TW387006B

TW387006B - Powder coating composition

Info

Publication number: TW387006B
Application number: TW85115946A
Authority: TW
Inventors: Yoshiki Matsuoka; Toshiaki Hayashi; Hiroshi Nakamura
Original assignee: Sumitomo Chemical Co
Priority date: 1996-12-24
Filing date: 1996-12-24
Publication date: 2000-04-11

Description

A7 B7 經濟部中央標準局員工消費合作社印製五、發明説明（1 ) - I 發明所 JL p 1 術 η 域 1 I 本發明傷有關可賦與硬化時提高環境衛生及塗膜表面 1 1 | 之平滑性高耐蝕性之聚酯 % 粉體塗料 0 /--N 1 I 請 I 知 η 術先閱 1 I 讀 1 I 長久以來 9 聚酯条粉體塗料舆溶劑条塗料相較時 .特背 1 之 1 別有所謂於表面上容易出現面圈 (r 0 U nd)之嚴重問題存在注意 1 1 事 0 於塗料科技期刊 (J • Co a t in g Te c h no 1 〇 gy) 6 0(762) 項再 1 導 il 39 (1 9 88 ), 掲示有使採用聚酯条粉體塗料之塗裝物之表面寫頁 1 高平滑化為標 • 而添加低熔融黏度之改質雙酚A型環氧 1 j 樹脂之技術〇 1 I 又 » 聚酯 % 粉體塗料與環氧条粉腾展塗料相較時 > 有耐 1 1 m 性低劣的問題 0 通常為提高耐蝕性 > 官試著添加數劣之訂 1 雙酚 Α型環氧樹脂之方法。然而，此方法隨著環氧樹脂之 1 1 低耐候性 9 Si 曰使聚酯 % 粉體塗料之耐候性特徴降低 C 1 I 再者 • 聚酯 % 粉體塗料僳採用基画封閉化 IPD I (基画 1 1 Ί 封閉化異佛爾酮二異氡酸酯 )作為硬化劑。然而採用此化 1 I 合物時 • 於烘烤時基團封閉劑 ε -己内醛胺會揮發、使烘 1 1 烤燧受污染 9 同時生成發生内醯胺惡臭等有礙作業 IS 境境之 i 1 問題 0 為解決此等問題 » 例如於厂粉體塗裝 J 20(3), 35 ( 1 1 1994)内掲示有四甲氣基甲基二醇脲基条之硬化劑。然而， 1 1 採用該硬化劑之塗料於 £kfey 化中之流動性 E3 變低且發生氣泡 1 I 9 産生在經過耐煮沸法及耐塩水噴霧法處理後之二次附著 1 1 1 性低劣等等的缺點〇 1 1 多元有機氰酸酯與含羥基之樹脂可得硬化物僳公知的 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 38 5 90 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（2 ) •例如，日本待公昭55-30750號公報掲示著具有羥基及/ 或環氣基之丙烯酸条共聚體之塗料用組成物。然而於此文獻内雖有低環境負載性及由揮發成分之減少引起的表面性提高（所謂氣泡性）有關的記載，然而對表面平滑性及高耐蝕性方面卻未曾提及。發明摘酉本發明欲解決的課題，偽舆習用的聚酯糸粉體塗料相較時，提供可更進一步提高硬化時之環境衛生，而且所得的塗膜之表面具高度平滑性，保持高耐蝕性之聚酯糸粉體塗料用組成物及其塗裝物。本發明人等經鋭意檢討，結果發現採用特定的多元有機氰酸酯作為含羥基聚酯樹脂之硬化劑可解決上述問題，以至完成本發明。亦即，本發明係有關由以（A)分子中具有至少二個游離羥基之聚酯樹脂及（B)以分子中具有至少二値以上之氰酸酯基之下列化學式A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (1)-I Inventory JL p 1 Surgical Field 1 I The invention relates to wounds that can be used to improve the environmental sanitation and harden the coating surface during hardening 1 1 | The smoothness and high corrosion resistance of the polyester% powder coating 0 / --N 1 I Please I know η first read 1 I read 1 I for a long time 9 polyester strip powder coating and solvent strip coating when compared. Back 1 of 1 Do n’t have the serious problem that the surface ring (r 0 U nd) is easy to appear on the surface. Attention 1 1 事 0 In the Journal of Coatings Science and Technology (J • Co at in g Te ch no 1 〇gy) 6 0 ( 762) Item 1 il 39 (1 9 88), which shows that the surface of the surface of the coating with polyester stripe powder coating sheet 1 is highly smoothed, and low melting is added. Modified bisphenol A epoxy 1 j resin technology 〇1 I Also »Polyester% powder coatings when compared with epoxy strip powder coatings > has a problem of poor resistance to 1 1 m 0 normal In order to improve the corrosion resistance, a method of adding a number of bad bisphenol A epoxy resins was tried. However, this method reduces the weather resistance of polyester% powder coatings with 1 1 low weather resistance 9 Si, and reduces the C 1 I. Furthermore, polyester% powder coatings use base paint to seal IPD I (Base picture 1 1 Ί blocked isophorone diisocyanate) as a hardener. However, when using this chemical compound I • The group blocking agent ε-caprolactam will volatilize during baking, contaminate the roasted 1 1 roast 燧 9 at the same time, and produce the odor of lactam, which will hinder the operation of the IS environment I 1 Problem 0 To solve these problems »For example, in the factory powder coating J 20 (3), 35 (1 1 1994), a hardener containing tetramethylaminomethyl glycol urea strip is shown. However, the fluidity E3 of the coating using this hardener in £ kfey becomes low and bubbles occur. 1 I 9 Produces secondary adhesion after boiling-resistant and water-resistant spraying. 1 1 1 Inferior properties, etc. Disadvantages such as 0 1 1 Multi-organic cyanate esters and hydroxyl-containing resins can be hardened. 僳 Well-known 1 1 This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 38 5 90 Central Bureau of Standards, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of the invention (2) • For example, Japanese Patent Publication No. 55-30750 discloses a coating composition for an acrylic bar copolymer having a hydroxyl group and / or a ring gas group. However, although there are records in this document about low environmental load and improved surface properties (so-called bubble properties) caused by reduction of volatile components, they have not mentioned the surface smoothness and high corrosion resistance. SUMMARY OF THE INVENTION The problem to be solved by the present invention is that when compared with the conventional polyester / powder powder coatings, it can provide improved environmental sanitation during hardening, and the surface of the resulting coating film has high smoothness and maintains high corrosion resistance. Composition and coating for polyester polyester powder coatings. The present inventors have made a deliberate review and found that the use of a specific polyorganocyanate as a hardener for a hydroxy-containing polyester resin can solve the above-mentioned problems and complete the present invention. That is, the present invention relates to the following chemical formulas based on (A) a polyester resin having at least two free hydroxyl groups in a molecule and (B) a cyanate group having at least two fluorene groups in a molecule

