TW203088B - - Google Patents

Description

Λ 6 It 6 五、發明説明（l ) 本發明係關於粉末狀塗覆用組成物，亦稱為#末塗料 ，其代表性混合物為含環氣樹脂基之丙烯酸酯樹脂及各種 硬化劑。 7 5 2 7 8 7 0 9 1 9 3 2 9 9 1 0 4 4 以含有環氧里《旨§之丙烯酸酯共聚合物作為本質黏合 劑之粉末塗料已被熟知。彼等被描述於，例如以下之專利 • U S 3, 730, 930, US 3 US 3, 781, 379, US 3 US 4,091,049,US4 US 3, 939, 127, US 3 US 3, 991, 132, US 3 US 4, 092, 373, US 4 US 4,374,954 DE 2,353,040 ,D E 2,441 。二元酸類，彼等之酸酐類，或在硬化條件之下形成二元 酸之材料被使用硬化劑。根據EP 299, 420,硬 化劑亦可為一多元酸酐與多元醇之反應産物。 經濟部屮央標準局貝工消费合作社印製 請 先 閱 讀 背 而 之 >主 意 事 項 -ft· % 8 7 0 5 2 1 0 4 8 3 6 7 13 3 0 7 0 14 4 8 8 6 4 10 及 U S 4,3 4 6 D E 2,4 2 3, 753 及 DE 2,509, 描述於以上諸專利之共聚合物僅包含高達3 0%以重 量計之丙烯酸酯縮水甘油酯或甲基丙烯酸縮水甘油酯；共 聚合物之剩餘材料包括其他不飽和單體。此類型之多數化 合物以此類不飽和化合物為適合，尤其是包含苯乙烯及丙 烯酸酯，而未列為參考之特別適當之丙烯酸酯類為包含三 级-丁基。根據先前技蓊之實例在大多數場合中於硬化其 中所描述之粉末塗料時必須相當高之溫度（在140t：以 MA張尺度逍用中B國家«準(CNS)T4規格(210X297公;tt) 81. 2. 20,000 五、發明説明（2 )Λ 6 It 6 V. Description of the invention (l) The present invention relates to a composition for powder coating, also known as # last coating, and its representative mixture is an acrylate resin containing a ring gas resin group and various hardeners. 7 5 2 7 8 7 0 9 1 9 3 2 9 9 1 0 4 4 Powder coatings containing acrylate copolymers of epoxy resin "intent §" as intrinsic binders are well known. They are described in, for example, the following patents • US 3, 730, 930, US 3 US 3, 781, 379, US 3 US 4,091,049, US4 US 3, 939, 127, US 3 US 3, 991, 132, US 3 US 4, 092, 373, US 4 US 4,374,954 DE 2,353,040, DE 2,441. Dibasic acids, their anhydrides, or materials that form dibasic acids under hardening conditions are used as hardeners. According to EP 299, 420, the hardener may also be the reaction product of a polyanhydride and a polyhydric alcohol. Printed by the Beigong Consumer Cooperative of the Bureau of Standards of the Ministry of Economics, please read the opposite first> Ideas-ft ·% 8 7 0 5 2 1 0 4 8 3 6 7 13 3 0 7 0 14 4 8 8 6 4 10 And US 4,3 4 6 DE 2,4 2 3, 753 and DE 2,509, the copolymers described in the above patents only contain up to 30% by weight of glycidyl acrylate or glycidyl methacrylate ; The remaining material of the copolymer includes other unsaturated monomers. Most compounds of this type are suitable for such unsaturated compounds, especially containing styrene and acrylates, and particularly suitable acrylates not listed as references include tertiary-butyl. According to the example of the previous technology, in most occasions, when hardening the powder coating described in it, the temperature must be quite high (at 140t: at the MA sheet scale, the B National Standard (CNS) T4 specification (210X297 public; tt ) 81. 2. 20,000 V. Description of the invention (2)

Tk 先 閲 讀 背 之 注 意 事 項 % 上）。然而，於很多應用中，例如於木材及塑膠之成型或 當使用作為於汽車尾整之溫度一敏感性底靥塗層上之上層 塗層，其優點為粉末狀塗覆用組成物在最低可能之溫度， 例如低至1 201C被硬化。 本發明之目的係提供粉末塗料条統，其在溫度低至 12 ου甚至於觸媒不存在或在觸媒存在置有可能最少置 下硬化级提供塗料具有令人滿意之性質。令人驚訝地，若 ----------- ' .— ..._.... . - • ----- ... _____ 含有環氧樹脂基之丙烯酸酯共聚合物中包含（甲基）丙烯 酸三级一丁酯作為共單體，此目的可被達成。為何丙烯酸 酯共聚合物之反應性視（甲基）丙烯酸酯三鈒一丁酯而定 尚不清楚。雖然，如以上之解釋，大置之含環氣樹脂丙烯 酸酯粉末塗料已被描述，而此令人驚訝之效果則未被論及 本發明僳關於一種粉末狀塗覆用組成物，其傜包含 (A) —種包含縮水甘油基之共聚合物， (B) —種脂肪族或環脂肪族二元酸，其酸酐或以多元醇 改質之二元酸之酸酐， 經濟部中央楳準局貝工消费合作社印31 (C) 選擇性地顔料及其他添加物。 共聚合物（A)具有分子量（Μη) 1, 000 — 1 ◦，◦ 0 0及3 0 — 9 0 1C之玻璃轉移溫度且僳一混合 之聚合物，其包含 a)至少1 0%以重量計丙烯酸縮水甘油酯或甲基丙烯酸 縮水甘油酯， 本紙张尺度逡用中a «家楳準(CNS)甲4規格(21叫297公*> 81. 2. 20,000 ,030^« Λ 6 η 6 五、發明説明（3 ) b) 5—50%以重董計丙烯酸三级一丁酯或甲基丙烯酸 三级_ 丁酯， c) 20-60%以重量計之一種或多種脂肪族不飽和單 羧酸或二羧酸類之烷基酯類及 d) ◦—50%以重量計之一種或多種其他烯屬烴類不飽 和單醯。 