟部中央標準局員工消费合作社印製酸性或 m 性溶液内歷24小時之方式測定附化學性，評估塗膜之變霣 $ 等级 A 其中*霣上未看到變霣，等级Β，其中看到明顬的變質〇所得结果被示於下表7。實施例 25 除了使用溶解於 200cc甲苯内之由8.2g乙醢丙醑酸鈷 (I II )、 1 .2g二丙釀甲烷嫌（Π)及〇.7g乙釀丙嗣酸嫌（ III) 所組成之塗佈溶液以外，K如實施例24相同方式製備热線反射玻璃〇以如實施例24相同方式檢驗所得热線反射玻璃〇所得结果被示於表7。實施例 26 除了使用具有度為12mn之納鈣矽玻璃作為玻璃底材並使用溶解於 200c c甲苯內之由8.2g乙醜丙鹂酸鈷（III) 、 1 · 2g 二丙釀甲烷鎳 (II)及〇.7g乙醢丙闞酸嫌（III)所組成之塗佈溶液以外 Μ如賁腌例24相同方式製備熱壤反射玻璃〇 Μ 如實腌例 24相同方式檢驗所得热線反射玻璃。所得结果被示於表 7 < ) 實施 27 除了使用具有厚度為6·»及透射色諝為齄色之納鈣矽玻璃作為玻璃底材以外，以如實旛例24相同方式製慟热鑲反射玻璃〇以如實施例24相同方式檢驗所得热嬢反射玻璃。所得结果被示於表 7 〇實 .施例 28 除了使用具有厚度為5m·及透射色調為綠色之納鈣矽玻璃作為玻璃底材 Μ 外，Μ如實施例24相同方式製備热線反 I 叫裝 11 ^ I I ( 丨線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐）(¾) u) (I) 0 0 /-1 — 1. 4.2 21.7 0.003 > 3 > 1.9 20.70.9 AA 3.8 8.30.7 AA 1.2 36.001.1 kh 6.7 21.-4 0.8 BA 2.N5JgCJlo.g3 > 3 »1.1 Private 6. .001. 0 ® A Time is too late 3 腼 aa5 _ _ 0 糨 h ¥ ------- Calling ------ Subscribe ----- ('line ( Please read the precautions on the back before filling out this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -i / U- A7 B7 Central China Bureau of Economic Affairs Employee consumption cooperation du printing 5. Invention Explanation U 9) From the results shown in Table 6, it is known that the suspected content in the coating is preferably 1.0% by weight or Μ, and Μ inhibits the conductivity of the coating, but if the content is too large, the coating film will last for a long time. The properties, especially the acid resistance, will deteriorate, so the content is preferably 4.5 weight X or less. If the spicy content is too large, the crystal structure of the gold oxide in the coating film will not become a spinel structure, causing problems such as high visible light transmittance. Therefore, in view of the durability of the coating film, the spicy content is preferably 5 to 40 weight! ϋ. Example 24 A nanocalcium silicate glass plate 150 mm long, 150 mm wide and 6 β β thick was washed and dried to prepare a substrate. The substrate was fixed in a kiln set at 650 ° with a hook and maintained for 5 minutes. Using a spray gun available on the market, at a pressure of 1.5 kg / cin2, an air flow of 501 / min, and a coating rate of 120 · 1 / min, dissolve 8.2 g of ethyl acetate in 200 cc of toluene. The coating solution composed of cobalt (III) acid and 1.2 g of dipropylosemethane nickel (II) was laid on the substrate taken out of the electric furnace for about 5 seconds. The visible light transmittance of the obtained hot-ray reflective glass was measured in accordance with JIS R 3 1 06-1 985. The chromaticity indexes a * and b * of the L * a * b * colorimetric system defined in accordance with JIS Z 8729-1 980 were measured in accordance with JIS R 3 1 06-1 985. Box X-ray diffraction spectroscopy was used to determine the crystal structure of the coating film. The surface resistivity of the coating film was measured by cutting the hot-wire reflective glass into 5X 4cm, applying a silver-like object on the longer edge of 5cm to a width of 0.5cb, Μ formed an electric pole, and the resistance was measured with a digital multimeter rate. Abrasion resistance * was measured in accordance with JIS R 3221-1990 W200 rotation of Taber truck wheels and the difference in the uniqueness values before and after the treatment was measured. K immersing the hotline reflective glass rose in JIS R 3221-= _ 2-2 ~-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please read the notes on the back before filling in This page) Γ • Binding line V. Description of the invention (20) A7 B7 The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives printed acidic or m-type solutions in 24 hours to determine the chemical properties and evaluate the change of the coating film $ Rank A where * is not seen on *, and rank B, where metamorphosis of Ming huang is seen. The results obtained are shown in Table 7 below. Example 25 Except for the use of 8.2 g of cobalt acetoacetate (I II), 1.2 g of dipropyl methanoate (Π) and 0.7 g of acetopropanoic acid (III) dissolved in 200 cc of toluene Except for the coating solution of the composition, K was used to prepare a heat reflecting glass in the same manner as in Example 24. The obtained heat reflecting glass was examined in the same manner as in Example 24. The results are shown in Table 7. Example 26 In addition to the use of nano-lime-silica glass with a degree of 12mn as the glass substrate and the use of 8.2g of cobalt (III) ethyl acetonate propionate dissolved in 200cc of toluene, 1.2g of dipropylene nickel (II) ) And .7g of the coating solution composed of acetopropanic acid (III). M is prepared in the same manner as in Example 24. Hot soil reflective glass is prepared. In the same manner as in Example 24, the resulting hot-line reflective glass is examined. The results obtained are shown in Table 7 <) Implementation 27 Except for the use of soda lime glass with a thickness of 6 · »and a transmission color as the color, as the glass substrate, the hot-mount reflection was prepared in the same way as in Example 24 Glass 〇 The obtained heat-reflecting glass was examined in the same manner as in Example 24. The results obtained are shown in Table 7. Example 28 Except for the use of nano-calcium silicate glass with a thickness of 5 m · and a transmission hue of green as the glass substrate M, M was prepared in the same manner as in Example 24. Install 11 ^ II (丨 line (please read the precautions on the back before filling in this page) This paper uses the Chinese National Standard (CNS) A4 specification (210X297mm)