[式内，A示磺數1以上6以下之烴基，二痼A亦可為互相不同者；X為單鍵鍵結、磺數1至20之烴基、羰基、碾基、二價之硫原子或氣原子；i為0以上3以下之整數值，且二値 i亦可為互相不同者，η示0或1]表示的多元有機氡酸酯及/ 或其預聚體為主要成分而成之粉體塗料用組成物。 (請先閲讀背面之注意事項再填寫本頁) J衣. 訂 4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29.7公釐） 4 385 9 0 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 | 發明詳細説明 1 以下詳細說明本發明。 1 1 I 至於本發明使用的多元有機氰酸酯之具體例，可列舉 /--N 請 1 1 計有 : 4 , 4 ' _二氟酸二苯基酯、 3 3 ' ，5 ,5 » 一四甲基 -4， 4 ' _ 先閱 1 I 讀 1 1 二氛酸二苯基酯、雙 (氟酸苯基酯 )甲烷、雙 1 -氣駿- 3, 5- η 1 I 之 1 I 二甲基苯基酯）甲浣·> 雙 (2 - 氡酸 -3- 第三丁基 -5 -甲基苯基 >王意 1 1 事 1 酯 )甲烷、雙（4-氰酸苯基酯 )乙烷 2 , 2 - 雙 (4- -氡酸苯基酯項再 ξ| )丙烷、 2 ,2 -雙 (3 ,5- -二甲基 -4 -氡酸苯基酯 )丙烷、 2 , 2- 魅又寫笨裝貢 1 (3 _甲基- 4- 氰酸苯基酯）丙烷、 2 2 - 雙 -(4- 氰駿-3 -第三丁 •—· 1 I 基苯基酯 )丙烷、 2,2-雙 (4- 氡酸 3 - 第三丁基 _ δ -甲基苯基 1 1 1 酯 )丙烷、 2 ，2 -雙 (3- -烯丙基 —4 _氛酸苯基酯 )丙院、 1 , 1- 雙 1 1 訂 1 (3 -第三丁基-4-氡酸 -6- 甲基苯基酯 )丁烷、 1 ，1-雙 (4 -氡酸苯基酯 )環己院、1 .,1 - 雙（4。氣酸- 3 - 甲基苯塞酯 >環己烷 1 1 、 1 , 1 - 雙 (4 -氰酸 -3- -環己基 -6 -甲酯 )丁烷、雙 (4 - 氟酸苯 1 | •基酯 )甲烷、雙 (4 -氰酸- 3,5 -二甲酯 )甲烷、雙 (4- 氟酸- 3 - 1 级第三丁基 -6 -甲基苯基酯 )甲院、雙（4- 氡酸苯基酯 >三環 [ 1 I 5 , 2 , 1 , 〇2 .6]癸烷、雙（4 -氛酸 3 5 二甲基苯：基酯 )三環 [ 1 1 5 , 2 , 1 , 02 .6 ]癸院、雙（4 -氰酸 -3-第三丁基 -6 -甲基苯酯 ) 1 1 二環 [5 ,2 ,1 ，〇2.6 ]癸院、雙 (4 -氡酸苯基酸 )硫醚、雙 (4 - 1 1 氣酸 -3 ,5 -二甲基苯基酯 )硫醚、雙（3- 第三丁基-4 -氣酸 - 1 I 6 - 甲基苯基酯硫化醚、雙（4- 氰酸苯基酯）通 m. 、又 (4- 氰酸 1 I 苯基酯 )羰基、雙 (4- -氡酸苯基酷醚等〇 1 1 I 其中以採用2 ,2- -雙（ 4 -氡酸苯基酯 )丙烷、 1,1 -雙 (3 - 1 1 1 第三丁基 -4 -氡酸，6 - -甲基苯基酷丁烷較佳 , 就對陚與塗 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 5 38 59 0 Μ Β7 經濟部中央標準局員工消費合作社印製五、發明説明（4 ) - 1 1 料耐叠黏性儲存壽命等之儲存安定性或賦與塗料過度烘 1 1 | 烤時之耐黃變性之情形而言 9 以採用 1 , 1 - 雙 (3 -第三丁基- 1 1 4- 氣酸 -6 -甲基苯基酯）丁烷及該氰酸酯化合物為主成分之 X—N I 請 1 1 預聚體尤佳 0 先閱 1 I 讀 1 | 此外 t 亦可使用具有藉由此等氣酸酯之氡酸酯基之三背 ιέ 1 1 之 1 聚化而形成的三畊環之分子量為至少 40 0以上6 000以下之注意 1 事 1 預聚體作為本發明之硬化劑〇於預聚體化之際 » 可 DO 早獨使項再填用或合併使用氰酸酯 αο 単體〇預聚體化偽以例如 .塩酸磷酸寫本 r 頁 1 等之質子酸氛化鋁三氟化硼錯合物氣化鋅代表的路 '—✓ 1 易士酸等之酸 • 酚兒萘酚 (P he η 〇 1 p y Γ 0 c a t e c h 〇 Π、二羥 1 1 基萘所代表的芳香族羥基化合物 9 磺烷酸鋅磺烷酸鈷 1 1 辛酸錫辛酸鈷等有機金屬塩乙醯基醋酮酸鋅乙醯基訂 1 醋酮酸銅乙醯基醋酮酸鋁等之有機金屬錯合物三乙胺 1 I % 三丁胺 N Df 啉異 Of 啉等第三级胺 9 氛化四甲基銨、溴 1 I 化四甲基銨所代表的四級銨塩咪唑類 t 氫氣化 m 院氣 1 ! 1 化納二吖雙環 [2 ,2 ,2]辛烷、三苯基隣；磺酸鈉、氯化鋰等之塩或此等混合物作為催化劑對上述氰酸酯予以聚 1 1 合而得〇 1 1 此等有機氰酸酯類及預聚體 H3ii 可各白 BO 早獨使用或合併使 1 | 用〇 1 | 本發明所用的有機氡酸酯及 /或其預聚體之添加量， 1 1 | 偽採用該組成物之硬化物中之膠化分率予以規定箸 0 本發 1 1 明之膠凝分率則採用以下方法測定〇以各種條件硬化已摻 1 1 合指定量的多元有機氣酸酯及 /或其預聚體之聚酯樹脂。 1 1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 6 3 8 5 9 0 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 ) - 1 1 將此硬化物浸漬於 25 t：之 Η , Η - 二甲基乙醯胺中 2 4小時 t 使 1 I 其膨潤〇其後於 25 V 水中浸漬該膨潤凝膠 2 4小時使其收 1 1 1 縮 > 再予壓擠以去除溶劑部分 9 並在加熱真空爐中乾操 • -N 1 卜請 1 1 將此經乾燥後之重量 (W C ) 與初期硬化物之重量 (Wo) 之此值先閱 1 讀 Γ | (tf c / W 〇 )定義成膠凝分率。惟W 0 * Me 像去除顔料添加条中之背 © I 之 1 1 顔料重量 $ 僅考慮黏結劑成分而予以算出者 0 注意 1 事 1 本發明之組成物像以添加多元有機氡酸酯及 /或其預項再 1 填 Ipi 聚體至使膠凝分率為 0 . 20以上 1 . 0 0以下者為佳 9 以 0 . 40以寫本 1 上 1 · 00以下者為更佳 0 膠凝分率較 0 . 20小時 9 其硬化並不頁 1 1 1 *s£s> 兀全 » 有未能製得所期待性能之塗膜的可能性〇且 9 膠凝 1 1 分率偽依使用的樹脂之種類 » 多元有 m 氡酸之種類及該等 1 1 物質之添加量甚而硬化條件之不同而異 * 有因應要求性能訂 1 小心配合之必要〇 1 I 本發明所用的含有羥基之聚酯樹脂 > 像終端及 /或側 1 I m 中具有羥基之主鍵經酯鍵鍵結生成的高分子 » 只要是可 1 使用於一般的粉體塗料者卽可 % 並未予特別限定〇又 > 本 Γ 發明所用之聚酯樹脂偽可用公知方法製得〇例如 9 以相對 1 1 於多元酸成分之過量的多元醇成分反應而得之方法 9 或為 1 一旦高聚合度形成時調整聚酯之分子量 > 使成枝鏈狀 9 進 1 | 一步採用三羥甲基丙焼 Ν 季戊四醇等多元醇解聚合之方法 1 I 〇以此等方法製得的樹脂之中 t 若考慮本發明之組成物為 1 | 粉體塗料時，則以採用羥值 20 60 m g Κ0Η/ δ > 數目平均分 1 1 子量 2 , 0 0 0 〜5 0， 000 , 玻璃轉移溫度40〜1 00 t! 左右者為宜 1 1 〇羥值在 20 m g _/ g以下時塗膜之硬化不足，而在6 0 m gKOH 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3 8 5 90 A7 B7 五、發明説明（6 ) /g以上時硬化塗膜之耐污染性有降低之可能性。此外，數目平均分子量在2,000以下時，塗料本身在室溫有形成糖飴狀之情形，有耐叠黏性（粉體粒子相互膠黏未能生成大約結塊之性質）方面低劣等不適用作粉體塗料用途之可能性。數目平均分子量5 0,000以上時則由於硬化時之熔融黏度較高，會於塗裝表面上容易殘存著圓圈。再者，玻璃轉移溫度在4〇υ以下時組成物之耐®黏性低劣，在100 °c以上時則有調整組成物之際之作業性低劣的可能性。經濟部中夬標隼局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 構成本發明所用之聚酯樹脂的成分，基本上傺由多元醇及多元羧酸而成，依情況而異可添加油（脂肪酸）等之改質劑。至於多元醇可例示有乙二醇、丙二醇、1,3 -丁二醇、1,6-己二醇、二乙二醇、二丙二醇、新戊二醇、三乙二醇等之二元醇，丙三醇三羥甲基乙烷、三羥甲基丙烷、參羥甲基胺基甲烷等三元醇類，季戊四醇、二季戊四醇等。至於多元羧酸、可例示有酞酸酐、異酞酸酐、對酞酸或此等之低级烷基酯、四氫酞酸酐、六氫酞酸酐、四溴酞酸酐、四氣酞酸酐、HET酸酐、3,6-橋亞甲基-Δ4-四氫酞酸酐、馬來酸醉、富馬酸、分解烏頭酸、琥珀酸、琥珀酸酐、己二酸、壬二酸、癸二酸等之二元羧酸類、偏苯三甲酸酐、偏苯三甲酸、甲基環己烯三羧酸等之三元羧酸類、1,2, 4,5 -苯四甲酸酑等。至於油（脂肪酸）之例，可列舉有亞麻仁油、桐油、脱水Μ麻子油、大豆油、葵花仔油、椰子油、蓖麻子油等之油、亞麻仁油脂肪酸、大豆油脂肪酸、高油脂肪酸等之脂肪酸。其他亦可採用添加有松香、酚類、本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 8 385 90 A7B7 五、發明説明（7 ) 環氣化合物、乙烯基化合物等進一步改質的樹脂經濟部中央標準局員工消費合作社印製氡用辛二二辛丙雙 I、烯，二 ξ 二基正二、化氣將使、酸酸二稀、物二^ 、酸酷、丁一一、錫氧錫在可塩桂來酸、錫)ζΐ戊、錫§?)錫基用亦醇月馬來錫基錫*^ί環基¾)馬基一一物基基辛利外屬二二馬基苯基 }、(,氧、化丁甲二的之金、、、苯三丁錫錫 -雙T丁錫氧正二、變此鹸錫錫錫三基正基£)-12基 Ξ 正基錫三— 、錫 |*彡酸正異不除、基基基氧丙一苯，丁基氧基基錫基。成。塩丁丁辛基烯(-三，,3ί 正丁甲丁胺，§)辛劑一劑酸二二二丙、雙!(§2,1雙二 g 正二正甲ίδ 二雙酸 1 錫油化可化磺酸酸酸烯錫、，基、_ 二基二二1{酸催亦催、乙羧羧、基錫 1<基丁錫酸、丁、、'基癸的，的物二代代錫甲η— 參氣正η二錫正錫物,s羥新駿矮- 基 ) S 用物用化、硫硫基三基醯二戊酸二化_'基二使合使氧e)、、了基-I 了乙、基4-@、ϊ 氧基甲、物化際氫at錫錫正丙丨正二錫2,丙錫£錫甲二錫成之之靨.2基基_.-烯雙 > 、3-基 -!(二酸基二、酸組應化金0C丁辛一_ 、、錫氫1,丁^2基基烯異乙、錫桂本反體類 S 二二氧錫錫基化、正T丁丙二錫基月明化聚土0U醇醇基基η丁氧錫基 — i 三基：、基甲二說硬預鹼 η 硫硫丙丁SI正過基丙(,. 第甲丨醚甲二基下化體或ta、、烯正-2=-錫丁烯雙一二二雙硫三酸.辛以催單MU 錫錫、1ili(-基正 Η 基、、基'錫基癸 Η 酯金錫基基錫一 Μ 雙丁三，丁} 錫丁,s基胺新、酸鹼酸丁丁基基< 、正基物正基基正-S丁甲二物 (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 ) A4規格（210X297公釐） 9 3 8 5 9 0 A7 B7 五、發明説明（8 ) 經濟部中央標準局員工消費合作社印製化物、二乙烯基二正丁基錫、1-乙氣基乙烯基三正丁基錫、乙炔基三正丁基錫、甲基丙烯酸氣基三正丁基錫、苯基乙炔基三正丁基錫、苯基三正丁基錫、四乙醯氧基錫、四烯丙基錫、四第三丁氣基錫、四正丁基錫、四乙基錫、四異丙氣基錫-異丙醇加成物、四異丙基錫、肆（二乙胺基）錫、肆（二甲胺基）錫、四甲基錫、四正辛基錫、四正戊基錫、四苯基錫、四乙烯基錫、三正丁基苯甲氣基錫、三正丁基乙氧基錫、三正丁基甲氧基錫、三正丁基錫、乙烯基三正丁基錫、苯基汞丙酸塩、辛烯酸鉛等之有機金屬化合物、三乙基胺、Ν,Μ -二甲基環己胺等之單胺類.、1,4 -二吖雙環-2,2,2 -辛烷、Ν,Ν,Ν’，Ν’-四甲基乙二胺、N,H,Ν’，Ν' -四甲基丙烷1,3-二胺、Ν,Ν,Ν',Ν’-四甲基己烷1,6-二胺等之二胺類，^,1(’，^”-五二甲基二乙三胺、《,^,^1’， Ν”，Ν”-五甲基二丙三胺、四甲基胍等之三胺類、.三乙二胺、^'-二甲基六氫吡畊、汉-甲基，《’-(2-二甲基胺基）乙基六氫吡哄、Ν-甲基嗎啉、Ν(Ν, Ν’-二甲基胺乙基）嗎啉、 1,2-二甲基咪唑等之環狀胺類、二甲基胺基乙醇、二甲基胺基乙氧基乙醇、Ν,Ν,Ν’-三甲基胺基乙基乙醇胺、Ν -甲基- Ν'-(2-羥乙基）-六氫吡肼、Η-(2-羥乙基）-嗎啉等之醇胺類、雙（2-甲基胺基乙基）醚乙二醇雙（3-二甲基）-胺基丙基醚等之醚胺類、進一步可使用氣化鈣、氛化鋰、溴化鋰、碘化鉀等之塩，惟以使用錫条之有機金屬錯合物、有機金屬塩作為催化劑為宜。此等催化劑可單獨使用亦可合併使用。且，使用的觸媒種類及添加量、傜依樹脂、多元本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 3 8 5 9 0 (請先閱讀背面之注意事項再填寫本頁) 10 A 7 B7 五、發明説明（9 ) 有機氟酸之種類及彼等之添加量甚而硬化條件之不同而異 ,有因應要求性能小心配合之必要，採用該等催化劑可於所期待的烘烤時間内有利的完成硬化。本發明之組成物視必要時亦可摻合顔料、阻燃劑、均展劑等之添加劑。至於顔料，可列舉計有：二氣化鈦、氣化鐵紅、黃色氧化鐵、碳黑、酞菁藍、酞菁綠、Of吖啶酮糸紅色顔料、異吲睬啉酮条黃色顔料等之著色顔料、滑石粉、二氣化矽、碩酸鈣、硫酸銷等之底質顔料、鋁粉、不銹鋼粉等之金颶粉、及雲母粉等。至於阻燃劑可列舉有三氧化銻、赤礎条阻燃劑、含溴条阻燃劑。再者為提高耐蝕性，亦可添加環氧樹脂。本發明之組成物，傜採用一般的方法混合及混練所期待成分，以使之微粉碎即可調整，例如以韓蘇（H e n s c h e 1 ) 混合機混合組成物後，用擠壓機熔融混練，用針型磨機（ p U m i 1 1 )予以徹粉碎，可作成粉體塗料，此外，於塗裝於鋼板等基材時，可用公知的粉體塗料之塗裝方法予以塗裝。經濟部中央標準局員工消費合作社印製奮掄例其次舉出實施例具體的說明本發明，惟本發明並非受此等實施例所限定。且，於實施例及比較例評估的各種特性值，為依下述方式而得的結果。 [膠凝分率] 使以各種條件硬化的塗膜於25t：之Ν,Ν -二甲基乙醯胺中浸漬24小時使其膨潤。其次，將膨潤塗膜於25 °C純水中本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3 8 5 9 0 (請先閲讀背面之注意事項再填寫本頁) 11 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) 浸漬2 4小時使其收縮、進一步將之歷碎以去除溶劑部分，乾燥後，测定收縮塗膜之乾燥重量（Wc)。以此tfc值除以浸漬於N,H-二甲基乙醯胺前的初期重量 (Wo)所得之值（Wc/Wo)作為顧凝分率。惟w〇, Wc偽除去顔料添加糸内中之顔料重量，僅考窳黏結劑成分而予算出者。 [塗膜性能] 1. 表面性：以表面平滑者為〇，不平滑者為X。 2. 光澤：以』15 1(5400第7.6節（6 0。鏡面反射率>為準。 3. 方格試驗：以<115 1(5400第8.5.1節為準，評估傺以方格之殘存率（殘存數/100)表示。 4. 鉛筆硬度：以』13 15400第8.4.2節為準。 5. 埃力克森（£)~1(：1)3611)試驗：以4115 1(5400第8.2.2節為準。 6 .耐煮沸試驗：令塗板浸漬於沸水中1小時後，觀察表面性狀。 7. 耐濕試驗：以』13 1(5400第9.2.2節為準進行测試3〇〇小時。 8. 耐酸性試驗：令塗板浸漬於25 t：, 5¾硫酸水溶液240 小時後，i察表面性狀。 9 .耐_性試驗：令塗板浸漬於2 5 t：、5 %氫氧化鈉水.溶液 240小時後，觀察表面性狀。 1 〇 ,耐塩水嗔霧試驗：以J I S K 5 4 0 0第9 . 1節為準，進行測試5 0 0小時。 11.硬化時之揮發成分之定量：採用SEIKO電子工業股份有 (請先閱讀背面之注意事項再填寫本頁)[In the formula, A represents a hydrocarbon group having a sulfonic number of 1 to 6; diamidine A may also be different from each other; X is a single bond, a hydrocarbon group of 1 to 20, a carbonyl group, an alkyl group, and a divalent sulfur atom. Or gas atom; i is an integer value of 0 to 3, and di 値 i may also be different from each other. Η is 0 or 1], and the polyorganic polyacetate and / or its prepolymer are the main components. Composition for powder coatings. (Please read the precautions on the back before filling out this page) J-clothing. Order 4- This paper size applies to China National Standard (CNS) A4 (210X29.7 mm) 4 385 9 0 A7 B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives V. Description of the Invention (3) 1 | Detailed Description of the Invention 1 The present invention will be described in detail below. 1 1 I As for specific examples of the polybasic organic cyanate used in the present invention, it can be listed as --- N. Please note that 1 1 has: 4, 4, '-difluoro diphenyl ester, 3 3', 5, 5 » Tetramethyl-4, 4 '_ Read 1 I Read 1 1 Diphenyl diphenyl acid, bis (phenyl fluoro acid) methane, bis 1-qijun-3, 5- η 1 I 1 I dimethylphenyl ester) Carbohydrate > Bis (2-gallic acid-3-tertiary butyl-5 -methylphenyl) > Wangyi 1 1 matter 1 ester) methane, bis (4-cyano Acid phenyl ester) ethane 2, 2-bis (4- -fluorenic acid phenyl ester term and then ξ |) propane, 2, 2 -bis (3,5- -dimethyl-4 -fluorenic acid phenyl ester ) Propane, 2, 2- charm and write stupid tribute 1 (3 _ methyl-4- phenyl cyanate) propane, 2 2-bis- (4- cyano-3-third butyl •-· 1 I-phenylphenyl ester) propane, 2,2-bis (4-acetic acid 3-third butyl-δ-methylphenyl 1 1 1 ester) propane, 2, 2-bis (3- -allyl —4 _Amino acid phenyl ester ) Cingyuan, 1, 1-bis-1 1 order 1 (3-third butyl-4-arsin-6-methylphenyl ester) butane, 1, 1-bis (4-arsanoate phenyl ester) ) Cyclohexan, 1., 1 -bis (4. Gas acid-3 -methylphenylcetoate > cyclohexane 1 1, 1, 1 -bis (4-cyano-3--3-cyclohexyl-6 -Methyl ester) butane, bis (4-fluorobenzoic acid 1 | • yl ester) methane, bis (4-cyanic acid-3,5-dimethyl ester) methane, bis (4-fluoric acid-3-1 grade Tertiary butyl-6-methylphenyl ester) methylamine, bis (4-phosphonic acid phenyl ester) > tricyclic [1 I 5, 2, 1, 〇2 .6] decane, bis (4- Aqueous acid 3 5 dimethylbenzene: yl ester) tricyclic [1 1 5, 2, 1, 02 .6] Kewon, bis (4-cyano-3-third butyl-6-methylphenyl ester ) 1 1 Bicyclo [5,2,1, 〇2.6] Guyuan, Bis (4-O-Phenyl Phenyl Acid) Sulfide, Bis (4-1 1 Phenyl-3,5-Diphenyl Phenyl Ester ) Thioether, bis (3- third butyl-4 -gas acid- 1 I 6 -methylphenyl ester sulfide, bis (4-cyanophenyl)) m., And (4-cyanate 1 I Phenyl ester) carbonyl, bis (4--gallate phenyl ether), etc. 〇1 1 I Among them, 2,2-bis (4-gallate phenyl ester) propane, 1,1-bis (3- 1 1 1 Tertiary butyl-4 -acetic acid, 6-methyl phenylcobutane is preferred, and it is suitable for rubidium and coating. 1 1 This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 5 38 59 0 Μ Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4)-1 1 Storage stability such as anti-adhesion storage life, or excessive coating drying 1 1 | When baking In the case of resistance to yellowing, 9 is based on the use of 1, 1 -bis (3 -third butyl-1 1 4 -gas acid-6 -methylphenyl ester) butane and the cyanate ester compound as a main component. X—NI Please 1 1 Prepolymer is better. 0 Read 1 I Read 1 | In addition, t can also be used with three backs of acetic acid ester groups with these gas esters 1 1 1 The molecular weight of the three-tillage ring formed by polymerization is at least 40 0 to 6 000. Note 1 The prepolymer is used as the hardener of the present invention. 0 On the occasion of prepolymerization, it can be DO. Fill in or combine the way represented by cyanate ester αο 単 body 〇 Prepolymerization, for example, proton acid phosphoric acid aluminum boron trifluoride complex of zinc acid phosphoric acid manuscript r page 1 etc. — ✓ 1 Acids such as isostic acid • Phenol naphthol (P he η 〇1 py Γ 0 catech 〇Π, dihydroxy 1 1 aryl naphthalene represented by aromatic naphthalene 9 zinc sulfonate zinc cobalt sulfonate 1 1 tin octoate Organometals such as cobalt octoate, zinc ethylacetonate, ethyl acetate, etc. Organometal complexes such as copper acetate ethylacetate, aluminum ethylacetonate, etc. Triethylamine 1 I% Tributylamine N Df Tertiary amines 9 Ammoniated tetramethylammonium, bromine, 1 quaternary ammonium represented by tetramethylammonium, imidazoles, t hydrogenation, m, and gas. 1! 1 NaCl, bicyclo [2,2,2] octane, three Phenyl o-phenylene; sodium sulfonate, lithium chloride, etc., or a mixture of these as a catalyst, the above cyanate esters can be polymerized together to obtain 01. These organic cyanate esters and prepolymers H3ii can each be white BO was used alone or combined earlier to make 1 | use 〇1 | the amount of organic phosphonate and / or its prepolymer used in the present invention, 1 1 | Regulation 箸 0 The gel fraction of this product is measured by the following method. The polyester resin that has been mixed with a specified amount of polyorganic acid ester and / or its prepolymer is mixed under various conditions. 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 6 3 8 5 9 0 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5)-1 1 The hardened product was immersed in 25 t: Η, Η-dimethylacetamide for 2 4 hours t to swell 1 I, and then immerse the swelling gel in 25 V water for 2 4 hours to make it 1 1 1 shrink > Pre-press to remove the solvent part 9 and dry in a heating vacuum furnace. -N 1 Please ask 1 1 This value of the weight after drying (WC) and the weight of the initial hardened product (Wo) are first Read 1 Read Γ | (tf c / W 〇) is defined as the gel fraction. However, W 0 * Me is like removing the back of the pigment addition bar © I 1 1 Pigment weight $ Calculated by considering only the binder component 0 Note 1 Matter 1 The composition image of the present invention is added with multiple organic phosphonates and / Or its pre-item, then fill in Ipi polymer to make the gel fraction 0. 20 or more 1. 0 0 or less is better 9 to 0. 40 to the writing 1 1 1. 00 or less is better 0 gel point The rate is less than 0.20 hours. 9 It hardens and does not cure. Page 1 1 1 * s £ s > Wuquan »There is a possibility that the coating film with the desired performance cannot be obtained. 0 9 Gel 1 1 Types of resins »There are various types of m acetic acid and the amount of these 1 1 substances added, and even the hardening conditions are different. * According to the required performance, 1 needs to be carefully formulated. 1 I The hydroxyl-containing polyester used in the present invention Resin > Macromolecules such as a terminal and / or side 1 I m having a hydroxyl group in the main bond via an ester bond »As long as it can be used in general powder coatings, it is not limited in particular%. The polyester resin used in the present invention can be prepared by a known method. For example, 9 is a method 9 obtained by reacting an excess of a polyol component with respect to a polyacid component of 1 1 or 9 or 1 when the degree of polymerization is formed. Molecular weight> Make branched chain 9 into 1 | Method 1 using trimethylolpropionate pentaerythritol and other polyhydric alcohols to depolymerize 1 I 〇 Among the resins prepared by such methods t If the composition of the present invention is considered For 1 | powder coating, the average value of the number of hydroxyl groups is 20 60 mg Κ0Η / δ > 1 1 sub-quantity 2, 0 0 0 ~ 5 0, 000, glass transition temperature 40 ~ 1 00 t! It is suitable that the hardening of the coating film when the hydroxyl value is less than 20 mg / g At 60 m gKOH 1 1 this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 3 8 5 90 A7 B7 V. Description of the invention (6) / g and above the pollution resistance of the hardened coating film Sexuality may decrease. In addition, when the number-average molecular weight is below 2,000, the coating itself may form a sugar-like shape at room temperature, and it is inferior in anti-adhesion properties (the properties of powder particles sticking to each other and failing to form an agglomerate). Possibility of powder coating application. When the number average molecular weight is more than 50,000, a circle tends to remain on the coating surface due to the high melt viscosity during hardening. In addition, when the glass transition temperature is lower than 40 ° C, the composition has poor tack resistance, and when the temperature is higher than 100 ° C, the workability may be poor when adjusting the composition. Printed by the Consumers' Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The constituents of the polyester resin used in the present invention are basically made of polyols and polycarboxylic acids. Depending on the situation, a modifier such as oil (fatty acid) can be added. Examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and triethylene glycol. , Triols such as glycerol trimethylolethane, trimethylolpropane, and p-methylolaminomethane, pentaerythritol, dipentaerythritol, etc. As for the polycarboxylic acid, phthalic anhydride, isophthalic anhydride, terephthalic acid or a lower alkyl ester thereof, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetragas phthalic anhydride, HET anhydride, 3,6-bridged methylene-Δ4-tetrahydrophthalic anhydride, maleic acid, fumaric acid, decomposed aconitic acid, succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, etc. Tricarboxylic acids such as carboxylic acids, trimellitic anhydride, trimellitic acid, methylcyclohexene tricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid. Examples of the oil (fatty acid) include linseed oil, tung oil, dehydrated sesame oil, soybean oil, sunflower oil, coconut oil, castor oil, etc., linseed oil fatty acid, soybean oil fatty acid, and high oil Fatty acids such as fatty acids. Others can also be added with rosin, phenols, this paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) 8 385 90 A7B7 V. Description of the invention (7) ring gas compounds, vinyl compounds, etc. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Quality and Economics of the People's Republic of China, octyl octyl octyl propylene bis I, ene, di ξ diyl dimethyl dioxane, chemical gas will make acid, acid dilute, material di ^, acid cool, butadiene, Tin oxide can be used in lauric acid, tin), zirconium, tin, §?) Tin group is also used. Maleic tin group. Makiphenyl), (, oxygen, butylated gold, ,, phenyltributyltin-di-t-butyltin-oxy-n-, changed to tin-tin-tin-tri-n-phenyl group) -12 group , Tin | * acetic acid is not different, yloxypropyl monobenzene, butyloxy tin. to make .塩 Butyloctyl ene (-tri ,, 3ί n-butylbutylamine, §) octant one dose of dimethyl dipropylene, bis! (§2,1 bis dig n-di-n-methyl δ δ dibisacid 1 tin oil Sulfuric acid succinic acid, allyl, di-, di-di-di 1 (acid catalyzed, ethyl carboxyl, di-tin 1 < butyl stannous acid, butyl, bis-, hexadecyl), second generation Tin Form η—Phenyl-n-Di-tin-tin, s-Hydroxyl dwarf-based) S for chemical use, thiothiotriylphosphonium divaleric acid di -'- dioxygenation e), , The group -I, the group B, the group 4- @, ϊ methoxymethyl, the physical and chemical hydrogen at tin tin n-propyl 丨 n-ditin 2, propyl tin £ tin methyl ditin into the 靥. 2 group _.- ene Bis >, 3-yl-! (Diacid group, acid group, 0C butyl octyl -1,, stannous hydrogen, 1, but ^ 2-based alkene isoethyl, stannyl complex dioxane Tin-tin-based, n-T-butyl-propylene-di-tinyl-methacrylic polymer, 0U alcohol, alcohol-based group, butoxytin group — i-triyl group: succinic pre-base, thiothiopropene, SI, peroxypropyl group ( ,. Dimethyl ether dimethyl ether or ta, ene--2--tin butene bis bis disulfide triacid. Octane urging MU tin tin, 1ili (-yl Fluorenyl, acyl'tinyldecanoate, goldtinyltin, 1M bisbutyltributyl, butyl} tin, succinylamine, acid-base acid butylbutyl <, n-based n-yl-n-S butane dimer (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 9 3 8 5 9 0 A7 B7 V. Description of Invention (8) Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Printed Products, Divinyl Di-n-Butyl Tin, 1-Ethyl Vinyl Tri-N-Butyl Tin, Acetyl Tri-N-Butyl Tin, Methacrylic Tri-N-Butyl Tin, Phenyl Acetyl Tri-N-Butyl Tin, Phenyl Tri-n-butyltin, tetraethoxytin, tetraallyltin, tetra-tert-butyltin, tetra-n-butyltin, tetraethyltin, tetraisopropyltin-isopropanol adduct, tetraisopropyl Propyltin, di (diethylamino) tin, di (dimethylamino) tin, tetramethyltin, tetra-n-octyltin, tetra-n-pentyltin, tetraphenyltin, tetravinyltin, triphenyltin N-butylbenzyltin, tri-n-butylethoxytin, tri-n-butyltin, tri-n-butyltin, vinyl Organometallic compounds such as n-butyltin, rhenium phenylmercurate, lead octoate, monoethylamines such as triethylamine, N, M-dimethylcyclohexylamine, etc. 2,2,2-octane, N, N, N ', N'-tetramethylethylenediamine, N, H, N', N '-tetramethylpropane 1,3-diamine, N, N , N ', N'-tetramethylhexane 1,6-diamine and other diamines, ^, 1 (', ^ "-pentadimethyldiethylenetriamine,", ^, ^ 1 ', Ν ", Ν"-pentamethyldipropanetriamine, tetramethylguanidine and other triamines, triethylenediamine, ^ '-dimethylhexahydropyridine, han-methyl, "'-( Rings of 2-dimethylamino) ethylhexahydropyridine, N-methylmorpholine, N (N, Ν'-dimethylaminoethyl) morpholine, 1,2-dimethylimidazole, etc. Amines, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N '-(2-hydroxyethyl Alcohol) amines such as hexahydropyrazine, hydrazone- (2-hydroxyethyl) -morpholine, bis (2-methylaminoethyl) ether glycol bis (3-dimethyl)- For ether amines such as aminopropyl ether, calcium gas, lithium lithium, lithium bromide, For the thallium such as potassium iodide, an organometallic complex containing tin bars and an organic metal thallium are preferably used as a catalyst. These catalysts may be used alone or in combination. In addition, the type and amount of the catalyst used, conversion resin, and multiple paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 3 8 5 9 0 (Please read the precautions on the back before filling this page ) 10 A 7 B7 V. Description of the invention (9) The types of organic fluoric acid and their addition amount and even the hardening conditions vary. It is necessary to carefully match the required performance according to the required performance. The use of these catalysts can be used in the desired drying The hardening is advantageously completed within the baking time. If necessary, the composition of the present invention may be blended with additives such as pigments, flame retardants, and leveling agents. As for the pigments, titanium dioxide, vaporized iron red, yellow iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, Ofacridone red pigment, isoindolinone yellow pigment, etc. Color pigments, talcum powder, silicon dioxide, calcium sulphate, sulfuric acid and other ground pigments, aluminum powder, stainless steel powder, etc., and mica powder. Examples of the flame retardant include antimony trioxide, red basic strip flame retardant, and bromine strip flame retardant. Furthermore, in order to improve the corrosion resistance, an epoxy resin may be added. The composition of the present invention is generally mixed and kneaded with desired ingredients by a general method, so that it can be adjusted by pulverization. For example, after mixing the composition with a Hensu 1 mixer, it is melt-kneaded with an extruder. It can be pulverized thoroughly with a pin mill (p U mi 1 1) to make a powder coating. In addition, when coating on a substrate such as a steel plate, it can be coated by a known coating method of powder coating. Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Examples The following examples specifically illustrate the present invention, but the present invention is not limited by these examples. The various characteristic values evaluated in the examples and comparative examples are the results obtained in the following manner. [Gelling fraction] The coating film hardened under various conditions was dipped in 25t: Ν, Ν-dimethylacetamide for 24 hours to swell. Secondly, apply the swelling coating film in pure water at 25 ° C. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 3 8 5 9 0 (Please read the precautions on the back before filling this page) 11 Economy Printed by A7 B7, Consumer Cooperatives of the Ministry of Standards and Standards of the People's Republic of China. 5. Description of the invention (10) Dip for 24 hours to shrink, and then crush it to remove the solvent part. After drying, measure the dry weight (Wc) of the shrinkage coating film. The value (Wc / Wo) obtained by dividing the tfc value by the initial weight (Wo) before immersion in N, H-dimethylacetamide was used as the coagulation fraction. However, w0, Wc is a pseudo-removal pigment. The weight of the pigment added to the paste is calculated based on the ingredients of the binder. [Coating film performance] 1. Surface property: The surface smoothness is 0, and the non-smoothness is X. 2. Gloss: "15 1 (5400 Section 7.6 (60. Specular Reflectivity) shall prevail. 3. Checker test: < 115 1 (5400 Section 8.5.1 shall prevail) The residual rate (remaining number / 100) of the grid is indicated. 4. Pencil hardness: "13 15400 section 8.4.2 shall prevail." 5. Erickson (£) ~ 1 (: 1) 3611) test: 4115 1 (Section 8.2.2 of 5400 shall prevail. 6. Boiling resistance test: After immersing the coated plate in boiling water for 1 hour, observe the surface properties. 7. Moisture resistance test: According to "13 1 (5400 Section 9.2.2 shall prevail) Test for 300 hours. 8. Acid resistance test: make the coated plate immersed in 25 t :, 5¾ sulfuric acid aqueous solution for 240 hours, check the surface properties. 9. Resistance test: make coated plate immersed in 2 5 t: 5 % Sodium hydroxide in water. The solution was observed for 240 hours after the solution was tested. 10, Water and fog resistance test: Based on JISK 5400 section 9.1, the test was performed for 500 hours. 11. When hardened Volatile component quantification: using SEIKO Electronics Industry Co., Ltd. (Please read the precautions on the back before filling in this page)