共聚合物（A)具有以下之組成物： 請 先 閲 iti 背 而 之 >主 意 事 項 # 堪 % Λ 經濟部屮央標準局ISC工消费合作社印31 14-43% 1 5 - 3 5 炻 1 2 - 5 1 % 0 - 4 0 % 14-43% 2 0 - 4 0 ¾ 10-30¾ 0-36¾ 5 - 2 0 % 像較佳 以重量計甲基丙烯酸縮水甘油酯， 以重董計丙烯酸三级一丁酯或甲基丙烯酸 三级一 丁酯， 以重量計丙烯酸或甲基丙烯酸烷酯及 以重董計其他烯羼烴性不飽和化合物，而 具有以下組成物之共聚合物： 以重量計甲基丙烯酸縮水甘油醋， 以重量計苯乙烯， 以重量計之不飽和二羧酸之二烷基酯， 以重量計丙烯酸或甲基丙烯酸烷酯及 •以重置計丙烯酸三级一丁酯或甲基丙烯酸 三级一 丁酯。 適當之不飽和羧酸類之烷基酯類僳丙烯酸或甲基丙烯 % il 轉 81. 2. 20,000 本紙張尺度遑用+覼_家#率(CNS)T4規格(210 X 297公龙) -5 - Λ 6 Π6 五、發明説明（4 )Tk read the note item on the back first%). However, in many applications, such as the molding of wood and plastic or when used as a top coat on a temperature-sensitive bottom coating for automobile finishing, the advantage is that the powder coating composition is at the lowest possible The temperature, for example, as low as 1 201C is hardened. The object of the present invention is to provide a powder coating system which has a hardening level at a temperature as low as 12 ου even in the absence of a catalyst or in the presence of a catalyst where it is possible to provide the coating with satisfactory properties. Surprisingly, if ----------- '.— ..._.....-• ----- ... _____ copolymerization of acrylates containing epoxy resin groups It contains tertiary monobutyl (meth) acrylate as a comonomer, which can be achieved. It is unclear why the reactivity of the acrylate copolymer depends on the (meth) acrylate tris-butyl ester. Although, as explained above, Oji ’s ring-containing resin acrylate powder coatings have been described, and this surprising effect has not been discussed. The present invention relates to a powder coating composition, which contains (A)-a copolymer containing a glycidyl group, (B)-an aliphatic or cycloaliphatic dibasic acid, its anhydride or an anhydride of a dibasic acid modified with a polyol, Central Ministry of Economic Affairs Beigong Consumer Cooperative Printed 31 (C) Selective pigments and other additives. Copolymer (A) has a molecular weight (Μη) 1,000-1 ◦, ◦0 0 and 3 0-9 0 1C glass transition temperature and a mixed polymer, which contains a) at least 10% by weight Including glycidyl acrylate or glycidyl methacrylate, this paper is used in a «Household Standard (CNS) A 4 specification (21 called 297 Gong *> 81. 2. 20,000, 030 ^« Λ 6 η 6 V. Description of the invention (3) b) 5-50% by weight of tertiary monobutyl acrylate or tertiary methacrylate_butyl ester, c) 20-60% by weight of one or more aliphatic Alkyl esters of saturated monocarboxylic acids or dicarboxylic acids and d) ◦—50% by weight of one or more other ethylenic hydrocarbon unsaturated monoacids. Copolymer (A) has the following composition: Please read iti back to the top> Idea Matters # kan% Λ ISC Industrial and Consumer Cooperative Society of the Bureau of Standards, Ministry of Economic Affairs, 31 31-43% 1 5-3 5 炻 1 2-5 1% 0-4 0% 14-43% 2 0-4 0 ¾ 10-30¾ 0-36¾ 5-2 0% like preferably glycidyl methacrylate by weight, triacrylic acid by weight Grade one butyl ester or tertiary grade butyl methacrylate, acrylic acid or alkyl methacrylate by weight and other ethylenically unsaturated compounds by weight, and copolymers with the following composition: by weight Calcium glycidyl methacrylate, styrene by weight, dialkyl ester of unsaturated dicarboxylic acid by weight, acrylic acid or alkyl methacrylate by weight, and • tertiary butyl acrylic acid by replacement Ester or methacrylate tertiary monobutyl ester. Appropriate unsaturated carboxylic acid alkyl esters acrylic acid or methacrylic acid% il turn 81. 2. 20,000 This paper standard use + 覼 _ 家 # rate (CNS) T4 specifications (210 X 297 male dragon) -5 -Λ 6 Π6 5. Description of the invention (4)