A 2 /f\ 明説明發五璃玻射反線热得所檢式方同相 4 2 ο 例 7 施表賞於如示 Μ 被〇果璃结玻得射所 ο IX 例較比A 2 / f \ Explain that the method of making five-glass glass anti-reflective heat is the same as that of the detection method 4 2 ο Example 7 Appreciation is shown as shown in the following figure. Μ was taken by the glass as a result of the glass shot ο IX cases are compared

鉻甲酸 CCB1 00丙 2 i 二解gz 溶80 Μ 使及了)' 除II 由之内苯鈷酸釅丙醢乙製反式媒方热同得相所 24驗例檢豳式實方如同 Μ 相外例 7 Μ 施表液實於溶如示佈 Μ 被塗。果之璃結成玻得組射所所反。 I)線璃 ί備射 (請先閱讀背面之注意事項再填寫本頁) 裝-Chromic acid CCB1 00 Propane 2 i Second solution gz Dissolve 80 Μ Make it up) 'Except II The benzene cobalt cobalt acid made of propylene acetic acid made the trans-medium heat with the same phase. In contrast, Example 7: The M solution is applied as shown in the figure and is coated. The fruit of the glass formed a glass to be opposed to the group shooting. I) Line glass ί 备射 (Please read the precautions on the back before filling out this page)

,1T -線經濟部中央梯準局員工消費合作社印製本紙張尺度適用中國國家標準（CNS ) Α4規格（210'〆297公釐）五、發明説明 A7 B7 喊薪鸢2办 W薪鸢25 嫌薪鸢26 W Μ 鸢 27 WM鸢 200 tCT-鵁鸢 1 0 ΓΟ5 30 11 35 33 30 ^sadi 汜踟出 )Bsnlm)eSIIIm ^m&i ^mB&l 31 . 5 -5 . 1 -1 . 1 一二 32.1-4.3 0.1 3.9 31 . 1 -5 . 5 -0 .Co^ ^ 31.9 -8.3 -2.7 3.6 32.8 -9.5 0.6tvsto 33.2 -2.2 0.3 3X 1001 m b* § / 书bl·) 00 ^ 徊薄 9SSOm 0 0 7 ^^^1 .^ϋ m^l 1^1 —^^1 n n 1^^1 n (請先閲讀背面之注意事項再填寫本頁) 訂 Ο .oo 0.9 0.8 Ο · 9 1.0 1.2, 1T-The Ministry of Economic Affairs, Central Bureau of Standards, and Employee Consumer Cooperatives printed this paper. The standard of the paper is applicable to the Chinese National Standard (CNS) Α4 specification (210'〆297 mm). V. Description of the invention A7 B7 Salary Kite 2 Office W Salary 25 Suspected kite 26 W Μ kite 27 WM kite 200 tCT- 鵁 kite 1 0 ΓΟ5 30 11 35 33 30 ^ sadi 渜出) Bsnlm) eSIIIm ^ m & i ^ mB & l 31. 5 -5. 1 -1. 1 one two 32.1-4.3 0.1 3.9 31. 1 -5. 5 -0 .Co ^ ^ 31.9 -8.3 -2.7 3.6 32.8 -9.5 0.6tvsto 33.2 -2.2 0.3 3X 1001 mb * § / book bl ·) 00 ^ thin 9SSOm 0 0 7 ^^^ 1. ^ Ϋ m ^ l 1 ^ 1 — ^^ 1 nn 1 ^^ 1 n (please read the precautions on the back before filling this page) Order Ο .oo 0.9 0.8 Ο · 9 1.0 1.2