<1T 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ297公釐） 12 38590 A7 B7 五、發明説明（11 ) 限公司製造之熱分析条统SSC5200,對各別的塗料進行熱重量分析，測定在180t：放置30分鐘（升溫速度50t：/ rain)後之重量減少率。 12.耐衝擊性：以』15 1(5400等8.3.2節為準。 [粉體塗料評估] 1. 耐叠黏性試驗：將裝有塗料之乙烯塑膠袋在40 t：供箱内放置一個月後，以目視評估其塗料之狀態。評估以〇表塗料有流動性，△表成塊狀可用手壓碎，X表正熔著中。 2. 儲存壽命試驗：將裝有塗料之乙烯塑膠袋在40t：烘箱内放置一個月後，用Ν,Ν-二甲基甲醒胺萃取該塗料之黏結劑，藉由離心分離而沈降分離出顔料。用GPC (東曹公司製造、HLC8 020 )評估己萃取出的黏結劑成分之分子量（Mw)上升率。 3. 耐黃變性試驗：採用未摻合添加劑之塗料進行過度烘烤探討。過度烘烤之條件為20〇υ 1小時及22010 1小時二點。色差（ΔΕ)傺以在1801C 30分鐘之標準條件硬經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 化的各値試料為基準而測得。会成例1 於附有溫度計、攪拌器、滴液漏斗及迴流冷凝管之反應器内，在氮氣籠罩下加入2,2-雙（4-羥基苯基）丙烷（三并東壓化學工業股份有限公司製造）114.2g(0,5raol)、甲基異丁基酮6 8 5 g ,在室溫溶解後，冷却溶液至0"〇。其次於2小時内滴下氣化氤6 7 . 7 g (1 . 1 m ο 1 )。自滴下氣化氰開始本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ,〇 0 0 _ n n id 〇〇 o y u 經濟部中央標準局員工消費合作社印製本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3 85 9 0 A7 B7 五、發明説明（12 ) 之5分鐘後，在0〜6¾下於2小時30分鐘内滴下三乙胺 111.2g(l.lmol·),進一步保持同溫度30分鐘。以3¾塩酸水3〇Og洗淨後，用水300s水洗2次並予分液。由所得的有機層中之二氰酸酯體含量得知反應率為99%，其次減壓濃縮此有機層至178g後，滴下異丙醇228g,冷却至5°C並予攪拌3小時，過濾出所得漿液，用異丙醇114g洗淨後，風乾而得熔點80t：之白色結晶121,lg(産率87% )。藉由LC( 液體層析法）未能檢出原料之雙酚及單氰酸酯體。藉由GC( 氣體層析法）分析所得白色結晶，未能檢出二乙基氰胺。又，藉由探用硝酸銀之電位差滴定法嘗試進行氮離子之分析，氣離子在lOppm以下。以下簡稱本物質為BPAC。管掄例1 於以針式磨機（Alpine公司製造）預粉碎的商品ER6610 [日本酯（ester*)股份有限公司製造，終端羥基聚酯樹脂、羥值31mgK0H/g]866g内加人合成例1合成的BPAC[2,2 -雙-( 4-氟酸苯基酯）丙烷]134S,用超级混合機- Y-5(河田股份有限公司製造）並予預備混合。其次，用Laboplastm_ill 30C150(東洋精機股份有限公司製造）在100Ό熔融混練此組成物後，用針式磨機（Alpine公司製造）予以微粉碎成粉體塗料。將此塗料靜電塗裝於日本試板（test panel)工業股份有限公司製造的磷酸鋅處理板JIS G3141(SPCC-SD)PB 137T上，在180Ϊ：之熱風烘箱内硬化30分鐘。如表2所示，塗膜顯示出良好的塗膜性能，與現行的 14 (請先閲讀背面之注意事項再填寫本頁) --^衣- 訂< 1T This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) 12 38590 A7 B7 V. Description of the invention (11) Thermal analysis system SSC5200 made by the company, thermal weight of each coating The weight loss rate after analysis was measured at 180 t: standing for 30 minutes (heating rate: 50 t: / rain). 12. Impact resistance: "15 1 (5400, etc. Section 8.3.2 shall prevail. [Powder coatings evaluation] 1. Stacking resistance test: Put the vinyl plastic bag with the coating in a 40 t: supply box One month later, the condition of the coating was evaluated visually. The surface of the coating was evaluated to be 0, and the △ table was lumpy and can be crushed by hand, and the X table was being fused. 2. Storage life test: The ethylene containing the coating was tested. After leaving the plastic bag in a 40t oven for one month, the adhesive of the coating was extracted with Ν, Ν-dimethylmethanamine, and the pigment was separated by sedimentation by centrifugation. GPC (manufactured by Tosoh Corporation, HLC8 020) ) Evaluate the rising rate of molecular weight (Mw) of the extracted binder components. 3. Yellowing resistance test: Use paint without additives to investigate over baking. The conditions for over baking are 20 〇 1 hour and 22010. 1 hour and 2 o'clock. The color difference (ΔΕ) 傺 is based on the test samples printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Hard Economy and the standard conditions at 1801C for 30 minutes (please read the precautions on the back before filling this page). Measured. Example 1 with thermometer and stirrer. In the reactor of the dropping funnel and the reflux condenser, under a nitrogen blanket, add 2,2-bis (4-hydroxyphenyl) propane (manufactured by Sannoto Chemical Co., Ltd.) 114.2g (0,5raol), 6 8 5 g of methyl isobutyl ketone, after dissolving at room temperature, cool the solution to 0 " 0. Next, the gasified 氤 6 7. 7 g (1.1 m ο 1) was dripped within 2 hours. The cyanide began to apply the Chinese National Standard (CNS) A4 specification (210X 297 mm), 〇 0 _ nn id 〇〇oyu printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the paper standards are applicable to the Chinese National Standard (CNS ) A4 specification (210X297 mm) 3 85 9 0 A7 B7 V. After 5 minutes of the description of the invention (12), 111.2 g (l.lmol ·) of triethylamine was dripped within 2 hours and 30 minutes at 0 ~ 6¾, It was further maintained at the same temperature for 30 minutes. After washing with 300 g of 3¾ acid water, it was washed twice with 300s of water and liquid-separated. From the dicyanate content in the obtained organic layer, the reaction rate was 99%, followed by After concentrating the organic layer under reduced pressure to 178 g, 228 g of isopropanol was dropped, cooled to 5 ° C and stirred for 3 hours, and the resulting solution was filtered off. Liquid, washed with 114g of isopropanol, and air-dried to obtain a white crystal with a melting point of 80t: 121, lg (yield 87%). The bisphenol and monocyanide of the raw materials could not be detected by LC (liquid chromatography). Ester body. The white crystals obtained by GC (gas chromatography) analysis failed to detect diethylcyanamide. In addition, the analysis of nitrogen ions was attempted by the potential difference titration method using silver nitrate. The gas ions were at 10 ppm. the following. This substance is hereinafter referred to as BPAC. Tube Example 1 A synthesis example was prepared by adding 866 g of a pre-milled product ER6610 [manufactured by Nippon Ester * Co., Ltd., a terminal hydroxyl polyester resin, a hydroxyl value of 31 mgK0H / g] with a pin mill (manufactured by Alpine Corporation). 1. Synthesized BPAC [2,2-bis- (4-fluoroacid phenyl) propane] 134S was premixed with a super mixer-Y-5 (manufactured by Kada Corporation). Next, this composition was melt-kneaded at 100op with Laboplastm_ill 30C150 (manufactured by Toyo Seiki Co., Ltd.), and then finely pulverized with a pin mill (manufactured by Alpine Corporation) into a powder coating. This coating was electrostatically coated on a zinc phosphate treated plate JIS G3141 (SPCC-SD) PB 137T manufactured by Japan Test Panel Industry Co., Ltd. and hardened in a hot air oven at 180 ° F for 30 minutes. As shown in Table 2, the coating film shows good coating film performance, which is in line with the current 14 (please read the precautions on the back before filling this page)-^ 衣-订