Tk 先 閲 ih 背 而 之 注 意 事 項 再 酸酯類，其傈源自單氫醇類，彼等較佳為具有1一18個 硪原子，特別者彼等較佳為具有1-12個硪原子，諸如 甲基，乙基，η—丙烷基，異丙基，η—丁基，異丁基，二 级一丁基，η—戊基，η—己基，2 —乙基己基，η—辛基 ,η—壬基，異壬基，η—癸基，η--h二院基，η--h三院 經濟部中央標準局貝工消t合作社印製 基，異三癸基，十四烷基，十六烷基，硬脂基，二十烷基 及異茨基。之丙烯酸酯或甲基丙烯酸酯。其亦有可能使用 小量，即高達5%以重量計，之二氫或三氫醇之二丙烯酸 酯或二甲基丙烯酸，諸如二丙烯酸二己醇酯或二丙烯酸或 二甲基丙烯酸二丁酯或三丙烯酸或三甲基丙烯酸三甲醇基 酯。可選擇性使用以與丙烯酸酯類或甲基丙烯酸酯類混备 之其他單體為α,乃一不飽和二羧酸類，諸如順丁烯二或 反丁烯二酸類之酯類及飽合單氳醇類之酯類，例如順丁烯 二酸二甲酯，反丁烯二酸二乙酯，順丁烯二酸二丁酯，反 丁烯二酸二丁酯，等等。其他合適之共單體像丙烯醯胺或 甲基丙烯醯胺，苯乙烯，乙烯甲苯，ex —甲基苯乙烯，三 级一丁基苯乙烯，氯乙烯，丙烯腈，甲基丙烯腈，或醋酸 乙烯酯（組成份d )。 丙烯酸酯樹脂可藉熟知之聚合反應製法，諸如溶液， 乳化，真珠或總體聚合反應製得。特別較佳之丙烯酸酯樹 脂像彼等，例如，於EP 56, 971所描述之藉溶液 聚合反應或藉總體聚合反應所製備得。 本紙張尺度遑用中β 家«卒(CHS)T4規格(210X297&*) 81. 2. 20,000 Λ 6 It 6 五、發明説明（5 ) 先 閲 ΐΛ 背 而 之 >主 意 事 項 再 堪 % 丙烯酸酯樹脂具有30 — 901C之玻璃轉移溫度。較 佳之玻璃轉移溫度於範圍介於30 — 60*0。分子置（以 聚苯乙烯為標準之數目平均）一般而言僳1, 〇〇〇— 10, 000,較佳 Γ, 000 — 5, 000。 使用於本發明之脂肪族二元酸類以作為硬化劑者一組 成份（B)—僳，例如，己二酸，庚二酸，辛二酸，壬二 酸，皮酯酸，丙二酸，丁二酸，戊二酸，1， 12—十二 雙酸，等等。此等酸類之酸酐亦可被使用，例如戊二酸酐 及丁二酸酐和此等二羧酸類之多元酸酐類。此等多元酸酐 類像經由已述之脂肪族二元二羧酸類之分子間縮合反應而 獲得。實例僳己二酸（多元）酸酐，壬二（多元）酸酐， 皮酯（多元）酸酐，十二雙酸（多元）酸酐，等等。多元 酸酐具有分子量（以聚苯乙烯為檫準之重量平均數） 經濟部十央橾準局貝工消许合作社印製 1, 000—5, 000。多元酸酐亦可被用多元醇改質 ，如EP299, 420所述者。多元酸酐在室溫下僳固 體。多元酸酐之製備藉二羧酸類與醋酸酐在120— 20010溫度下反應進行之，較佳為1 20 — 1 70Ό。 於此反應中醋酸被分離開。醋酸之移除可藉在真空中之蒸 腺予以加速。 多元酸酐亦可被使用作為硬化劑以與脂肪族二元二羧 酸類混合或與具有溶點介於4010及1 50t：間之羥基羧 酸類混合，例如12 -羥基硬脂酸，2 —或3 —或10 — S1. 2. 20,000 本紙张尺度逍用中β Η家樣準(CNS)甲4規格(210X297公*) -7 - Λ 6 Μ 6 五、發明説明（6 ) 羥基硬脂酸，2—羥基十四酸，等等Tk first read the notes on the back of ih, and then the esters, which are derived from monohydrogen alcohols, they preferably have 1-18 atomic atoms, in particular they preferably have 1-12 atomic atoms , Such as methyl, ethyl, η-propanyl, isopropyl, η-butyl, isobutyl, secondary monobutyl, η-pentyl, η-hexyl, 2-ethylhexyl, η-octyl Base, η-nonyl, isononyl, η-decyl, η-h second-institution base, η-h third-industry Central Bureau of Economic Affairs Beigongxiaot cooperative printing base, isosindecyl, ten Tetraalkyl, hexadecyl, stearyl, eicosyl and isoyl. Acrylate or methacrylate. It is also possible to use small amounts, ie up to 5% by weight, of dihydrogen or trihydroalcohol diacrylate or dimethacrylic acid, such as dihexyl diacrylate or diacrylic acid or dibutyl dimethacrylate Ester or trimethacrylate or trimethacrylate. Other monomers mixed with acrylic esters or methacrylic esters can be selectively used as α, which is an unsaturated dicarboxylic acid, such as maleic or fumaric acid esters and saturated monomers. Ester alcohol esters, such as dimethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate, etc. Other suitable comonomers like acrylamide or methacrylamide, styrene, vinyltoluene, ex-methylstyrene, tertiary monobutylstyrene, vinyl chloride, acrylonitrile, methacrylonitrile, or Vinyl acetate (component d). Acrylic resins can be prepared by well-known polymerization methods, such as solution, emulsification, real beads or bulk polymerization. Particularly preferred acrylate resins are those prepared by solution polymerization or bulk polymerization as described in EP 56, 971, for example. The standard of this paper is not in the middle of the β family «Pawn (CHS) T4 specification (210X297 & *) 81. 2. 20,000 Λ 6 It 6 V. Description of the invention (5) First read ΛΛ Contrary to the above> The idea is worth more than acrylic acid The ester resin has a glass transition temperature of 30-901C. A better glass transition temperature is in the range of 30-60 * 0. The molecular weight (averaged by the number of polystyrene standards) is generally 10,000 to 10,000, preferably Γ, 5,000 to 5,000. Aliphatic dibasic acids used in the present invention as a set of ingredients (B)-as a hardener, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malonic acid, Succinic acid, glutaric acid, 1, 12-dodecanedioic acid, etc. Anhydrides of these acids can also be used, such as glutaric anhydride and succinic anhydride, and polyanhydrides of these dicarboxylic acids. These polybasic acid anhydrides are obtained by the intermolecular condensation reaction of the aliphatic dicarboxylic acids described above. Examples: Adipic acid (poly) anhydride, azelaic (poly) anhydride, hide ester (poly) anhydride, dodecanedioic acid (poly) anhydride, etc. Polyanhydride has a molecular weight (weight average with polystyrene as the standard weight). The Shiyang Central Bureau of Economics, Ministry of Economic Affairs, printed by the Beigongxu Cooperative Society 1,000-5,000. Polyanhydrides can also be modified with polyols, as described in EP 299,420. Polyanhydrides are solid at room temperature. The preparation of polybasic acid anhydride is carried out by reacting dicarboxylic acids and acetic anhydride at a temperature of 120-20010, preferably 1 20-1 70Ό. Acetic acid is separated in this reaction. The removal of acetic acid can be accelerated by steam glands in a vacuum. Polyanhydrides can also be used as hardeners for mixing with aliphatic dicarboxylic acids or with hydroxycarboxylic acids having a melting point between 4010 and 150t: for example 12-hydroxystearic acid, 2- or 3. —Or 10 — S1. 2. 20,000 copies of this paper are used in the beta β Η home sample standard (CNS) A 4 specifications (210X297 g *) -7-Λ 6 Μ 6 V. Description of the invention (6) hydroxystearic acid, 2-Hydroxytetradecanoic acid, etc.

Tk 先 閲 背 而 之 注 % % 項 再 酸酐及酸類之量，使用作為硬化劑-組成份Β —,以 丙烯酸酯樹脂為基準，可在一廣泛地範圍内改變且僳由在 丙烯酸酯樹脂内之環氧樹脂基之數目所決定。大致及言， 羧基或酸酐基之莫耳比被選定為〇. 4 — 1. 4: 1,較 佳 0 . 8 — 1 . 2 : 1 〇 粉末塗料可包含常用之顔料及缜料。此外，其亦可包 含一觸媒以增加交聯速率及降低硬化溫度。合適之觸媒像 四烷基銨或鐽鹽，眯唑，三级胺類，有機羧酸讀或磷化氫 之金羼鹽。然而，於大多數之場合觸媒存在為不必要。 經濟部屮央櫺準局员工消费合作社印^ 粉末塗料亦能夠另外包含各種添加物，諸如彼等在粉 末塗料中所慣例使用者，特別是脱氣劑，諸如安息香，一 般使用量為0.1—3%以重置計。另外，有可能使用癍 動控制劑，例如寡聚合性聚（甲基）丙烯酸酯，諸如聚（ 甲基）丙烯酸月桂酯，聚（甲基）丙烯酸丁酯，聚（甲基 )丙烯酸2 —乙基己酯或氟化聚合物或聚矽氣烷。為了改 良抗氣候性，熟知之紫外線吸收劑及抗氧化劑可被加入。 粉末塗料之組成份A, B及C首先被混合乾燥然後在 80—130C,較佳為80—100¾溫度下使用一雙 螺桿擠製機被擠製。在被冷卻並在混練機中粉碎之後，擠 81. 2. 20,000 本紙張尺;1逍用中國家樣毕（CNS)甲4規格(210X297公教) -8 - 五、發明説明（7 ) ih it 閲 讀 背 而 之 注 意 事 項 再 % 製物被磨成粉，目標作成20—90毫撖米之平均撖粒尺 寸，較佳為40 — 7 0毫撤米。任何存在之特大撤粒，可 藉篩子加以移除。 粉末塗料利用傳統之方法加以使用，例如利用靜電噴 覆或摩擦噴覆法。在塗覆之後硬化在1 20 — 200*0之 溫度進行，硬化溫度較佳為1 30— 1 60*0。 粉末塗料特別適合使用作為水溶液底層塗層之清澈塗 層。具有特別表面，光澤及抗化學藥品與抗氣候性之2 — 塗層成形品被獲得。 實例 含環氣樹脂基丙烯酸酯之製備 1.1樹脂1巳一10 經濟部屮央橾準局ΕΪ工消#合作杜印製Tk first read the notes of%% and then the amount of anhydride and acid, used as a hardener-component B-, based on acrylate resin, it can be changed in a wide range and it is made in acrylate resin Determined by the number of epoxy resin bases. Roughly speaking, the molar ratio of the carboxyl group or the acid anhydride group is selected to be 0.4 to 1.4: 1, preferably 0.8 to 1.2: 1. The powder coating may contain commonly used pigments and refining materials. In addition, it can also contain a catalyst to increase the cross-linking rate and lower the hardening temperature. Suitable catalysts are like tetraalkylammonium or ammonium salts, azoles, tertiary amines, organic carboxylic acids or phosphine gold salts. However, the presence of catalyst is unnecessary in most cases. Printed