A A A A B AA A A A B A

A A A A A A 嫌霣 a 靦 afb 0 個阵 ‘線_ 經濟部中央標準局員工消費合作社印製本紙張尺度適用中國國家標牟（CNS ) A4規格（210X297公釐） J條正 • V t年月曰 j補充 85.2.07 β77 五、發明説明（22 ) 由表7所示之结果可知，在使用納鈣玻璃作為底材之實施例2 4〜2 6中，依照L * a * b *比色系統之色度指數a *及b *具有下面範圍： -7.0蝱 a*S -3.0 -5.0 含 b=i 芸 4.0 具有上述範圍内之色調之反射光為綠色色調，其通常對外觀有利。依照本發明之熱腺反射玻璃可藉一基於塗佈溶液之熱分解之方法製成，該方法具有優異生產力。本發明提供一種對電磁波反射、塗膜之耐久性及反射光之色調之改良，其在顧及環保之實用上可能為嚴重問題，同時可保持具有含氧化鈷及氣化鎳之塗膜之熱線反射玻璃之特性，即，可見光透射率及太陽幅射透射率可被控制在特定位準Μ下。 (請先閱讀背面之注意事項再填寫本頁) 裝· ，1Τ 經濟部中央標準局員工消費合作社印製 25修正買本紙張尺度逋用中國國家標準（CNS ) Α4規格（210Χ 297公釐）AAAAAA 飣霣 a 腼 afb 0 array line_The printed paper standard of the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) J Article positive • V t year month j Supplement 85.2.07 β77 V. Description of the invention (22) From the results shown in Table 7, it can be seen that in Examples 2 4 to 2 6 using soda lime glass as the substrate, according to the L * a * b * colorimetric system The chromaticity indexes a * and b * have the following ranges: -7.0 蝱 a * S -3.0 -5.0 with b = i Yun 4.0 The reflected light having a hue within the above range is a green hue, which is generally good for appearance. The heat gland reflective glass according to the present invention can be made by a method based on thermal decomposition of the coating solution, which has excellent productivity. The present invention provides an improvement of electromagnetic wave reflection, durability of coating film and hue of reflected light, which may be a serious problem in consideration of environmental protection, while maintaining hot-line reflection with a coating film containing cobalt oxide and vaporized nickel The characteristics of glass, that is, visible light transmittance and solar radiation transmittance can be controlled at a specific level M. (Please read the precautions on the back and then fill out this page) Installed, printed by the 1TC Central Standards Bureau Employee Consumer Cooperative 25 revised and purchased This paper uses the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm)