B 明目卜兑夕將条此曰 I 發D / P 、 I 五之度寬銹生側單之〇部越格優方其之尤後面驗方試性蓀面噴表水在塩 , 耐較，顯部格方的餘其 ο 已而處 1 有僅〇置性位蝕其耐惟好 , 良 min之 2 B 0 為 1 值約大出最示量之質物發 E· 擇時 LL 化彳硬 ii H. 0 I 與察 1 t 了觀彳^ 0 為 » VI/ 者置再裝析分用採量重熱結 ο 定測之線曲溫升的等同時為少減量 S S 之鐘分 ο 3 後始開定测例較 f-h 經濟部中央標準局員工消費合作社印製於以針式磨機（Alpine公司製造）預粉碎的商品ER6610 (曰本酯股份有限公司製造，終端羥基聚酯樹脂、羥值 31mgK0H/g)828g内加人合成例1合成的商品Kureram UI (住友拜耳尿烷股份有限公司製造、基團封閉化異佛爾酮二異氡酸酯）169s、二月桂酸二丁基錫（東京化成股份有限公司製造）3g、Seikol Z[商品名，精工社股份有限公司製造、安息香（benzoin)]4.64g、 resiflow P67(商品名，Estron 化學公司製造，丙烯酸酯条聚合體）4. 64g,用超级混合機 Y-5(河田股份有限公司製造）予以預混合。其次，用 Laboplastmill 30C150(東洋精機股份有限公司製造）在 100¾熔融混練此組成物後，用針式磨機（AlpUe公司製造 )予以徹粉碎成粉體塗料。將此塗料靜電塗裝於日本試板工業股份有限公司製造的磷酸鋅處理板』1503141(5卩(：(：-50)卩8 1371'上，在1801 之熱風烘箱内硬化30分鐘，塗膜性能如表2所示，表面上殘留著圓圈。此外，耐塩水噴霧試驗後之方格部之單側生 (請先閱讀背面之注意事項再填寫本頁) 訂 V· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 15 38 5 90 A7 B7五、發明説明（14 ) 銹寬度約占整體3 m b。再者，伴隨著硬化時揮發物質損失之重量減少為2.7 % 〇表1 經濟部中央標準局員工消費合作社印製實施例1 比較例1 ER66 1 0 866 828 Kurerain U I - 169 BP AC 13 4 - 二月桂酸二丁基錫 - 3 S e i k 〇 1 Z -. 4.64 Resiflow-P67 - 4.64 (請先閱讀背面之注意事項再填寫本頁) _· 訂本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 3 8 59 0B Ming Mu Bu Dui Xi will say I issued D / P, I five degrees of wide rust raw side single sheet of the 0 part of the grid is better than the other, the test is followed by a trial spray water on the surface, resistant, The significant part of the square is more than ο where it is at 1. There is only 0 permissive pitting. Its resistance is good, 2 min 0 of the good min is 1. The value is about larger than the most indicated quality. ii H. 0 I and 1 1 t 了彳彳 0 0 is »VI / the re-installation of the analysis and recovery of the separation and use of heat recovery ο the line temperature rise of the measured line at the same time is the minute of the reduction SS ο 3 The test case was started later. It is printed on the product ER6610 (manufactured by Ben Ester Co., Ltd., terminal hydroxyl polyester resin, Value: 31 mgK0H / g) 828 g of Kureram UI (composed by Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate manufactured by Sumitomo Bayer Co., Ltd.) 169s, dibutyltin dilaurate (Tokyo Made by Kasei Co., Ltd.) 3g, Seikol Z [商Name, manufactured by Seiko Co., Ltd., benzoin] 4.64 g, resiflow P67 (trade name, manufactured by Estron Chemical Co., Ltd., acrylic strip polymer) 4. 64 g, using a super mixer Y-5 (Kawata Co., Ltd. (Manufactured) to be premixed. Next, this composition was melt-kneaded at 100¾ with Laboplastmill 30C150 (manufactured by Toyo Seiki Co., Ltd.), and then thoroughly pulverized into a powder coating with a pin mill (manufactured by AlpUe). This coating was electrostatically coated on a zinc phosphate-treated plate manufactured by Japan Test Plate Industry Co., Ltd. "1503141 (5 卩 (: (:-50) 卩 8 1371 ', and was hardened in a hot air oven of 1801 for 30 minutes. The performance is shown in Table 2. Circles remain on the surface. In addition, the side of the checkered section after the water spray resistance test (please read the precautions on the back before filling this page) Order V · This paper size applies to China Standard (CNS) A4 specification (210X297 mm) 15 38 5 90 A7 B7 V. Description of the invention (14) The rust width accounts for about 3 mb as a whole. In addition, the weight loss associated with the loss of volatile materials during hardening is 2.7%. 1 Example printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 Comparative Example 1 ER66 1 0 866 828 Kurerain UI-169 BP AC 13 4-Dibutyltin dilaurate-3 S eik 〇1 Z-. 4.64 Resiflow-P67- 4.64 (Please read the precautions on the back before filling in this page) _ · The size of the paper used in this edition applies to the Chinese National Standard (CNS) A4 (210X297 mm) 3 8 59 0