by the Employee Consumer Cooperative of the Ministry of Economic Affairs, Ministry of Economic Affairs ^ Powder coatings can also contain various additives, such as their conventional users in powder coatings, especially degassing agents, such as benzoin, generally used in amounts of 0.1-3 % Is reset. In addition, it is possible to use motion control agents such as oligopolymerizable poly (meth) acrylates, such as poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate 2-B Hexyl esters or fluorinated polymers or polysilanes. In order to improve weather resistance, well-known ultraviolet absorbers and antioxidants can be added. The components A, B and C of the powder coating are first mixed and dried and then extruded using a twin-screw extruder at a temperature of 80 to 130C, preferably 80 to 100¾. After being cooled and crushed in the kneading machine, squeeze 81. 2. 20,000 paper rulers; 1 use Chinese national sample (CNS) A 4 specifications (210X297 public teaching) -8-V. Invention description (7) ih it After reading the precautions, the product is ground into a powder, and the target is made into an average grain size of 20-90 millimetres, preferably 40-70 millimetres. Any extra large grains that exist can be removed by sieve. Powder coatings are used by traditional methods, such as electrostatic spraying or friction spraying. After coating, hardening is performed at a temperature of 1 20-200 * 0, and the hardening temperature is preferably 1 30-1 60 * 0. Powder coatings are particularly suitable for the use of clear coatings as primers for aqueous solutions. 2-Coated molded products with special surface, gloss, chemical resistance and weather resistance are obtained. Example Preparation of acrylate resin containing ring gas 1.1 Resin 1 巳 10 10 Ministry of Economic Affairs 屮 央 橾 准 局 ΕΪ 工 消 # Cooperation Du Printed

Solves so 100在氮氣中被加熱至150¾。然後 單體隨同起始劑之混合物在150¾下經7小時以均勻速 率被加入。在加入之後，反應混合物被保持在1 50*0經 另外2小時且然後 Solvesso 在150t：及正常壓力下 ,最後為1701C及18毫巴，被蒸餾出。一種固體，無 色之樹脂被獲得。配方及參數整理列於表1 (份以重量計 =pbw) ·· 本紙》尺度遑用中B B家榣準(CNS)甲4規格(210父297公龙> 81. 2. 20,000 6 6 ΛΠ 經濟部屮央櫺準扃β工消赀合作社印製 五、發明説明（8 ) 表1 1 a lb 1 c Id 1 e - Solvesso 10 0 15.00 pbw 15.00 pbw 15.00 pbw 15.00 pbw 15.00 pbw 甲基丙烯酸 31·64 " 31.64 M 31.64 " 31.64 " 31.64 " 縮水甘油酯 丙嫌酸t-丁麵 15.56 Η — 15.56 " — 7.78 H 甲基丙烯酸甲酯 12.80 " 12.80 " 32.80 32.80 " 32.80 H 苯乙烯 40.00 " 40.00 " 20.00 H 20.00 " 20.00 " 甲基丙稀，-丁繊 — 15.56 " — 15.56 " 7.78 H 二-三级丁基舰化物 1.50 ” 1.50 M 1.50 H 1·50 " 1.50 n 黏度（Ubbelohde, 於醋酸TB8之5 0% 360 290 190 300 230 niPa.s 溶液，2 01C sasffi® 54 47 45 41 42 *C MW 20,400 13.000 14,500 9,300 9.800 職樹臟5£ 500 495 500 480 480 35/莫耳 (請先間請背而之注意^項办吼寫{ 本紙51尺度边用中曲《家標準(CNS)甲4規格（210x297公龙) 81. 2. 20,000 宇 _ 10 _ 8 6 ο 3 ο -3 Λ 6 It 6 五、發明説明（9 ) 1 . 2 樹脂 2 a , 2 b 順丁烯二酸二異丙酯被預先加熱至1 7 5t：。然後單 饈隨同起始剤之混合物在1 5 0*C下經7小時以均勻速率 被加入。然後反應混合物被保持在此溫度經另外1小時且 然後揮發性組成份（起始劑之分解産物）在真空中（18 毫巴）被蒸皤出。一種固體，無色之樹脂被獲得。配方及 參數整理於表2 : 經濟部中央標準扁貝工消t合作社印91 表2 2 a 2 b 順丁烯二酸二一異丙基醏 22 · 00 pbw 22.00 pbw 甲基丙烯酸縮水甘油酯 28.50 " 28.50 " 甲基丙烯酸甲酯 5.00 " — 丙烯酸t-丁酯 ——— 5.00 苯乙烯 44.00 " 44.00 ·. 二-三级一丁基過氣化物 0.50 .. 0.50 " 黏度（板，圓錐體， 2.100 3，900 m Pa . s =1 0 0, 17010) 玻璃溫度 45 43 t： M w 6,600 19,000 環氣樹脂當量重 535 535 本紙張尺度遑用中國·家《準(CNS)T4規格(210x297公釐） 81. 2. 20,000 - 絲- -11 -Solves so 100 is heated to 150¾ in nitrogen. The monomer and initiator mixture were then added at a uniform rate over 150 hours over 7 hours. After the addition, the reaction mixture was kept at 150 * 0 for another 2 hours and then Solvesso was distilled off at 150t: and normal pressure, finally 1701C and 18 mbar. A solid, colorless resin was obtained. The formula and parameters are listed in Table 1 (parts by weight = pbw) · This paper is used in the standard BB family standard (CNS) A 4 specifications (210 father 297 male dragon> 81. 2. 20,000 6 6 ΛΠ Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs, Beta-Consumer Cooperative Society V. Description of Invention (8) Table 1 1 a lb 1 c Id 1 e-Solvesso 10 0 15.00 pbw 15.00 pbw 15.00 pbw 15.00 pbw 15.00 pbw methacrylic acid 31 64 " 31.64 M 31.64 " 31.64 " 31.64 " glycidyl propionate t-butyl noodles 15.56 Η — 15.56 " — 7.78 H methyl methacrylate 12.80 " 12.80 " 32.80 32.80 " 32.80 H Styrene 40.00 " 40.00 " 20.00 H 20.00 " 20.00 " Methyl Acrylate,-Ding Yi — 15.56 " — 15.56 " 7.78 H Two-tertiary butyl naphthate 1.50 ”1.50 M 1.50 H 1 · 50 " 1.50 n Viscosity (Ubbelohde, 5 0% of TB8 acetate 360 290 190 300 230 niPa.s solution, 2 01C sasffi® 54 47 45 41 42 * C MW 20,400 13.000 14,500 9,300 9.800 Professional tree dirty 5 £ 500 495 500 480 480 35 / mole (please pay attention to the back ^ item How to write {This paper 51-scale side song "Chinese Standard (CNS) A 4 specifications (210x297 male dragon) 81. 2. 20,000 _ 10 _ 8 6 ο 3 ο -3 Λ 6 It 6 V. Description of invention (9 ) 1.2 Resin 2 a, 2 b Diisopropyl maleate was pre-heated to 1 7 5t: Then the mono-conjugate with the starting mixture at 1 5 0 * C for 7 hours at a uniform rate Was added. The reaction mixture was then kept at this temperature for an additional hour and then the volatile components (decomposition products of the initiator) were distilled off in a vacuum (18 mbar). A solid, colorless resin was obtained 。Recipes and parameters are summarized in Table 2: Central Ministry of Economy, Ministry of Economy, Standard Shellfish Cooperative, Cooperative Society Print 91 Table 2 2 a 2 b Diisopropyl maleate 22 · 00 pbw 22.00 pbw Glycidyl methacrylate 28.50 " 28.50 " Methyl methacrylate 5.00 " — t-butyl acrylate —— 5.00 Styrene 44.00 " 44.00 ·. Two-three-level monobutyl pergasification 0.50 .. 0.50 " Viscosity ( Plate, cone, 2.100 3,900 m Pa. S = 1 0 0, 17010) Glass temperature 45 43 t: M w 6,60 0 19,000 Equivalent weight of the ring gas resin 535 535 This paper is based on the standard of China National Standard (CNS) T4 (210x297 mm) 81. 2. 20,000-Silk--11-

經濟部中央橾準局貝工消t合作社印31 五、發明説明（IQ 2.十二雙酸多元酸酐之製備 69.27 Pbw 十二雙酸與3 0. 7 3 pbw醋酸酐 被加熱至1 50¾。於此操作中醋酸藉蒸皤移除。在醋酸 不再被蒸餾出時，溫度被提高17〇t：且更多醋酸被蒸躕 出，首先在正常壓力下，然後於真空中。控制真空之方式 為僅讓醋酸蒸皤出而無醋酸酐蒸皤出。然後反應混合物被 保持在1701/20毫巴經另外3小時，然後冷卻。殘 留物具有841C之溶點。 3.粉末清漆塗料之製備及测試 737公克樹脂2a, 2b, 224公克十二雙酸多 元酸酐（或726公克樹脂la- le及27 1公克十二 雙酸多元酸酐）及3公克安息香首先被混合乾燥。然後此 混合物在80 — 1 201C下於一實驗室擠製機中在熔融態 下被分散。在冷卻與被置於先行之粉碎後，擠出物在吹製 機中被磨成5 0微米平均微粒尺寸之粉粒而形成一粉末塗 料。具有尺寸大於9 0撇米之微粒藉筛子移除。使用6 0 kv之靜電噴覆搶，粉末塗料被噴覆在去脂，漂白處理過 之鋼板上，以使在140Ό/30分鐘烘烤之後獲得60 微米膜厚。測試結果整理於表3 : (請先閲讀背而之注意事項/Η成寫'Printed by the Ministry of Economic Affairs, Central Bureau of Industry, Beigongxiao Cooperative Society 31 V. Description of the invention (IQ 2. Preparation of Dodecanedioic acid polyanhydride 69.27 Pbw Dodecanedioic acid and 3 0.7 3 pbw acetic anhydride were heated to 1 50¾. In this operation, the acetic acid is removed by steaming. When the acetic acid is no longer distilled, the temperature is increased by 170t: and more acetic acid is distilled off, first under normal pressure, then in a vacuum. Control the vacuum The method is to only distill out the acetic acid without distilling out the acetic anhydride. Then the reaction mixture is kept at 1701/20 mbar for another 3 hours and then cooled. The residue has a melting point of 841C. 3. Preparation of powder varnish paint And test 737 grams of resin 2a, 2b, 224 grams of dodecanedioic acid polyanhydride (or 726 grams of resin lale and 27 1 grams of dodecanedioic acid polyanhydride) and 3 grams of benzoin are first mixed and dried. Dispersed in a molten state in a laboratory extruder at 80-1 201C. After cooling and being crushed in advance, the extrudate is ground into a powder with an average particle size of 50 microns in the blower Particles to form a powder coating with a size greater than 9 The 0-millimeter particles are removed by a sieve. Use 60 kv of electrostatic spraying, powder coating is sprayed on the degreased and bleached steel plate to obtain a 60 micron film after baking at 140Ό / 30 minutes Thick. The test results are summarized in Table 3: (Please read the precautions first / Η 成 写 '

SL 絲. 本紙Λ尺度遑用中家«準(CNS>T4規格(210X29/公») 81. 2. 20,000 -12 - Λ 6 II 6 經濟部中央榣準局β工消你合作社印製 五、發明説明（11) 表3 la lb 1 c Id 1 e 2a 2b 膠化時間（I40t0 175 195 200 235 230 240 110秒 在 1401C 獅隨 (DIN 169 16aJ) 65 80 117 123 136 130 78縣 光澤度（6〇υ DIN 675 30) 103 107 106 108 107 102 107。 流出 極佳 極佳 極佳 極佳 極佳 極佳 極佳 Erichsen 凹痕測試 (DIN 53 156) 10.4 10.8 11.9 12.3 11.9 10.0 9.3齡 Cros shatch測試 (DIN 5 2 1 5 1) 0 0 0 0 0 0 0 耐讎測試 (ASTM D2 7 94 ； 反ώ) 160 80 160 20 80 20 160 i.p. α)稱量重：0.2公克；基質：腿_板；平放1分鐘, 驗在6 Οΐ：下傾斜 η 中 用 逍 度 w 81. 2. 20,000 (請先閲讀背而之注念^-項#-填寫' 裝. 線.· 13 k,030C8 經濟部中央梂準局貝工消t合作杜印製 五、發明説明（1¾含丙烯酸t一丁基酯之産物比較於無丙烯酸t-丁基酯 之樹脂呈現較大之反應性及較良好之耐衝擊凹痕測試。 本紙張尺度边用中BB家榣準(CNS)f4規格(210X297公; 81. 2. 20,000 -14 -SL silk. This paper is printed on the Λ standard using the standard «Zone (CNS > T4 specification (210X29 / Public»)) 81. 2. 20,000 -12-Λ 6 II 6 Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs β Gongxiaoyou Cooperative Description of the invention (11) Table 3 la lb 1 c Id 1 e 2a 2b gelation time (I40t0 175 195 200 235 230 240 110 seconds at 1401C lion (DIN 169 16aJ) 65 80 117 123 136 130 78 County gloss (6 〇υ DIN 675 30) 103 107 106 108 107 102 107. Outflow excellent excellent excellent excellent excellent excellent excellent excellent Erichsen dent test (DIN 53 156) 10.4 10.8 11.9 12.3 11.9 10.0 9.3 age Cross shatch test ( DIN 5 2 1 5 1) 0 0 0 0 0 0 0 0 test (ASTM D2 7 94; reverse) 160 80 160 20 80 20 160 ip α) Weighing: 0.2 g; substrate: leg_plate; flat Put it for 1 minute, and check it at 6 Ο 1: Downward tilt η, use Xiao w. 81. 2. 20,000 (please read the note ^ -item # -fill in first, install. Line. · 13 k, 030C8 Central Ministry of Economic Affairs Printed in cooperation with the Ministry of Industry and Commerce. 5. Description of the invention (1¾ The product containing t-butyl acrylate is more reactive and better than the resin without t-butyl acrylate. Good impact dent test. The paper is used in the BB home standard (CNS) f4 specification (210X297 male; 81. 2. 20,000 -14-

Claims (1)

知' 今’， A7 B7 C7 D7 六、申請專利範面 附件2 A : 第81101968號專利申請案 中文申請專利範圍修正本 民國82年1月修正 經消部屮央標準局貝工消背合作社印製 1. 一種粉末狀塗覆用組成物，其僳由以下組成： (A) 70 — 80%重之共聚合物，具有分子量 (Μη) 1, 000-10，000 及 30 — 90¾ 之玻 璃轉移溫度，且傺一混合之聚合物，其由以下組成： a) 25 — 35炻重之丙烯酸縮水甘油酯， b) 5—20%重之丙烯酸第三丁酯或甲基丙烯酸第三丁 酯， c) ◦一 35%重之丙烯酸C2_C4烷酯或甲基丙烯酸 C 2 - C 4烷酯， d) 0 — 25%重之順式丁烯二酸Cz-C 4烷酯或反式丁 烯二酸C ;一 C 4烷酯， e ) 2 0 — 5 ◦ %重之苯乙烯， f)◦一25%重之丙烯酸異冰片酯或甲基丙烯酸異冰Η 酯， (Β) 20—30%重之十二烷雙酸多元酸酐， (C )最多1 %重之二苯乙醇酮。 2. 如申請專利範圍第1項之塗覆用組成物，共聚合 物（Α)僳藉溶液或總體聚合反應製備得。 3. 如申請專利範圍第1項之塗覆用組成物，傜用以 産製塗料。 (請先ΚΙ讀背面之注意事項再填穽本页) 本紙張尺度適用中Η Β家標毕(CNS)甲4規格(210x297公#) 1 A7 B7 C7 D7 六、申請專利範圍 4.如申請專利範圍第1項之塗覆用組成物，俗作為 水性底塗層之清澈塗層。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 本紙張尺度適用中囷國家標準（CNS)甲4规格（210 X 297公处〉 81.9.10,000Knowing 'now', A7 B7 C7 D7 6. Attachment of the patent application profile 2 A: Amendment of the patent application in the Chinese Patent Application No. 81101968 Preparation 1. A composition for powder coating, whose composition consists of the following: (A) 70-80% by weight of a copolymer, having a glass transition with a molecular weight (Μη) of 1,000-10,000 and 30-90¾ Temperature, and a mixed polymer of Ye, which consists of the following: a) 25-35 stone weight glycidyl acrylate, b) 5-20% weight of third butyl acrylate or third butyl methacrylate, c) ◦A 35% by weight C2_C4 alkyl acrylate or C 2 -C 4 alkyl methacrylate, d) 0-25% by weight Cz-C 4 alkyl cis-crotonate or trans-butadiene Acid C; a C 4 alkyl ester, e) 2 0 — 5 ◦% by weight of styrene, f) ◦ 25% by weight of isobornyl acrylate or methacrylic acid isoborn Η ester, (Β) 20-30% Dodecanedioic acid polyanhydride, (C) up to 1% benzophenone. 2. For the coating composition of item 1 of the patent application, the copolymer (Α) is prepared by solution or bulk polymerization. 3. If the coating composition of item 1 of the patent application is applied, Tong is used to produce coatings. (Please read the precautions on the back first and then fill in this page.) The paper size is applicable to CN Β A Standard (CNS) A 4 specifications (210x297 public #) 1 A7 B7 C7 D7 6. Application for patent scope 4. If applying The coating composition of item 1 of the patent scope is commonly used as a clear coating of an aqueous base coat. (Please read the precautions on the back before filling out this page) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. This paper scale is applicable to the China National Standard (CNS) A 4 specifications (210 X 297 public office) 81.9.10,000 附件~' : 第81101968號申請案中文補充資料 民國82年1月呈 表1(鑲） 1 f 1 g Solvesso 100 15.00 pbw 15.00 pbw 甲基0嫌酸缩水甘令ώϋ 31.64 " 31.64 " 15.56 " 甲基丙締酸甲ρ 12.80 " 12.80 · 苯乙嫌 20.00 " 20.00 " 甲基丙嫌酸正丁醋 15.56 " 甲基丙輝酉饌冰片酉旨 20.00 " 20.00 " 二-第三丁基過雜匕物 • I 1.50 " 黏度OJbbe 1 ohde，方领昔酸丁 醋之50¾容·碑，20 °C) 200 mPa.s 180 mPa.s 玻璃 58 °C 53 °C Mw , 17,000 15,000 環氣樹月體a* 480 g/mol 480 g/mol 表3(續） 1 f 1 g 月翏化時間（140。〇 205 s 230 s 在140°C流動距離 (DIN 16916a)) 120 mm 128 mm 光澤韩0。，DIN 67530 105 % 106 % 流出. 極隹 極佳 凹痕L目JJ試 （DIN 53156) 10.7 mm 11.0 mm Crosshatch 測試DIN 52151 0 0 耐權潔測試0STM D 2794, 反 ιίπ 160 20Attachment ~ ': Chinese Supplementary Information for Application No. 81101968 submitted in January 1 of the Republic of China Form 1 (inlaid) 1 f 1 g Solvesso 100 15.00 pbw 15.00 pbw Methyl 0 acid shrinkage order 31.64 " 31.64 " 15.56 " Methacrylic acid methyl 12.80 " 12.80 · Phenyl ethyl 20.00 " 20.00 " Methyl propionic acid n-butyl vinegar 15.56 " Methyl propyl hydra You You borneol unitary purpose 20.00 " 20.00 " two- Tertiary butyl super dagger • I 1.50 " Viscosity OJbbe 1 ohde, 50% capacity of butyl vinegar with square collar oxalate, monument, 20 ° C) 200 mPa.s 180 mPa.s glass 58 ° C 53 ° C Mw , 17,000 15,000 Ambient tree lunar body a * 480 g / mol 480 g / mol Table 3 (continued) 1 f 1 g monthly decay time (140.205 s 230 s at 140 ° C flow distance (DIN 16916a)) 120 mm 128 mm gloss Han 0. , DIN 67530 105% 106% outflow. Polar clam very good Dent L mesh JJ test (DIN 53156) 10.7 mm 11.0 mm Crosshatch test DIN 52151 0 0 Resistance to cleanliness test 0STM D 2794, reverse ιίπ 160 20