Claims

1. A hot-line reflective glass rose, comprising a glass substrate with a coating film containing cobalt oxide and nickel oxide on its surface, and the surface electric bile rate of the coating film is not less than 4 Ω / square and the thickness is not less than 10 nm, the content of cobalt in the coating film is 60 ~ 90% of the total content of gold per unit area, although S :, and the content of nickel in the coating film is 1 〇 ~ 40% by weight of the total content of gold per unit area By. 2. For the application of the patented hotline reflective glass item 1, where the coating film has a thickness not exceeding 130 nm. 3. As the hotline reflective glass in the second item of the patent application, the content of cobalt in the coating film is 68 ~ 87 weight of the total gold ring content per unit! ", And the content of nickel in the coating film is 13 ~ 32 weight S of the total metal content per block area; 4. A kind of hot-line reflective glass, including a glass substrate, with a coating film containing cobalt oxide and nickel oxide on its surface * Printed by the Employee Consumer Cooperative of the Central Escalation Bureau of the Ministry of Economy Page) 'The coating film further contains a gold oxide oxide * which contains at least one gold oxide selected from titanium, vanadium, chromium, manganese, copper and zirconium, and its surface electrical bladder rate is not less than 104 Ω / square and Thickness is not less than lOnm, * The content of cobalt in the coating is 60 ~ 89 of the total weight of the gold per unit area! "The content of nickel in the coating film is 10 to 3 9% of the total amount of gold per unit area, and at least one selected from titanium, vanadium, chromium, manganese, nets and sold gold in the coating film The original paper standard is printed in Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 223005 A8 B8 C8 D8 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 6. The patent application range Ί 1 I contains the most 9 Each unit contains 1 ~ 30 weights of gold and gold. 1 1 1 5. As for the application of the patent hotline item 4 of the hot-line reflective glass, where the coating film I | with a thickness of not more than 130η m C * Please first read 1 6. A hot-line reflective glass Yu, including a glass Substrate} Its surface has It's back 1 side I coating film containing cobalt oxide and nickel oxide, Zhuyin 1 The coating film still contains oxide m and its surface resistivity is not less than 104 Ω / Item I then I square and Thickness not less than 1 0 7 0 η πι 4% The content of m in this coating film is 1 · 0 ~ of the total content of gold per unit area. · Page 1 I 4. 5 weight inferior 〇1 1 I 7. If applied Hotline reflective glass in the 6th patent scope, wherein the content of nickel in the 1 1 coating film is 5-40 per weight of the entire gold content per unit area. Weight -40. Weight 8. Order 8. If Φ, please apply for patent scope 1, 2 or 3 items of hotline reflective glass Among them, 1 1 The reflection hue seen from the reverse side of the hot-line reflective glass of the coating film is green 1 I series color 〇1 1 I 9. As the hot-line reflective glass of the patent application scope item 4 or 5, white 1 The reflective hue of the reflective glass of the coating film on the reverse side of the coating is the green series 1 1 color 0 1 1 10. For the thermal reflective glass of patent application item 6 or 7 of which 1 I white Hi The coating film The reflective hue seen on the reverse side of the hot-line reflective glass is green 1 1 I column colors 0 1 1 11. If the heat medium reflective glass of patent application items 1, 2 or 3, 1 of which the coating film is mainly composed of The oxide composed of spinel structure is 0 1 1 12. For example, the hot wire reflective glass of patent application No. 4 or 5 wherein the 1 I coating film is mainly composed of oxide with spinel structure 0 1 1 This paper standard adopts China National Standard (CNS) A4 regulations Scope (210X297mm) of 2i-3〇QS A8 B8 C8 D8 applies for the scope of patents. Among them, the item of glass radiation retroreflective heat 7 or 6 is included in the patent application. The glass is shot into the heat of the anti-composition line. The chemical structure of the JJ oxygen structure stone crystal tip has the main film to be coated. Possible shot through <-VI <-Λ8 · b <-where the shot is within the range of the inner envelope or adjusted in size I body® J 肖色 Jrl ο Table I ^ show 45 generation II display S • 5S · Please β * b ^ a and see VI * Ru Ding 5 a · -¾. Through the glass and glass anti-reflective heat item (please read the precautions on the back before filling this page) <-Λ! · B <-The person who is under the inner circle or the training, §6 color place, draw ½, 5 degrees, light and translucent color J, a table Μ | 不専 b J " and see $ as I a. May 16 In the penetration, the item of glass-glass anti-reflective heat <-a VI < _ and ο *. A 3 J The number of its VI indicates the color table on behalf of the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printed the first example Li Zhuan please Φ as in the case where the glass glass shoots the anti-linear heat item 3 or the display light shows that it can be shot to the opposite side to see the glass The hot surface of the anti-surrounding line of the shot should be painted on the film under the film. The self-reflecting <-<-<-Λ8 · b VI refers to the chromatic index of b and B, which is its own glass Reverse shot. Line cooked item 5 or 4th Fan Wei Li's application for the paper standard of China National Standards (CNS> A4 specifications (210X297 mm) 3 3 5 ο ο €) AB CD Central Ministry of Economic Standards Bureau of Consumer Labor Cooperative Institution Sixth, the scope of patent application The reflected visible light seen on the reverse side of the hot-line reflective glass of the coating film shows the reflected hue in the following fan garden: -7.0 < -3.0 -5.0 ^ 4.0 where a < = And b * represents the color index. 19. For the hot-line reflective glass as claimed in item 6 or 7 of the patent application scope, where the reflected visible light seen from the reverse side of the hot-line reflective glass of the coating film shows the reflected hue in the following fan garden -7.0S -3.0 -5.0S 4.0 where a * and b * represent chromaticity index. 20. A kind of hot-line reflective glass, including a glass substrate, on the surface of which has a coating film containing vaporized cobalt and nickel oxide, the coating film is mainly composed of oxides having a spinel structure including cobalt oxide and nickel oxide Composition *, with a surface electrical bladder rate of not less than 104 Ω / square and a thickness of 10 to 70 nm, and the reflection tone seen from the reverse side of the hot-line reflective glass of the coating film is a green series color. This paper wave scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297mm) ---------- tM ------ order ------ line ((Jing first read the notes on the back (Fill in this page again)