7 B 五、發明説明（15 ) 表2 經濟部中央標準局員工消費合作社印製實施例1 比較例1 烘烤條件 180 t： . 30 分 1 80 Ό , 30分膠凝分率 0.77 0.80 表面性〇 X 光澤（％ ) 103 98 方格試驗 100/100 100/100 鉛筆硬度 F F 埃力克森 8 m m合格 8 in hi合格耐煮沸試驗無異常無異常耐濕試驗無異常無異常耐酸性試驗無異常無異常耐鹼性試驗無異常無異常耐塩水噴霧試驗單側 2 m m 單倒 3 a m 硬化時重童減少（％ ) 0 . 2 2.7 ---------,πϊ-- (請先閲讀背面之注意事項再填寫本頁) — ，丄一、va 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 17 38 590 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（16 ) 会成例2 於附有溫度計，攪拌器、滴液漏斗及迴流冷凝管之反應器内，在氮氣簏罩下加入Sumilize「BBM-S [商品名，住友化學工業股份有限公司製造，1,1-雙（4-羥基-3-第三丁基-6-甲基苯基）丁烷] 200s(0.5228莫耳）、甲基異丁基酮800g,在室溫溶解後，添加三乙胺148.1s(1.464莫耳）。冷却溶液至0°C後，在0 〜61C下於2小時内滴下氮化氰89.99g(1.464莫耳），保持同溫度1小時。以300g水洗滌3次後，藉由減壓濃縮濃縮溶劑使成650g後滴下甲醇400g冷却至5¾並予攪拌3小時，過濾出所得皂漿液，用甲醇200g洗淨後減壓乾燥而得熔點 123t：之白色結晶208g(産率92¾ )。藉由LC(液體層析法）而得之二氡酸酯體之純度為98.0%。且，水洗後甲基異丁基酮溶液中之二乙基氣胺含量為1.90 %,以下簡稱本物質為 BBMC。審掄例2 於以針式磨機（Alpine公司製造）預粉碎的ER661M商品名，日本酯股份有限公司製造、終端羥基聚酯樹脂） 559g内加人 Tipure-R90[商品名，（Dupont Japan)股份有限公司製造，二氧化鈦]333g，合成例1合成的BPAC[2,2-雙- (4-氡酸苯基酯）丙烷]108g,二月桂酸二丁基錫（東京化成股份有限公司製造）0.07g，用超级混合機Y-5(河田股份有限公司製造）予以預混合。其次，用關西棍股份有限公司製造的二只棍輪LABORATORY MIL,在前锟輪20rPm, (請先閲讀背面之注意事項再填寫本頁)7 B V. Description of the invention (15) Table 2 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 1 Comparative Example 1 Baking conditions 180 t:. 30 minutes 1 80 Ό, 30 minutes gel fraction 0.77 0.80 surface properties 〇X gloss (%) 103 98 grid test 100/100 100/100 pencil hardness FF Elixon 8 mm qualified 8 in hi qualified boiling resistance test no abnormality no abnormal humidity resistance test no abnormality no abnormal acid resistance test no abnormality no Abnormal Alkali Resistance Test No Abnormal No Water Resistance Spray Test 2mm on one side and 3am on single down 3% reduction in hardening (%) 0. 2 2.7 ---------, πϊ-- (Please read first Note on the back page, please fill in this page again) —, 丄, va This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 17 38 590 Printed by the Consumer Standards Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs A7 B7 Explanation (16) Example 2 In a reactor with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, add Sumilize "BBM-S [trade name, manufactured by Sumitomo Chemical Industries, Ltd.] under a nitrogen blanket. , 1,1- (4-hydroxy-3-tertiary butyl-6-methylphenyl) butane] 200s (0.5228 moles), 800g of methyl isobutyl ketone, dissolved at room temperature, and then added triethylamine 148.1s ( 1.464 moles). After cooling the solution to 0 ° C, drop 89.99 g of cyanogen nitride (1.464 moles) within 2 hours at 0 to 61C, and keep the same temperature for 1 hour. After washing 3 times with 300 g of water, The solvent was concentrated under reduced pressure to make 650 g of methanol dropwise, and 400 g of methanol was dropped to 5¾ and stirred for 3 hours. The obtained soap slurry was filtered, washed with 200g of methanol, and dried under reduced pressure to obtain a melting point of 123t: 208g of white crystals (yield 92¾). The purity of the diacetate obtained by LC (Liquid Chromatography) is 98.0%. The diethyl amine content in the methyl isobutyl ketone solution after washing with water is 1.90%. The substance is BBMC. Examination Example 2 559g was pre-pulverized with a pin mill (manufactured by Alpine) under the trade name of ER661M, manufactured by Japan Ester Co., Ltd., and terminated with hydroxypolyester resin. Tipure-R90 [trade name, (Dupont Japan) Co., Ltd., Titanium Dioxide] 333 g, BPAC [2,2-bis- (4-phosphonic acid phenyl ester) synthesized in Synthesis Example 1 Propane] 108g, dibutyl tin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.07g, be pre-mixed with a super mixer Y-5 (parts share Kawata Co., Ltd.). Secondly, two stick wheels LABORATORY MIL made by Kansai Stick Co., Ltd. are used at the front wheel 20rPm, (Please read the precautions on the back before filling this page)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 18 3 8 59 0 經濟部中央標準局員工消費合作社印策 A7 -----!Z___ 五、發明説明（17 ) 8〇t：、後棍輪24r*pn, liot：之條件下混練此組成物。其後用針式磨機（Alpine公司製造）予以微粉碎成粉體塗料。將此塗料靜電塗裝於日本試板工業股份有限公司製造的磷酸鐘處理板 J I S G 3 1 4 1 ( S P C C - S D ) P B 1 3 7 T 上，在 1 8 0 t：之熱風供箱内使硬化30分鐘。塗膜表面上亦無氣泡生成， a顯示出如表4所示的良好塗膜性能。This paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) 18 3 8 59 0 Printing policy A7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -----! Z___ 5. Description of the invention (17) 8〇 t :, the rear stick wheel 24r * pn, liot: under the condition of mixing this composition. Thereafter, it was finely pulverized with a pin mill (manufactured by Alpine) into a powder coating. This coating was electrostatically coated on a phosphoric acid bell processing board JISG 3 1 4 1 (SPCC-SD) PB 1 3 7 T manufactured by Japan Trial Industry Co., Ltd. and hardened in a hot air supply box at 180 t: 30 minutes. No bubbles were formed on the surface of the coating film, and a showed good coating film performance as shown in Table 4.

以表3之配方為準，於以針式磨機（Alpine公司製造）預粉碎的ER6610(商品名，日本酯股份有限公司製造，終端羥基聚酯樹脂）565s内，加人Tipure-R9 02 (商品名，曰本杜邦股份有限公司製造，二氣化鈦）333g,合成例2合成的BBMC(1,1-雙（3-第三丁基-4-氡酸-6-甲基苯基酯）丁烷 l〇2g、二月桂酸二丁基錫（東京化成股份有限公司製造） 0.334s、用超級混合機Y-5(河田股份有限公司製造）予以預混合。其次，用闋西輥股份有限公司製造的二只锟輪 LABORATORY MIL,在前親輪 20rpm, 80t：、後提輪 24γ*ρ η, 11〇υ之條件下混練此組成物。其後用針式磨機（Alpine公司製造）予以微粉碎，採用140篩目之篩網分级成粉體塗料 Ο 將此塗料靜電塗裝於日本試板工業股份有限公司製造的璘酸鋅處理板 JIS G3141(SPCC-SD)PB 137T上，在 18〇υ 之熱風烘箱内硬化30分鐘。硬化塗膜之表面未觀察到有突起的現象。塗料及塗膜性能如表4所示般良好。尤其是關於保存壽命之評估，分子量（Mw)之上升率只不過為0.6 % (請先閲讀背面之注意事項再填寫本頁)Based on the formula in Table 3, add Tipure-R9 02 to ER6610 (trade name, manufactured by Nippon Ester Co., Ltd., terminal hydroxy polyester resin) pre-pulverized with a pin mill (manufactured by Alpine Corporation). Trade name, manufactured by DuPont Co., Ltd., 333 g of titanium digas, BBMC (1,1-bis (3-tert-butyl-4-arsonate-6-methylphenyl ester) synthesized in Synthesis Example 2 ) 102 g of butane, dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.334s, and pre-mixed with a super mixer Y-5 (manufactured by Kota Co., Ltd.). The two labyrinth wheels manufactured by LABORATORY MIL were kneaded under the conditions of a front pro wheel 20rpm, 80t :, and a rear lift wheel 24γ * ρ η, 11〇υ. After that, they were mixed with a pin mill (manufactured by Alpine). Finely pulverized and classified into a powder coating using a 140-mesh sieve. This coating was electrostatically coated on a zinc gallate treated board JIS G3141 (SPCC-SD) PB 137T manufactured by Japan Trial Industry Co., Ltd. at 18 〇υ Harden in a hot air oven for 30 minutes. No protrusions were observed on the surface of the hardened coating film The phenomenon of coatings and coatings is as good as shown in Table 4. Especially for the evaluation of storage life, the increase rate of molecular weight (Mw) is only 0.6% (please read the precautions on the back before filling this page)

本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 19 38590 A7 B7 五、發明説明（18 ) 而已，與比較例2之使用基圃封閉化IPDI作為硬化劑者相較下，明顯可見保存壽命特佳。This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 19 38590 A7 B7 V. Description of the invention (18) It is obviously different from the comparative example 2 in which the base closed IPDI is used as the hardener. It can be seen that the storage life is particularly good.

奮旃锎A 將實施例3諏裂之塗料靜電塗裝於曰本試板工業股份有限公司製造之磷酸鋅處理板JIS G3141(SPCC-SD)PB 137T上。塗裝後再於各為200t：及2 20t：熱風烘箱中，進行燒烤60分鐘。以於180t!進行硬化30分鐘之塗板為基準，測量此塗板之色差（ΔΕ值）。（參照表5)此時所得塗板之 △E值於200 t；為0.73,於220t為2.9,相較於比較例3之 △ E值，顯示出更優越之耐黃變性。比較俐？經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 於以針式磨機（Alpine公司製）預粉碎之ER6610(商品名，日本酯股份有限公司製；終端羥基聚酯樹酯）548g中，加入TipUre-R902(商品名，日本杜邦股份有限公司製；二氧化鈦）331s、Kureram ϋΐ (住友拜耳尿烷股份有限公司製 ;基團封閉化異佛爾酮異氰酸酯）112g、二月桂基二丁基錫（東京化成股份有限公司製）1.98g、SeikolZ(商品名，精工社股份有限公司製；安息香）3.3U、Res〖flow-P67( 商品名，Estron化學公司製；丙烯酸聚合體）3.31g，以超级混合機Y-5 (河田股份有限公司製）預混合。接著•以關西锟製之2只LABORATORY MIL在前辊輪20rpm, 80T、後棍輪24rPn, UOt：的條件下混練該組成物。其後，用針式磨機（Alpine公司製）予以微粉碎，用140網目之篩網予以分级，作為粉體塗料。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 2〇_ 3 859 0 A7 B7 五、發明説明（19 ) 將此塗料靜電塗裝於日本試板工業股份有限公司製之磷酸鋅處理板 JIS G3141(SPCC-SD)PB 137T上，於 180ΊΟ 之熱風供箱中硬化30分鐘。塗膜性能示於表4。其機槭性能雖然優越，但於1個月後分子量（Mw)上升率為2.1 %,與實施例4之0 . 6 %相較，可判知習知者在儲存時反應進行得相當顯著。將實施例4製備的塗料靜電塗裝於日本試板工業股份有限公司製造的磷酸鋅處理板JIS G3141(SPCC-SD)PB 137T上。塗装後置於200 t：及2 20 ¾之熱風供箱中各供烤 60分鐘。以180°C、硬化30分鐘之塗板為基準、測量此等塗板之色差（AE值）。表5顯示該ΔΕ值在200C為1.7,在 220 10為4.1，與實施例4相較，在各溫度均嚴重變色。 (請先閱讀背面之注意事項再填寫本頁) *]· 訂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準（CNS ) A4規格（2丨0X297公釐） 21 3 8 590 五、發明説明（2〇 ) 表3 經濟部中央標隼局員工消費合作社印製實施例2 實施例3、4 比較例2 比較例3 ER6610 559 565 548 553 BPAC 108 - - - BBMC — 102 - - Kureram UI - - 112 113 二月桂酸二丁基錫 0.07 0.334 1.98 2.00 Tipure-R902 333 333 331 333 Seikol Z - - 3.31 - Resiflow - - 3.31 - (請先閱讀背面之注意事項再填寫本頁) 袭- 訂 k 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 22 38590Fenzhi A Electrostatically applied the cracked coating of Example 3 on a zinc phosphate treated board JIS G3141 (SPCC-SD) PB 137T manufactured by Japan Test Panel Industry Co., Ltd. After painting, grill in a 200t: and 2 20t: hot air oven for 60 minutes each. The color difference (ΔE value) of the coated plate was measured on the basis of a coated plate that was cured at 180 t! For 30 minutes. (Refer to Table 5) At this time, the ΔE value of the obtained coated plate was 200 t; it was 0.73 and 220 t was 2.9. Compared with the Δ E value of Comparative Example 3, it showed superior yellowing resistance. More slick? Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) ER6610 (trade name, manufactured by Japan Ester Co., Ltd.) pre-pulverized with a pin mill (manufactured by Alpine) To 548 g of hydroxypolyester resin), added TipUre-R902 (trade name, made by Japan DuPont Co., Ltd .; titanium dioxide) 331s, Kureram ϋΐ (made by Sumitomo Bayer Urethane Co., Ltd .; group-blocked isophorone isocyanate) 112g, dilauryl dibutyltin (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.98g, SeikolZ (trade name, manufactured by Seiko Co., Ltd .; benzoin) 3.3U, Res flow-P67 (trade name, manufactured by Estron Chemical Co., Ltd .; acrylic acid Polymer) 3.31 g, pre-mixed with Super Mixer Y-5 (manufactured by Kada Corporation). Next • Mix the composition with two LABORATORY MILs manufactured by Kansai under the conditions of 20rpm front roller, 80T, 24rPn rear roller, UOt :. Thereafter, it was finely pulverized with a pin mill (manufactured by Alpine Corporation) and classified with a 140-mesh sieve to obtain a powder coating. This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) 2〇_ 3 859 0 A7 B7 V. Description of the invention (19) This coating is electrostatically applied to zinc phosphate manufactured by Japan Test Plate Industry Co., Ltd. The treatment board is JIS G3141 (SPCC-SD) PB 137T and hardened in a hot air supply box at 180 ° C for 30 minutes. The coating film performance is shown in Table 4. Although its organic maple performance is superior, the increase rate of molecular weight (Mw) after one month is 2.1%, compared with 0.6% of Example 4, it can be judged that the reaction progressed significantly when the learner stored it. The coating material prepared in Example 4 was electrostatically coated on a zinc phosphate-treated plate JIS G3141 (SPCC-SD) PB 137T manufactured by Japan Test Plate Industry Co., Ltd. After painting, place them in a hot air supply box of 200 t: and 2 20 ¾ for 60 minutes each. Measure the color difference (AE value) of these coated plates based on 180 ° C and cured for 30 minutes. Table 5 shows that the ΔE value was 1.7 at 200C and 4.1 at 220 10, and compared with Example 4, the color was severely discolored at each temperature. (Please read the notes on the back before filling this page) *] · Order the paper size printed by the Employees Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs to apply the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 21 3 8 590 V. Description of the invention (20) Table 3 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 2 Examples 3 and 4 Comparative Example 2 Comparative Example 3 ER6610 559 565 548 553 BPAC 108---BBMC — 102-- Kureram UI--112 113 Dibutyltin dilaurate 0.07 0.334 1.98 2.00 Tipure-R902 333 333 331 333 Seikol Z--3.31-Resiflow--3.31-(Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 22 38590

7 7 A B 五、發明説明（21 ) 表4 經濟部中央標準局員工消費合作社印製實施例2 實施例3 比較例2 比較例3 烘烤條件 180t： 30分 180t： 30分 180t： 30分 180¾ 30分膠化分率 0.84 0.83 0.80 0.82 塗方格試驗 100/100 100/100 100/100 100/100 膜鉛筆硬度 Η Η Η Η 物埃力克森 8oim 8mm 8mni 8ώπι 性耐衝擊性 50cra 50cm 50cm 50cm 揮發量 0.5¾ 0.4¾ 2.1¾ 1.7% 塗料物性耐S黏性 - 〇 - 〇 Mw初期值 - 49,900 - 47,500 Mw —痼月後 - 50,200 - 49,400 Mw增加率 - 0.6 % - 1Λ% 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 23 38590 (請先閱讀背面之注意事項再填寫本頁) ""· 訂-- A · 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準（CNS ) A4規格（210X297公釐） 3 8 590 A7 B7 五、發明説明（22 ) 表5 實施例4 比較例3 l-Za-Zb- △ E值 LVaVb* △ E值基準值 91.21/-0.81/-3.32 - 93.82/-0.69/-2.10 - 200¾ 91.52/-0.46/-2.71 0.73 92.32/-0.68/-3.42 1.7 220°C 91.61/-0.54/-0.49 2.9 94.05/-1.15/1.33 4.7 奮掄例5 以表6之配方為準，於以針式磨機（Alpine公司製造）預粉碎的ER6610(商品名，日本酯股份有限公司製造，終端羥基聚酯樹脂）595g内，加人Tipure-R700(商品名，日本杜邦股份有限公司製造，二氣化鈦）333g,合成例2合成的BBMC[1，1-雙（3 -第三丁基-4-氡酸-6-甲基苯基酯）丁烷 72s,二丁基錫氣化物（東京化成股份有限公司製造]0.4g 、用超级混合機Y-5(河田股份有限公司製造）予以預混合。其次，用關西棍股份有限公司製造的二只棍輪 L A Β 0 R A Τ 0 R Υ Μ I L ,在前棍輪 2 0 r ρ in、8 0 t：、後觀輪 2 4 r ρ in、 1151之條件下混練此組成物，其後用針式磨機（Alpine公司製造）予以徹粉碎，採用140篩目之篩網分級成粉體塗料 24 ---------------w------' i (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 387006 a7 ___ B7 --- -:-：~： - 五 '發明説明（23 ) Ο 將此塗料靜電塗裝於日本試板工業股份有限公司製造的璘酸鋅處理板 JIS G3141(SPCC-SD)PB137T上，在 1801C 之熱風烘箱内硬化30分鐘。如表7所示般，硬化塗膜表面之基本物性良好。比-較期| 4 以表6之配方為準，於以針式磨機（/U P i n e公司製造）預粉碎的EP661〇(商品名，日本酯股份有限公司製造，終端羥基聚醱樹脂）559s内，加入Tipur*e-R902(商品名，曰本杜邦股份有限公司製造，二氣化鈦>333g，合成例1合成的以&(：(2,2-雙（4-氡酸苯基酷）丙烷>108^環烷酸鋅（ kishida化學股份有限公司製造），1.33g,用超级混合機卜5(河田股份有限公司製造）予以預混合。其次，用關西锟股份有限公司製造的二只棍輪LAB0RAT0RY MIL,在前辊輪2〇rpn, 80t：,後棍輪24「ρβ , 1 15 t：之條件下混練此組成物。其後用針式磨機（Alpine公司製造）予以徹粉碎，採用140篩目之篩網分级成粉醱塗料。此粉體塗料之膠凝時間偽與採用二月桂酸二丁基錫的情形時相同，而予以製備為3分鐘者。將此塗料靜電塗裝於日本試板工業股份有限公司製造的磷酸鋅處理板 J I S G 3 1 4 1 ( S P C C - S D > P B 1 3 7 T 上，在 1 8 0 t! 之熱風烘箱内硬化30分鐘。如表7所示，其硬化塗膜全未滿足基本物性。 (請先閱讀背面之注意事項再填寫本頁) 訂本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 25 38 59 0 A7 S870〇e B7 五、發明説明（24 ) 表6 經濟部中央樣準局員工消費合作社印製實施例5 比較例4 ER6610 595 559 BBMC 72 - BPAC - 108 二丁基錫氣化物 0.4 - 環烷酸鋅 - 1.33 Tipure-R700 333 - Tipure-R902 - 333 (請先閲讀背面之注意事項再填寫本頁) 袭- ^ ^ flit —nil· ^111 —In a^ln ff 、V5" 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 26 38 590 五、發明説明（25) 表7 經濟部中央標準局員工消費合作社印製實施例5 比較例4 烘烤條件 180Ό 30 分 180t 30 分不溶性謬凝分率 0.80 形成糊狀而不能測定方格試驗 100/100 57/100 鉛筆硬度 Η 4B 埃力克森 8mm 1 mia 耐衝擊性 50cbi 1 Ocin 揮發量 0.3¾ - 由本發明之粉體塗料而得的塗膜，於硬化時之環境衡生良好，表面具高度平滑、有高耐蝕性。本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 27 38 5 90 (請先閱讀背面之注意事項再填寫本頁)7 7 AB V. Description of the invention (21) Table 4 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 2 Example 3 Comparative Example 2 Comparative Example 3 Baking conditions 180t: 30 minutes 180t: 30 minutes 180t: 30 minutes 180¾ 30 points gelatinization ratio 0.84 0.83 0.80 0.82 coated square test 100/100 100/100 100/100 100/100 film pencil hardness Η Η Η Η Ericson 8oim 8mm 8mni 8 FREE and impact resistance 50cra 50cm 50cm 50cm volatile Amount 0.5¾ 0.4¾ 2.1¾ 1.7% Physical properties of coatings S-resistant-〇- 〇 Initial value of Mw-49,900-47,500 Mw —after the month-50,200-49,400 Mw increase rate-0.6%-1Λ% Standard (CNS) A4 specification (210X297 mm) 23 38590 (Please read the precautions on the back before filling out this page) " " · Order-A · Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Cooperatives, this paper is suitable for this paper China National Standard (CNS) A4 specification (210X297 mm) 3 8 590 A7 B7 V. Description of the invention (22) Table 5 Example 4 Comparative Example 3 l-Za-Zb- △ E value LVaVb * △ E value reference value 91.21 /-0.81/-3.32-93.82 / -0 .69 / -2.10-200¾ 91.52 / -0.46 / -2.71 0.73 92.32 / -0.68 / -3.42 1.7 220 ° C 91.61 / -0.54 / -0.49 2.9 94.05 / -1.15 / 1.33 4.7 Example 5 Formula according to Table 6 As standard, Tipure-R700 (trade name, Japan DuPont Co., Ltd.) was added to 595 g of ER6610 (trade name, manufactured by Japan Ester Co., Ltd., terminal hydroxy polyester resin) pre-pulverized with a pin mill (manufactured by Alpine). Co., Ltd., titanium digas) 333g, BBMC synthesized in Synthesis Example 2 [1,1-bis (3-Third-butyl-4-arsanoic acid-6-methylphenyl ester) butane 72s, dibutyltin Gasification (manufactured by Tokyo Kasei Co., Ltd.) 0.4 g, pre-mixed with a super mixer Y-5 (manufactured by Kawada Co., Ltd.). Second, two stick wheels LA Β 0 RA Τ manufactured by Kansai Stick Co., Ltd. 0 R Υ ΜIL, this composition is kneaded under the conditions of a front stick wheel 20 r ρ in, 8 0 t :, a rear view wheel 2 4 r ρ in, 1151, and then a pin mill (manufactured by Alpine Corporation) ) Thoroughly crushed and classified into powder coatings with a sieve of 140 mesh 24 --------------- w ------ 'i (Please read the precautions on the back first Fill in again Page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 387006 a7 ___ B7 ----:-: ~:-Five 'Invention Description (23) 〇 This coating was electrostatically applied to a product manufactured by Japan Test Plate Industry Co., Ltd. The zinc gallate treated plate was hardened in a hot air oven at 1801C on JIS G3141 (SPCC-SD) PB137T for 30 minutes. As shown in Table 7, the basic physical properties of the cured coating film surface were good. Than-Long Period | 4 Based on the formula in Table 6, based on a pin mill (manufactured by / UPine Co., Ltd.) pre-pulverized EP661〇 (trade name, manufactured by Japan Ester Co., Ltd., terminal hydroxypolyfluorene resin) 559s In addition, Tipur * e-R902 (trade name, manufactured by DuPont Co., Ltd., titanium dioxide> 333g, synthesized in Synthesis Example 1 with & (:( 2,2-bis (4-fluoric acid benzene Base) propane> 108 ^ zinc naphthenate (manufactured by Kishida Chemical Co., Ltd.), 1.33 g, pre-mixed with a super mixer # 5 (manufactured by Kawada Co., Ltd.). Second, manufactured by Kansai Sakai Co., Ltd. The two rollers LAB0RAT0RY MIL are kneaded under the conditions of front rollers 20rpn, 80t :, rear rollers 24 "ρβ, 1 15 t :. Then use a pin mill (manufactured by Alpine) It was pulverized thoroughly and classified into a powder coating with a sieve of 140 mesh. The gel time of this powder coating was the same as that when dibutyltin dilaurate was used, and it was prepared for 3 minutes. This coating was electrostatically charged. Coated on Zinc Phosphate Treatment Board J manufactured by Japan Test Plate Industry Co., Ltd. ISG 3 1 4 1 (SPCC-SD > PB 1 3 7 T, hardened in a hot air oven at 180 t! For 30 minutes. As shown in Table 7, the hardened coating film did not meet the basic physical properties. (Please Please read the notes on the back before filling in this page) The size of the paper used for this edition applies to the Chinese National Standard (CNS) A4 (210X297 mm) 25 38 59 0 A7 S870〇e B7 V. Description of the invention (24) Table 6 Central Ministry of Economic Affairs Printed in Example 5 by Consumer Cooperative Cooperative Example 5 Comparative Example 4 ER6610 595 559 BBMC 72-BPAC-108 Dibutyltin gaseous 0.4-Zinc naphthenate-1.33 Tipure-R700 333-Tipure-R902-333 (Please read the back first Please pay attention to this page and fill in this page again.)-^ ^ Flit —nil · ^ 111 —In a ^ ln ff, V5 " This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 26 38 590 V. Description of the invention (25) Table 7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics Example 5 Comparative Example 4 Baking conditions 180Ό 30 minutes 180t 30 minutes Insoluble coagulation rate 0.80 Forms a paste and cannot measure the square test 100/100 57/100 pencil hardness Η 4B eli Sen 8mm 1 mia impact resistance 50cbi 1 Ocin volatilization 0.3¾ - coating the powder coating film obtained by the present invention, when the raw value of the ambient cured well, highly smooth surface, high corrosion resistance. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 27 38 5 90 (Please read the precautions on the back before filling this page)

Claims

J87006 male%

88. 7 'Ιθ __j H3 Attachment Printed by the Employee Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs No. 85115946 Application for Proposal and Inspection of Profits _Public Amendment (July 19, 1988) A powder coating product made by K < A > A poly-tree tree having at least two Burmese free hydroxyl groups in the molecule and (B) M having two cyano groups in the molecule

0-C = N [In the formula, A shows an alkyl group with a carbon number of 1M or less, and two fluorene A may also be different from each other; X is a fluorene bond, an alkyl group with a carbon number of 1 to 20, 》 Basic or divalent suspicion or oxygen Kangzi; i is an integer value from 0M to 3M, the two i can also be different from each other, η indicates 0 or 1] multi-component organic cyanate ft and / Poly (fluorene) is the main component; in which (A) the molecular weight of the poly-resin having at least two free-living hydroxyl groups is more than 20igK0H / g above β0 · 8K0Η, and the number average molecular weight is 2000W to 50000W And the glass transition waterfall is above 40 * 0 and 100 tM; wherein the ratio of the cyanate group in the component (B) to the hydroxyl group in the component (A) is 0.7 to 3.0. 2. For example, if you apply for the powder coating material of the first item, the alkyl group (A) in the polyorganic cyanate group is located in the ortho position of the cyano group. The powder ff coating composition of item 1 or 2 of the application patent, wherein the polyorganic cyanate is 1,3-bis (3-third butyl-4-carboxylic acid-6-methylphenyl) Ii) Butane. This paper size applies to China National Standard (CNS) A4 (210 X 297, $ 38,590, J87006,%)

0-C = N [In the formula, A shows an alkyl group with a carbon number of 1M or less, and two fluorene A may also be different from each other; X is a fluorene bond, an alkyl group with a carbon number of 1 to 20, 》 Basic or divalent suspicion or oxygen Kangzi; i is an integer value from 0M to 3M, the two i can also be different from each other, η indicates 0 or 1] multi-component organic cyanate ft and / Poly (fluorene) is the main component; in which (A) the molecular weight of the poly-resin having at least two free-living hydroxyl groups is more than 20igK0H / g above β0 · 8K0Η, and the number average molecular weight is 2000W to 50000W And the glass transition waterfall is above 40 * 0 and 100 tM; wherein the ratio of the cyanate group in the component (B) to the hydroxyl group in the component (A) is 0.7 to 3.0. 2. For example, if you apply for the powder coating material of the first item, the alkyl group (A) in the polyorganic cyanate group is located in the ortho position of the cyano group. The powder ff coating composition of item 1 or 2 of the application patent, wherein the polyorganic cyanate is 1,3-bis (3-third butyl-4-carboxylic acid-6-methylphenyl) Ii) Butane. This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297, $ 38,590,387,006 printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs)