200808847 九、發明說明： 【發明所屬之技術領域】 發明領域 本發明是關於一種用於一烷化胺基塑膠樹脂的製備方 5法，本發明再者是關於由根據本發明的方法得到的胺基塑 膠樹脂。此外’本發明是關於該等胺基塑膠樹脂的用途， 例如，作為在塗層組成物中的交聯劑。 【月υ 】 發明背景 10 胺基塑膠樹脂就其本身而論是已知的。已知的樹脂的 例子是六（甲氧曱基）三聚氰胺(ΗΜΜΜ)或六（丁氧甲基）三 聚氰胺(ΗΒΜΜ)。也已知的是使用ΗΜΜΜ或ΗΒΜΜ或此等 之混合物在諸如聚酯粉末塗層的塗層中作為交聯劑。可 是，有關ΗΜΜΜ及/或ΗΒΜΜ的用途的缺點是它們具有約 15 _60°C的一低的玻璃轉移溫度(Tg)。當ΗΜΜΜ及/或ΗΒΜΜ以 一有效的量（通常是一塗層組成物的1 〇wt%至20wt%)被使 用時，含有一ΗΜΜΜ或ΗΒΜΜ的粉末塗層組成物的1^被降 低至不希望的低的數值，常常在室溫以下。 【發明内容】 2〇 發明概要 本發明的目的是減少或甚至消除前面提到的缺點。 該目的是經由一胺基塑膠樹脂而被達到，胺基塑膠樹 脂是透過包含使如下組合並且反應的步驟的一方法而得到： •一C5-C3()醇；以及 200808847 •一個或多個選自如下構成之群組：一胺基塑膠樹脂， 一胺基和一醛之一混合物，以及由一製備的一烷化 胺基塑膠樹脂。 根據本發明的該等烧化胺基塑膠樹脂的一優點是它們 5具有比已知的烧化胺基塑膠樹脂一較高的Tg，而仍提供允 許該烷化胺基塑膠樹脂被用於已知的方法中的官能基，例 如作為交聯劑。 本發明是關於一種用於製備一烷化胺基塑膠樹脂的方 法。術語樹脂是指每個分子具有至少兩個反應性基團的低 10分子量募聚物。一樹脂的分子量通常符合從約200至約 6,000或更多的一寬廣的範圍。應注意的是像hmmM或 HBMM的產品是相對小的但是仍屬於如本文所使用的術語 的範圍’儘管它們不總在文獻中以這種方式被提及。在一 树脂中該等反應性基團的存在是重要的，是因為這些反應 15性基團經由一化學反應透過共價交聯鍵形成一些化學手柄 來使寡聚的或聚合物鏈連接到一起。交聯方法也是指“固 化”或“硬化”。 如在本發明中被製備的該等樹脂是胺基塑膠樹脂。胺 基塑膠樹脂就其本身而論是已知的，它們被理解為是由包 20含一胺基化合物(也就是具有至少一-NH或-NH2基團的一化 合物，或者胺基化合物域一醛或醛之混合物的混合物）的原 料製備的樹脂。在胺基塑膠樹脂的製備中使用最廣泛的胺 基化合物是尿素及/或三聚氰胺。通常在一胺基塑膠中，與 該駿反應的該等化合物的大部分是胺基化合物。可是與該 6 200808847 β 5 • 越反應的其他化合物也可存在，這樣的一化合物的例子是 酚。在胺基塑膠樹脂的製備中一通常被使用的醛是甲醛。 在本發明的正文中，術語甲醛也包含能釋放曱醛的化合 物，諸如三聚甲醛和三噚汕。在本發明的方法中可被用作 原料的醛的其他例子包括丙醛、苯甲醛和烷醇半縮醛；烷 醇半縮醛的例子包括甲基乙醛酸甲醇半縮醛（GMHA™， DSM Fine Chemicals，Linz)和乙基乙酸酸乙醇半縮酸 (GMHATM，DSM Fine Chemicals，Linz) 〇 在本發明中，該等胺基塑膠樹脂是烷化的。術語烷化 10 胺基塑膠樹脂是指可透過使用一醇改質在一胺基塑膠樹脂 中的至少部分胺基-醛鍵而得到的樹脂。一烷化胺基塑膠樹 脂的一已知的例子是HMMM ;在HMMM中，該醇是甲醇。 根據本發明的方法包含使原料組合並且確保它們反應 的步驟。 -15 該等原料包含根據本發明的一 c5-c3O醇。這樣的醇就其 • 20 本身而論是已知的。該等醇的例子包括戊醇、己醇、環己 醇、四氫糠醇(THFA)和硬脂醇。術語CVCso醇在本文可指 各種CVCm醇的一混合物。較佳地，在c5-C3〇醇中的羥基是 脂肪族基團或被連接到一環烷基基團；發現使用烯丙（不飽 和的）醇可導致不希望的副作用，諸如變色。較佳地，該 醇不包含一芳香族環；在羥基-芳香族化合物中的 -OH基團被發現可能不具有建立烷化反應的充分反應性；更 佳地，該(^-(^醇不是盼。該cvc^醇較佳地是—單羥基 醇；發現使用單羥基醇製備的烷化胺基塑膠樹脂的穩定性 7 200808847 高於使用多經基醇(諸如二醇）製備的烷化胺基塑膠樹脂的 穩定性。穩定性在本文中被定性定義為該烷化胺基塑膠樹 脂經過自反應的趨勢，可見的如自發的膠形成。 根據本發明特別較佳的是該C5-C3G醇是環己醇或THFA 5或此等之一混合物。發現使用THFA作為該C5-C30醇（部分） 能導致一烧化胺基塑膠樹脂具有一非常有利的性質之組 合；一種這樣的性質是對水性系統或有機溶劑的一增加的 親和性，藉此與使用其他醇製備的烷化胺基塑膠樹脂比較 可得到在水中或有機溶劑中的一較高的溶解度，或至少具 10有一降低的需求對於為了增加溶解度而實施特別的測量， 諸如酸化。 在根據本發明的方法中被組合的該等原料還包含一個 或多個選自如下之群組： •一胺基化合物和一盤之一混合物； 15 •一胺基塑膠樹脂；以及 •由一 Cl_C4醇製備的一烧化胺基塑膠樹脂。 這個群組的三個部分的每一個的一選擇表示了本發明 的一主要具體例，其中要注意的是該等主要具體例可彼此 組合。 20 在本發明的一第一主要具體例中，與該C5-C4組合的 該等原料包含-胺基化合物和一駿之一混合物；藉此一反 應混合物被形成。該胺基化合物和該酸因此本質上就其本 身而論被帶入該反應混合物内，也就是沒有在一胺基塑膠 樹脂内反應。在這個第-主要具體例中，因此，該胺基塑 200808847 膠樹脂的形成以及通常接下來該炫化胺基塑膠樹脂的形成 可在相同的反應空間内發生。 該反應混合物的形成在這個第一主要具體例中被稱為 步驟a)。當在步驟幻形成該反應混合物時，不但該胺基化合 5 物和該醛被組合，而且一C5_C3O醇和選擇性地一溶劑也被組 合。較佳地，該胺基化合物包含三聚氰胺或甚至本質上是 由三聚氰胺構成。更佳的是該醛包含甲醛或甚至本質上是 由甲醛構成。 該等術語“本質上由…構成”、“本質上組成全部，，或均 10 等物具有普通的含義，沒有出現或使用別的對本發明的操 作、作用或達到的目的具有相當大的影響的化合物或測量。 較佳的是在步驟a)中確保該等反應物之間的莫爾比例 保持在一定限度内。 在該醛(D)和該胺基化合物(A)之間的莫爾比例較佳地 15 是在一定限度内。因為該醛通常會與該胺基化合物的一_NH 官能基反應，並且因為較佳地被用於根據本發明的方法中 的該等胺基化合物（諸如三聚氰胺或尿素）通常包含多個 -NH及/或NH2官能基，較佳的是依據每-Nh2官能基的駿分 子的量來表示在D和A之間的莫爾比例。此外，僅僅由於實 20際原因並且考慮到作為胺基化合物的三聚氰胺的較佳位 置，較佳的是考慮每三個-NH2基團的一醛化合物的比例。 該因此定義的D/(NH2)3比例是根據本發明較佳地至少是 3，這樣具有的優點是大體上每一個-NH2官能基與一駿分子 反應’精此一充分複合的樹脂發展可發生。該D/(njj2)3比 9 200808847 例根據本發明較佳地至多是7 ;這樣具有的優點是本質上全 一 -NH g此基能與一酸分子反應，运樣最終導致在該終產物 中最高可能性的烧化程度。 同樣在該C5-C3〇醇(L)和該胺基化合物(A)之間的莫爾 5 比例較佳地是在一定限度内。如前面所給出的該等相同的 原因，較佳的是考慮在一醇和三個·ΝΗ2基團之間的莫爾比 例，該L/(NH2)3比例。該l/(NH2)3比例較佳地至少是i。這 樣具有的優點是一最小充分的烧化程度能發生。在很多情 況中，有利的是不但在作為反應物的c5-c30醇的功能中而且 10在作為一溶劑的作用中使用它；因此有利的是確保在該反 應混合物中L/(NH2)3比例具有高於6的該化學計量最大值的 數值，諸如20、15或10。然而，例如在該醇沒有必要來作 為溶劑例子中，有利的是使該L/(NH2)3比例至多限定至8， 更佳地至少是4 ;這樣具有的優點是依據本發明方法的實 15現，避免了在該反應混合物中的一高的量的殘餘醇。此外， 較佳地，該L/(NH2)3比例是在1.5至3之間。 此外較佳的是當考慮給出的有關上面顯示的莫爾 D/(NH2)3和L/(NH2)3的方針，該莫爾d/L比例可在0.25至5之 間變化；藉此注意的是低於1的一D/L的數值主要在該醇(L) 20被用作溶解和用作反應物的情況中是有利的；除此以外， D/L的數值較佳地至少是1，較佳地至少是15 ;該莫爾d/l 比例較佳地至多是4或3。 如上面給出的該等莫爾比例D/(NH2)3、L/(NH2)3和D/L 的較佳範圍適用於該等原料，是因為它們被組合，它們也 200808847 原則上適用於該燒化胺基塑膠樹脂的較佳範圍，除了過量 的比例(諸如一 D/(NH2)3比例是在6之上，一 l/(NH2)3比例是 在6之上或一D/L比例是在1之下）是不可應用以外。當參照 該烷化胺基塑膠樹脂時，該等比例應與歸因於該等單獨的 5原料的该烷化胺基塑膠樹脂的結構要素有關（也就是，D、 L、A或挪）。 在根據本發明的步驟a)中的該反應混合物的形成中， 正如所瞭解的，有利的是加入一溶劑；較佳的溶劑是C5_c% 醇或水。 1〇 忒反應混合物在根據本發明的第一主要具體例中的步 驟b)中被调節到在1至7之間的一pH。發現該烷化胺基塑膠 樹脂的形成以及尤其是該烷化次步驟（其中該醇被併入該 胺基塑膠樹脂中）在酸性條件下進行的最好；較佳地，該反 應混合物被調節到2至6之間或3至5之間的—pH。如果該反 15應混合物的pH在其形成時不在所欲的範圍β，那麼它應透 過热悉技術之人士瞭解的方式被帶入，例如，透過加入— Brostedt酸(諸如硫酸或甲酸）或一鹼。較佳地，該pH被保持 在貫穿步驟b)和c)的該範圍内。 為了使該反應步驟有效地發生，該反應混合物不但應 20被調節到-定的pH範圍内，而且應被調節到一定的溫度範 圍内。根據本發明的該第_主要具體例包含一步驟c)，其 中該反應混合物被調節到位於8〇〇c至i 3〇〇c之間的_溫 度。步驟〇的完成會通常使該反應混合物的-加熱成為必 要。種加熱可透過就其本身而論已知的方式而被得到， 11 200808847 諸如一熱交換器。 一旦該反應混合物被調節到該溫度範圍内，該烷化胺 基塑膠樹脂的形成可發生。為使其發生，該反應混合物在 該溫度範圍内應保持持續一所欲的時間量。必需的時間量 5會取決於就其本身而論是熟悉技術之人士所瞭解的因素。 本文中重要的因素是該實際溫度、該實際？11和該烷化胺基 塑膠樹脂的所欲的成分。正如所瞭解的，該實際溫度的影 響是一溫度的增加，該溫度的增加會導致為達到所欲結果 所需的時間縮短。正如所瞭解的，該實際pH的影響是該pH 10的一降低，該PH的降低會導致為達到所欲結果所需的時間 縮短。然而，一太低的pH，諸如低於丨的一pH，不是太有 利的，因為發現於是不希望的副反應（諸如一胺基化合物的 一-NH官能基的去質子化或自發自縮合導致的膠形成）可提 升或可增加至充分大的位準；此外，一非常低的pH在被進 15行的步驟d)的情況中（在下面會詳細討論)是不利的，因為一 非常鬲的ϊ的驗必須繼而被加入。同樣進行步驟幻的所需 的時間的影響是該烷化胺基塑膠樹脂的所欲的成分：所欲 的該烧化胺基塑膠樹脂的分子量越高，步驟c)需要被完成 的就越長。在實際中，這可指完成步驟幻所需的時間長度 20可在寬廣的範圍限度内改變，例如在5或1〇分鐘與18〇或甚 至240分鐘之間。完成步驟c)所需的實際最佳時間可簡單地 經由常規的實驗被測量，其中如上所確定的諸如溫度和pH 的該等因素可被改變並且其中該烷化胺基塑膠樹脂的發展 是經由在固定間隔下提取樣品並且透過測試的方式分析被 12 200808847 監視的’运些測试就其本身而論是已知的’諸如（但不限制 在)濁點測量、耐水測量、紅外線分析、NMR分析。 在本發明的該第一主要具體例中，步驟a)、1^和幻可按 順序被完成或它們可被同時完成。 5 當元成步驟c)時，希望的是停止該反應及/或分離出所 形成的該烷化胺基塑膠樹脂。這可透過實施該等較佳步驟 d)和同樣可能地e)和f)而被達到。在步驟幻中，該反應混合 物的pH被調節至位於9至13之間的一數值。這可透過就其本 身而論已知的方式而被得到，諸如透過加入一驗，像(水性) 10氫氧化納。該PH增加的最重要的影響是該烷化胺基塑膠樹 脂的形成或進一步形成是被有效地停頓下來。現在可能的 是使用該烷化胺基塑膠樹脂；可是，也希望的是從未反應 的原料中分離出該烷化胺基塑膠樹脂，尤其是該c5_C3〇醇。 在這種情況中，較佳的是使在一步驟幻中的該反應混合物 15的溫度調節至諸如該醇的這些揮發性被蒸發的一數 值，然後是一步驟〇，其中本質上全部揮發性組分(諸如該 C5-C3〇醇)被蒸發並且該烷化胺基塑膠因此被回收。對於該 反應混合物在步驟e)中產生的溫度較佳地是在常壓下該 醇的沸點。為了促進該醇的蒸發及/或避免該烷化胺 20基塑膠樹脂的分解，必要有利的在真空中操作步驟f)。揮發 性組分被定義為經由加熱及/或蒸餾及/或暴露於真空，沒有 士致相^大的该炫化胺基塑膠樹脂的分解，從該烧化胺基 塑膠樹脂中分離的那些化合物。 在本發明的一第二主要具體例中，一反應系統被形 13 200808847 成，首先該系統不包含該(^七如醇。然而，一烷化胺基塑膠 樹脂首先被形成’然後接下來是一烷化步驟。本發明的該 第二主要具體例因此包含如下步驟： L使一胺基化合物（較佳地包含三聚氰胺)與一醛以及 5 選擇性地一溶劑組合而形成一反應系統； ii·使該反應系統的pH調節到7至1〇之間； iii.使该反應糸統的溫度調節到6〇°c至回流之間並且允 許该反應系統在该溫度範圍内保持持續一所欲的時間量， 藉此一胺基塑膠樹脂被形成； 10 lv•使該反應系統的PH調節到1至7之間，並且向該反廡 糸統加入一 C5-C30醇； ν·允許該反應系統在7(TC至回流的溫度範圍内保留持 續一所欲的時間量，藉此該烷化胺基塑膠樹脂被形成。 儘管考慮到本具體例的該等特徵，步驟(i)至(iii)是就其 15本身而論在胺基塑膠樹脂的製備的方法中已知的步驟，並 且了根據傳統的工業插作而被進行。這些術語的解釋是根 據前面的主要具體例，除非以其他方式被注明。 在步驟⑴中，一胺基化合物和該醛被帶入就其本身而 論本質上的該反應混合物内，也就是，不在一胺基塑膠樹 2〇脂内反應。該胺基化合物較佳地包含三聚氰胺，或甚至本 質上是由三聚氰胺構成。如被使用的該醛可包含甲醛，並 且較隹地本質上是由甲醛構成。可是，也可能的是使用另 種駿’諸如在這個描述中前面提到的該等酸之一。同樣 在這個第二主要具體例中，該D/(1S[H2)3比例較佳地至少是3 14 200808847 並且較佳地至多是7。在步驟(i)中該溶馳佳地是水。200808847 IX. OBJECTS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a process for the preparation of an alkylated amine-based plastic resin, and the invention further relates to an amine obtained by the process according to the invention. Based on plastic resin. Further, the present invention relates to the use of such amine-based plastic resins, for example, as a crosslinking agent in a coating composition. [月υ] Background of the Invention 10 Amine-based plastic resins are known per se. An example of a known resin is hexakis(meth) melamine (ruthenium) or hexakis(butoxymethyl) melamine (ruthenium). It is also known to use ruthenium or osmium or a mixture of these as a crosslinking agent in a coating such as a polyester powder coating. However, a disadvantage with regard to the use of bismuth and/or bismuth is that they have a low glass transition temperature (Tg) of about 15 _60 °C. When ruthenium and/or ruthenium is used in an effective amount (usually from 1 〇 wt% to 20 wt% of a coating composition), the composition of the powder coating composition containing a ruthenium or osmium is reduced to no The low value desired is often below room temperature. SUMMARY OF THE INVENTION 2〇 SUMMARY OF THE INVENTION It is an object of the present invention to reduce or even eliminate the aforementioned disadvantages. The object is achieved by an amine-based plastic resin obtained by a process comprising the steps of combining and reacting as follows: • a C5-C3 () alcohol; and 200808847 • one or more choices From the group consisting of an amine-based plastic resin, a mixture of an amine group and an aldehyde, and an alkylated amine-based plastic resin prepared by one. An advantage of the burnt-off amine-based plastic resins according to the present invention is that they have a higher Tg than known burnt amine-based plastic resins, while still providing the alkylated amine-based plastic resin to be used for known purposes. The functional group in the process, for example as a crosslinking agent. This invention relates to a process for preparing an alkylated amine based plastic resin. The term resin refers to a low 10 molecular weight polymer having at least two reactive groups per molecule. The molecular weight of a resin generally conforms to a broad range from about 200 to about 6,000 or more. It should be noted that products like hmmM or HBMM are relatively small but still fall within the scope of the term as used herein, although they are not always mentioned in this manner in the literature. The presence of such reactive groups in a resin is important because these reactive 15-groups form a chemical handle through a chemical reaction through covalent crosslinks to link the oligomeric or polymer chains together. . The crosslinking method also means "curing" or "hardening". The resins as prepared in the present invention are amine based plastic resins. Amine-based plastic resins are known per se, and they are understood to consist of a compound containing an amine compound (i.e., a compound having at least one -NH or -NH2 group, or an amine compound domain). A resin prepared from a raw material of a mixture of aldehydes or aldehydes. The most widely used amine compounds in the preparation of amine based plastic resins are urea and/or melamine. Typically, in an amine based plastic, most of the compounds reacted with the amine are amine based compounds. However, other compounds which are more reactive with the 6 200808847 β 5 • may also be present, and an example of such a compound is phenol. One commonly used aldehyde in the preparation of amine based plastic resins is formaldehyde. In the context of the present invention, the term formaldehyde also encompasses compounds which release furfural, such as trioxane and triterpene. Other examples of aldehydes which can be used as starting materials in the process of the present invention include propionaldehyde, benzaldehyde and alkanol hemiacetals; examples of alkanol hemiacetals include methylglyoxylic acid hemiacetal (GMHATM, DSM Fine Chemicals, Linz) and ethyl acetic acid ethanol hemi-succinic acid (GMHATM, DSM Fine Chemicals, Linz) In the present invention, the amine-based plastic resins are alkylated. The term alkylation 10 Amine-based plastic resin means a resin obtainable by modifying at least a part of an amine-aldehyde bond in an amine-based plastic resin using an alcohol. A known example of an alkylated amine based plastic resin is HMMM; in HMMM, the alcohol is methanol. The method according to the invention comprises the step of combining the starting materials and ensuring their reaction. -15 These materials comprise a c5-c3O alcohol according to the invention. Such alcohols are known in their entirety. Examples of such alcohols include pentanol, hexanol, cyclohexanol, tetrahydrofurfuryl alcohol (THFA), and stearyl alcohol. The term CVCso alcohol may be referred to herein as a mixture of various CVCm alcohols. Preferably, the hydroxyl group in the c5-C3 sterol is an aliphatic group or is attached to a cycloalkyl group; it has been found that the use of an allylic (unsaturated) alcohol can cause undesirable side effects such as discoloration. Preferably, the alcohol does not contain an aromatic ring; the -OH group in the hydroxy-aromatic compound is found to have insufficient reactivity to establish an alkylation reaction; more preferably, the (^-() alcohol It is not desirable. The cvc^ alcohol is preferably a monohydric alcohol; the stability of an alkylated amine-based plastic resin prepared using a monohydric alcohol is found to be higher than the alkylation prepared using a polyhydric alcohol such as a diol. Stability of the amine-based plastic resin. Stability is defined herein as the tendency of the alkylated amine-based plastic resin to undergo self-reaction, such as spontaneous gel formation. The C5-C3G is particularly preferred in accordance with the present invention. The alcohol is cyclohexanol or THFA 5 or a mixture of these. It has been found that the use of THFA as the C5-C30 alcohol (partially) can result in a combination of a very advantageous property of the burnt amine-based plastic resin; one such property is An increased affinity of an aqueous system or an organic solvent whereby a higher solubility in water or an organic solvent can be obtained compared to an alkylated amine-based plastic resin prepared using other alcohols, or at least 10 has a reduced demand for Special measures are carried out to increase the solubility, such as acidification. The materials which are combined in the process according to the invention further comprise one or more groups selected from the group consisting of: • a mixture of an amine compound and a disk; 15 • an amine-based plastic resin; and • an aromatized amine-based plastic resin prepared from a Cl_C4 alcohol. A selection of each of the three portions of the group represents a major embodiment of the invention, wherein It is such a main specific example that they can be combined with each other. 20 In a first main embodiment of the present invention, the raw materials combined with the C5-C4 comprise a mixture of an amine compound and a precursor; thereby a reaction mixture The amine-based compound and the acid are thus introduced into the reaction mixture intrinsically, that is, without reacting in an amine-based plastic resin. In this first-principle specific example, therefore, The formation of the amine-based plastic 200808847 resin and, in general, the formation of the sclerosing amine-based plastic resin can occur in the same reaction space. The formation of the reaction mixture is in this A main specific example is referred to as step a). When the reaction mixture is formed in the step, not only the amino compound and the aldehyde are combined, but also a C5_C3O alcohol and optionally a solvent are combined. Preferably, the amine compound comprises melamine or even consists essentially of melamine. More preferably, the aldehyde comprises formaldehyde or even consists essentially of formaldehyde. The terms "consisting essentially of" and "essentially consisting entirely of , or all of them have the ordinary meaning, and no other compounds or measurements that have a considerable influence on the operation, action or purpose of the present invention are present or used. It is preferred to ensure these in step a). The molar ratio between the reactants is kept within a certain limit. The molar ratio between the aldehyde (D) and the amine compound (A) is preferably 15 within a certain limit. Since the aldehyde typically reacts with a -NH functional group of the amine compound, and because the amine compounds (such as melamine or urea) which are preferably used in the process according to the invention typically comprise a plurality of -NH And/or the NH2 functional group, preferably the molar ratio between D and A is expressed in terms of the amount of the molecule per -Nh2 functional group. Further, it is preferable to consider the ratio of the monoaldehyde compound per three -NH 2 groups, merely for practical reasons and considering the preferred position of the melamine as the amine compound. The thus defined D/(NH2)3 ratio is preferably at least 3 according to the invention, which has the advantage that substantially every -NH2 functional group reacts with a precursor molecule. occur. The D/(njj2)3 to 9 200808847 is preferably at most 7 according to the invention; this has the advantage that essentially all-NH g can react with an acid molecule, which ultimately leads to the end product. The highest degree of burning in the middle. Also, the molar ratio of the C5-C3 sterol (L) and the amine compound (A) is preferably within a certain limit. For the same reasons as given above, it is preferred to consider the molar ratio between an alcohol and a tris(R) group, the L/(NH2)3 ratio. The l/(NH2)3 ratio is preferably at least i. This has the advantage that a minimum sufficient degree of burnout can occur. In many cases, it is advantageous to use it not only in the function of the c5-c30 alcohol as a reactant but also in the action as a solvent; it is therefore advantageous to ensure the ratio of L/(NH2)3 in the reaction mixture. A value having a stoichiometric maximum above 6, such as 20, 15, or 10. However, for example, in the case where the alcohol is not necessary as a solvent, it is advantageous to make the L/(NH2)3 ratio at most limited to 8, more preferably at least 4; this has the advantage that the method according to the invention is 15 Now, a high amount of residual alcohol in the reaction mixture is avoided. Further, preferably, the L/(NH2)3 ratio is between 1.5 and 3. Further preferably, when considering the given guidelines regarding Mohr D/(NH2)3 and L/(NH2)3 shown above, the Moir d/L ratio may vary between 0.25 and 5; It is noted that a value of D/L of less than 1 is mainly advantageous in the case where the alcohol (L) 20 is used as a solvent and as a reactant; in addition, the value of D/L is preferably at least Is 1, preferably at least 15; the moiré d/l ratio is preferably at most 4 or 3. The preferred ranges of the Mohr ratios D/(NH2)3, L/(NH2)3 and D/L as given above apply to these materials because they are combined and they are also suitable for use in principle. The preferred range of the burnt amine-based plastic resin, except for the excess ratio (such as a D / (NH2) 3 ratio is above 6, a l / (NH2) 3 ratio is above 6 or a D / L The ratio is below 1) is not applicable outside. When referring to the alkylated amine-based plastic resin, the ratios should be related to the structural elements of the alkylated amine-based plastic resin attributed to the individual raw materials (i.e., D, L, A or N). In the formation of the reaction mixture in step a) according to the invention, as is known, it is advantageous to add a solvent; preferred solvents are C5_c% alcohol or water. The hydrazine reaction mixture is adjusted to a pH between 1 and 7 in the step b) in the first main embodiment according to the present invention. It is found that the formation of the alkylated amine-based plastic resin and especially the sub-alkylation step in which the alcohol is incorporated into the amine-based plastic resin are carried out under acidic conditions; preferably, the reaction mixture is adjusted To a pH between 2 and 6 or between 3 and 5. If the pH of the counter- 15 mixture is not in the desired range β when it is formed, it should be carried in a manner known to those skilled in the art, for example, by the addition of a Brostedt acid (such as sulfuric acid or formic acid) or a Alkali. Preferably, the pH is maintained throughout this range of steps b) and c). In order for the reaction step to occur effectively, the reaction mixture should be adjusted not only to a predetermined pH range but also to a certain temperature range. This first major embodiment according to the invention comprises a step c) wherein the reaction mixture is adjusted to a temperature between 8 〇〇 c and i 3 〇〇 c. The completion of the step 通常 usually makes the heating of the reaction mixture necessary. Heating can be obtained in a manner known per se, 11 200808847 such as a heat exchanger. Once the reaction mixture is adjusted to this temperature range, the formation of the alkylated amine-based plastic resin can occur. To effect this, the reaction mixture should be maintained in this temperature range for a desired amount of time. The amount of time required 5 will depend on factors that are known to those skilled in the art. The important factor in this article is the actual temperature, the actual? 11 and the desired component of the alkylated amine-based plastic resin. As will be appreciated, the effect of this actual temperature is an increase in temperature that causes the time required to achieve the desired result to be shortened. As will be appreciated, the effect of this actual pH is a decrease in pH 10 which results in a reduction in the time required to achieve the desired result. However, a too low pH, such as a pH lower than hydrazine, is not too advantageous because undesired side reactions such as deprotonation or spontaneous self-condensation of an -NH functional group of an amine compound are found. The gel formation can be increased or can be increased to a sufficiently large level; in addition, a very low pH is disadvantageous in the case of step d) which is carried out in 15 rows (discussed in detail below) because a very The test of cockroaches must be followed. The effect of the time required to perform the phantom step is also the desired component of the alkylated amine-based plastic resin: the higher the molecular weight of the burned amine-based plastic resin, the longer the step c) needs to be completed. In practice, this may mean that the length of time 20 required to complete the step illusion may vary within a wide range of limits, such as between 5 or 1 minute and 18 inches or even 240 minutes. The actual optimum time required to complete step c) can be measured simply by routine experimentation, wherein such factors as temperature and pH as determined above can be varied and wherein the development of the alkylated amine based plastic resin is via Samples were taken at regular intervals and analyzed by means of a test. The tests monitored by 12 200808847 are known in their own right, such as (but not limited to) cloud point measurement, water resistance measurement, infrared analysis, NMR. analysis. In this first main embodiment of the invention, steps a), 1^ and illusion are completed in order or they can be completed simultaneously. 5 When the step c) is carried out, it is desirable to stop the reaction and/or separate the alkylated amine-based plastic resin formed. This can be achieved by implementing these preferred steps d) and possibly also e) and f). In the step illusion, the pH of the reaction mixture is adjusted to a value between 9 and 13. This can be obtained in a manner known per se, such as by adding a test, like (aqueous) 10 NaOH. The most important effect of this increase in pH is that the formation or further formation of the alkylated amine-based plastic resin is effectively stopped. It is now possible to use the alkylated amine based plastic resin; however, it is also desirable to separate the alkylated amine based plastic resin from the unreacted starting materials, especially the c5_C3 sterol. In this case, it is preferred to adjust the temperature of the reaction mixture 15 in a step to a value such as evaporation of the volatility of the alcohol, followed by a step 〇 in which all volatility is essential The component, such as the C5-C3 sterol, is evaporated and the alkylated amine based plastic is thus recovered. The temperature at which the reaction mixture is produced in step e) is preferably the boiling point of the alcohol at atmospheric pressure. In order to promote the evaporation of the alcohol and/or to avoid decomposition of the alkylated amine 20-based plastic resin, it is necessary to advantageously operate step f) in a vacuum. The volatile component is defined as those compounds which are separated from the burnt amine-based plastic resin by heating and/or distillation and/or exposure to a vacuum, without decomposition of the sclerosing amine-based plastic resin. In a second main embodiment of the present invention, a reaction system is formed in the form of 200808847. First, the system does not contain the same. However, an alkylated amine-based plastic resin is first formed, and then An alkylation step. The second major embodiment of the invention thus comprises the steps of: L combining an amine compound, preferably comprising melamine, with a monoaldehyde and 5 optionally a solvent to form a reaction system; • adjusting the pH of the reaction system to between 7 and 1 Torr; iii. adjusting the temperature of the reaction system to between 6 ° C and reflux and allowing the reaction system to remain in the temperature range for a desired period of time The amount of time, whereby an amine-based plastic resin is formed; 10 lv• adjust the pH of the reaction system to between 1 and 7, and add a C5-C30 alcohol to the ruthenium; ν·allow the reaction The system is retained for a desired amount of time in the temperature range of 7 (TC to reflow) whereby the alkylated amine based plastic resin is formed. Although taking into account these features of this particular example, steps (i) through (iii) ) is about its 15 itself in the amine-based plastic tree The steps are known in the method of preparation, and are carried out according to conventional industrial interpolation. The interpretation of these terms is based on the previous main examples unless otherwise noted. In step (1), an amine group The compound and the aldehyde are carried in the reaction mixture in its own right, that is, not reacted in an amine-based plastic tree 2 ruthenium. The amine-based compound preferably comprises melamine, or even essentially It is composed of melamine. The aldehyde which is used may contain formaldehyde, and is relatively composed of formaldehyde in nature. However, it is also possible to use another kind of such as one of the acids mentioned earlier in this description. Also in this second main embodiment, the D/(1S[H2)3 ratio is preferably at least 3 14 200808847 and preferably at most 7. In step (i) the solitude is preferably water .
進行步驟(iii)所需的所欲的時間量是由被形成的該胺 基塑膠樹脂的該等所欲的特徵而被主要測量的。如所瞭解 的’在步师ii)中的-延長的反應時間會導致該胺基塑膠樹 5脂的分子量的-增加；該增加能進行至濁點被達到的程 度’或甚至财水性被降低至2、i或甚至〇的程度。發現在步 驟㈣中的分子量的-增加會導致在步驟(v)巾接下來形二 的該烧化胺基塑膠樹脂的玻璃轉移溫度Tg的增加。如所瞭 解的，-職_水性蚊義為在職脂變關之前在 10 20°c下被加入到1克樹脂中的水量的克數。 在步驟⑴中該莫爾D/(NH2)3比例是低於6的情況中，在 步驟(iii)之中或之後並且在步驟(iv)操作及進一步在下面所 討論之前，有利的是引入一D-混合步驟(iiia)和一D_結合步 驟(mb)。在D-混合步驟(iiia)中，該胺基塑膠樹脂與一量的 15 一醛化合物0組合，藉此在該反應系統中該全部莫爾 D/(NH2)3比例增加至少是〇·3，較佳地至少是〇.5或丨，並且 至多藉此在該反應系統中該全部莫爾D/(NH2)〇u?,〗被產生 至8。在D-結合步驟(iiib)中，然後，該反應系統被產生該自 由酸能與該胺基塑膠樹脂反應的條件，藉此一富含醛的胺 20基塑膠樹脂被形成。在步驟(iiib)中的該等條件類似於步驟 (iii)的條件或甚至與步驟(iii)的條件相同。如在步驟(出幻中 被引入該反應系統的該醛克與如在步驟⑴中被引入的該醛 相同或者它可是一不同的駿。 在該胺基塑膠樹脂或富含醛的胺基塑膠樹脂的形成之 15 200808847 後，該反應系統的pH被降低並且該烷化步驟被進行；這反 應了本發明的步驟(iv)和(v)。被加入的C5-C3〇醇的量同樣在 該第二主要具體例中被設計較佳地經由該C5-C3〇醇(L)和該 胺基化合物（A)(經由該-NH官能基）之間的莫爾比例。該 5 L/(NH2)3比例較佳地至少是1和較佳地至多是4，並且更佳地 是位於1.5至3之間。D/L比例的較佳態樣正如前面的主要具 體例中所給出的。 操作步驟(v)所需的所欲的時間量主要是透過充分被進 行的該烷化所需的時間而被測量的。雖然通常較佳的是進 10 行該烷化直到該等主要的反應條件會允許的程度，但是也 可能的是僅僅是進行一部分，例如，至最大烧化的5〇%至 75%。 當該第二主要具體例的步驟(v)完成時，所欲的是停止 該烧化反應；也所欲的是回收由該反應系統形成的該烷化 15 胺基樹脂。本發明因此進一步包含該等較佳的如下步驟； vi·使該反應系統的pH調節到9至13之間； vii·使該反應系統的溫度調節至一數值以使得揮發性 組分被蒸發；以及 V111·蒸發本質上全部揮發性組分並且回收該烷化胺基 20 塑膠樹脂。 步驟(vi)、（vii)和(viii)的完成類似於步驟幻、e)和f)的完 成被進行。 在本發明的一第三具體例中，一反應組成物在一步驟幻 中被形成。該反應組成物不同於該較早被定義的反應混合 16 200808847 物和反應系統，是因為被組合的該等原料不包含就其本身 而論至任何相當大的程度的一胺基化合物，並且也不包含 就其本身而論至任何相當大的程度的一醛。反之，它們以 反應的形式被帶入該反應組成物内，尤其是以由一Ci-C4. 5製備的一烷化胺基塑膠樹脂的形式。在該反應組成物中的 未反應的形式中胺基化合物和醛的量較佳地被限制在小於 15wt%、l〇wt%或5wt%，較佳地是小於胺基化合物或醛的 總量的lwt%的2wt%，也就是包括由_Ci_C4醇製備的該烷 化胺基塑膠樹脂的被使用的該等量。較佳地，hmmm* 10 HBMM被使用作為由_crC4醇製備的烧化胺基樹脂。大體 上有利的是使用一由三聚氰胺作為胺基化合物的一烷化胺 基塑膠樹脂。在另一較佳具體例中，異丙醇被使用作為該 CrC4醇。本發明的該第三主要具體例因此由本質上一再烷 化方法構成並且包含該等如下步驟： 15 α)使由一 Ci-C4醇製備的一烷化胺基塑膠樹脂與一 C5-C30醇 和選擇性地一溶劑組合而形成一反應組成物，溶劑諸如 例如水； β)使該反應組成物的pH調節到1至7之間； γ)使該反應組成物處於在60。(：至130°C之間的一溫度並且允 20 許該反應組成物在該溫度内保持持續一所欲的時間量， 其中該烷化胺基塑膠樹脂被形成。 步驟α)、β)和γ)可根據傳統的工業操作被進行，而考慮 本發明的該等特徵。術語的解釋正如在前面的主要具體例 中的一樣，除非以其他方式被注目。在一較佳具體例中， 17 200808847 由一 CrC4醇的該烷化胺基塑膠樹脂是HMMM及/或 HBMM。 完成本發明的步驟γ)所需的所欲的時間量主要是透過 為達到一充分程度的烧化所需的時間而被測量的。雖然通 5常較佳的疋進行該烧化直到該等主要的反應條件會允許的 程度，但是也可能的是僅僅是進行一部分，例如最大再燒 化的50%至75%。 當該第三主要具體例的步驟γ)完成時，所欲的是停止 該再烷化反應；也所欲的是回收由該反應組成物形成的該 10烷化胺基塑膠樹脂。本發明因此還包含該等如下較佳的步驟： δ)使該反應組成物的pH調節到9至13之間； ε)使該反應系統的溫度調節至一數值以使得揮發性組分被 蒸發； ζ)蒸發本質上全部揮發性組分並且回收該烷化胺基塑膠樹脂。 15 步驟δ)、幻和ζ)的完成類似於步驟d)、e)和f)以及(Vi)、 (vii)和(viii)的完成被進行。 如早先所指出的，可能的是以某些方式使該等主要具 體例彼此組合，其中本發明的進一步的主要具體例被明 確。這樣一組合的一例子是像使用在本發明的步驟c)中形 2〇 成的一烷化胺基塑膠樹脂作為在步驟α)中的原料，部分地 或全部地代替由一CrC4醇製備的該烷化胺基塑膠樹脂。類 似地，可能的是使用如在本發明的步驟(v)中形成的該烷化 胺基塑膠樹脂來部分地或全部地代替在步驟α)由一 CVC4醇 製備的該烷化胺基塑膠樹脂。 18 200808847 對於這些化合物的全部主要具體例的某些組合是尤其 車父佳的，諸如選擇三聚氰胺作為胺基化合物，選擇環己醇 或THFA作為該醇並且選擇甲駿作為駿。可是，較佳 的是在不含甲醛的條件下操作。在這樣一情況中，早先提 5到的該專選擇性的盤之一，諸如丙酸、苯甲盤或GMHA是 較佳的，與作為胺基化合物的三聚氰胺組合並且與作為該 Q-C%醇的環己醇或GMHA組合。 前面描述的該等主要具體例與烷化胺基塑膠樹脂的製 備方法是有關的。在製備該烷化胺基塑膠樹脂中，發現該 10莫爾D/(NH2)3比例對該烷化胺基塑膠樹脂的玻璃轉移溫度 Tg具有影響；發現一低的D/(NH2)3比例（可是如在給出的範 圍内是較佳的）能導致該Tg的一增加；可是，必須要注音的 是在這樣的情況中該烷化胺基塑膠樹脂的穩定性沒有太多 受損。穩定性在本文中被定性定義為該烷化胺基塑膠樹脂 15 經過自反應的趨勢，由自發的膠形成可見。同樣發現該莫 爾L/(NH2)3比例對該烧化胺基塑膠樹脂的玻璃轉移溫度丁 g 具有影響；發現一低的L/(NH2)3比例（可是如在給出的範圍 内是較佳的）能導致該Tg的一增加；可是，必須要注音的是 在這樣的情況中該烷化胺基塑膠樹脂的穩定性沒有太多受 2〇損。已發現特定種類的醇對該烷化胺基塑膠樹脂的穩定性 具有影響·’大體上說’ Cs-Qo醇比CVQ醇能導致更穩定的 烷化胺基塑膠樹脂。 驚奇地，可能根據本發明製備具有一高Tg(在1 〇°c、丨 或20°C，或者甚至在25°C、30°C、40°C或更高）並且具有一 19 200808847 好的穩定性的烷化胺基塑膠樹脂，其中該等胺基烷化塑膠 樹脂仍具有某些用途所需的反應性，諸如在例如塗層組成 物中作為交聯劑的用途。 本發明因此是進一步關於根據該等上面描述的主要具 5 體例中的任何一個得到的烷化胺基塑膠樹脂。在某些情況 中，可能的是透過下面的化學式⑴來表示根據本發明的該 烧化胺基塑膠樹脂：The desired amount of time required to carry out step (iii) is primarily measured by the desired characteristics of the amine-based plastic resin being formed. As understood, in 'Step ii' - the extended reaction time leads to an increase in the molecular weight of the amine-based plastic tree 5 lipid; this increase can be made to the extent that the cloud point is reached' or even the water content is lowered To the extent of 2, i or even awkward. It has been found that the increase in molecular weight in the step (IV) causes an increase in the glass transition temperature Tg of the burnt-amine-based plastic resin in the next step of the step (v). As understood, the number of water-based mosquitoes is the number of grams of water added to 1 gram of resin at 10 20 ° C before the in-service fat change. In the case where the Mohr D/(NH2)3 ratio is lower than 6 in the step (1), it is advantageous to introduce in or after the step (iii) and before the step (iv) and further discussed below. A D-mixing step (iiia) and a D_ combining step (mb). In the D-mixing step (iiia), the amine-based plastic resin is combined with an amount of 15-monoaldehyde compound 0, whereby the total Mohr D/(NH2)3 ratio is increased by at least 〇·3 in the reaction system. Preferably, it is at least 〇.5 or 丨, and at most the entire Mohr D/(NH2)〇u? is produced to 8 in the reaction system. In the D-binding step (iiib), the reaction system is then subjected to a condition in which the free acid can react with the amine-based plastic resin, whereby an aldehyde-rich amine 20-based plastic resin is formed. The conditions in step (iiib) are similar to the conditions of step (iii) or even the conditions of step (iii). The aldehyde gram which is introduced into the reaction system in the step is the same as the aldehyde introduced as in the step (1) or it may be a different one. The amine-based plastic resin or the aldehyde-rich amine-based plastic is used. After the formation of the resin 15 200808847, the pH of the reaction system is lowered and the alkylation step is carried out; this reflects the steps (iv) and (v) of the present invention. The amount of C5-C3 sterol added is also The second major embodiment is designed to preferably pass the molar ratio between the C5-C3 sterol (L) and the amine compound (A) (via the -NH functional group). The 5 L/( The NH2)3 ratio is preferably at least 1 and preferably at most 4, and more preferably between 1.5 and 3. Preferred aspects of the D/L ratio are as given in the previous main examples. The amount of time required to operate step (v) is primarily measured by the time required for the alkylation to be sufficiently carried out, although it is generally preferred to carry out the alkylation until the main The extent to which the reaction conditions will be allowed, but it is also possible to carry out only a part, for example, from 5% to 75% of the maximum burnout. When step (v) of the second main embodiment is completed, it is desirable to stop the burning reaction; it is also desirable to recover the alkylated 15 amine-based resin formed by the reaction system. The present invention therefore further encompasses And preferably the following steps; vi· adjusting the pH of the reaction system to between 9 and 13; vii· adjusting the temperature of the reaction system to a value such that the volatile components are evaporated; and V111·evaporation is essentially All volatile components are recovered and the alkylated amine 20 plastic resin is recovered. The completion of steps (vi), (vii) and (viii) is carried out analogously to the completion of steps illus, e) and f). In a third embodiment of the invention, a reactive composition is formed in a phantom. The reaction composition is different from the earlier defined reaction mixture 16 200808847 and the reaction system because the combined raw materials do not contain an amine compound to any significant extent as such, and It does not contain any considerable degree of monoaldehyde as far as it is. Instead, they are brought into the reaction composition in the form of a reaction, especially in the form of an alkylated amine-based plastic resin prepared from a Ci-C4.5. The amount of the amine compound and the aldehyde in the unreacted form in the reaction composition is preferably limited to less than 15% by weight, 1% by weight or 5% by weight, preferably less than the total amount of the amine compound or aldehyde. 2 wt% of lwt%, that is, the equivalent amount of the alkylated amine-based plastic resin prepared from the _Ci_C4 alcohol. Preferably, hmmm* 10 HBMM is used as the burnt amine-based resin prepared from _crC4 alcohol. It is generally advantageous to use an alkylated amine based plastic resin from melamine as the amine compound. In another preferred embodiment, isopropanol is used as the CrC4 alcohol. This third major embodiment of the invention thus consists essentially of the re-alkylation process and comprises the steps of: 15) a monoalkylated amino-based plastic resin prepared from a Ci-C4 alcohol and a C5-C30 alcohol and Optionally, a solvent combination is combined to form a reactive composition such as, for example, water; β) to adjust the pH of the reaction composition to between 1 and 7; γ) to bring the reaction composition at 60. (: a temperature between 130 ° C and allowing the reaction composition to remain at this temperature for a desired amount of time, wherein the alkylated amine-based plastic resin is formed. Steps α), β) and γ) can be carried out according to conventional industrial operations, taking into account these features of the invention. The interpretation of the terms is as in the previous main examples unless otherwise noted. In a preferred embodiment, 17 200808847 the alkylated amine based plastic resin from a CrC4 alcohol is HMMM and/or HBMM. The desired amount of time required to complete step y) of the present invention is primarily measured by the time required to achieve a sufficient degree of firing. Although it is often preferred to carry out the burning until the extent that the main reaction conditions are tolerated, it is also possible to carry out only a part, for example 50% to 75% of the maximum re-sintering. When the step γ) of the third main embodiment is completed, it is desirable to stop the realkylation reaction; it is also desirable to recover the 10 alkylated amine-based plastic resin formed from the reaction composition. The invention therefore also comprises the following preferred steps: δ) adjusting the pH of the reaction composition to between 9 and 13; ε) adjusting the temperature of the reaction system to a value such that the volatile components are evaporated ζ) Evaporates all volatile components in nature and recovers the alkylated amine-based plastic resin. The completion of the steps 15 δ), illusion and ζ) is performed similarly to the completion of steps d), e) and f) and (Vi), (vii) and (viii). As indicated earlier, it is possible to combine the main embodiments with each other in some manner, with further major specific examples of the invention being clarified. An example of such a combination is the use of an alkylated amine-based plastic resin formed in the step c) of the present invention as a raw material in the step α), partially or completely replacing the preparation of a CrC4 alcohol. The alkylated amine based plastic resin. Similarly, it is possible to partially or completely replace the alkylated amine-based plastic resin prepared from a CVC4 alcohol in step a) using the alkylated amine-based plastic resin as formed in step (v) of the present invention. . 18 200808847 Some combinations of all the main specific examples of these compounds are especially good for the car, such as selecting melamine as the amine compound, selecting cyclohexanol or THFA as the alcohol and selecting A. However, it is preferred to operate in the absence of formaldehyde. In such a case, one of the specifically selected disks, such as propionic acid, benzopyrene or GMHA, which is mentioned earlier, is preferably combined with melamine as an amine compound and with the QC% alcohol. A combination of cyclohexanol or GMHA. The main specific examples described above are related to the preparation method of the alkylated amine-based plastic resin. In the preparation of the alkylated amine-based plastic resin, it was found that the 10-mole D/(NH2)3 ratio has an influence on the glass transition temperature Tg of the alkylated amine-based plastic resin; a low D/(NH2)3 ratio was found. (But preferred in the range given) can result in an increase in the Tg; however, it must be noted that in such a case the stability of the alkylated amine-based plastic resin is not much impaired. Stability is qualitatively defined herein as the tendency of the alkylated amine-based plastic resin 15 to undergo self-reaction, as seen by spontaneous gel formation. It was also found that the Mohr L/(NH2)3 ratio had an effect on the glass transition temperature of the burnt amine-based plastic resin; a low L/(NH2)3 ratio was found (but as in the range given) Good) can lead to an increase in the Tg; however, it must be noted that in such a case, the stability of the alkylated amine-based plastic resin is not much less affected. It has been found that certain types of alcohols have an effect on the stability of the alkylated amine-based plastic resin. 'Generally speaking, Cs-Qo alcohols can lead to more stable alkylated amine-based plastic resins than CVQ alcohols. Surprisingly, it may be prepared according to the invention to have a high Tg (at 1 ° C, 丨 or 20 ° C, or even at 25 ° C, 30 ° C, 40 ° C or higher) and with a 19 200808847 A stabilized alkylated amine based plastic resin wherein the amine alkylated plastic resin still has the requisite reactivity required for certain applications, such as the use as a crosslinking agent in, for example, a coating composition. The present invention is therefore further directed to an alkylated amine-based plastic resin obtained according to any of the above-described main embodiments. In some cases, it is possible to express the burnt amine-based plastic resin according to the present invention by the following chemical formula (1):
(I) 其中 10 A1是一胺基化合物核心； X至少是2 ; B是H、CH2OR、根據化學式(II)的一基團或者根據化學式(III) 的一基團，其中： 1是11或減去一_OH基團的C5-C30醇；(I) wherein 10 A1 is a monoamine compound core; X is at least 2; B is H, CH2OR, a group according to formula (II) or a group according to formula (III), wherein: 1 is 11 or Subtracting an _OH group of C5-C30 alcohol;
15 化學式(II)是：15 Chemical formula (II) is:
20 200808847 藉此： 至少30%或40%，較佳地50%、60%，或甚至是7〇%或邮 的全部B基團疋CH2〇Ri ’ R〗是減去一-OH基團的醇 作為一整體的該樹脂的每一個“A1，，部分包含至夕 ’ 5 10 15 20 夕1.5或 1·3，較佳地至多ΐ·〇、〇·8、〇·7或甚至至多〇 6、〇 5戈〇 -ΝΗ基團； ·固 該樹脂的重量平均分子量是200至1〇,〇〇〇之間；較隹地上 樹脂的該重量平均分子量是位於3〇〇至9,5〇〇之間，争 文佳地 是位於400或500或1，〇〇〇與9,〇〇〇之間。 根據本發明的烷化胺基塑膠樹脂適合於廣泛的應用. 一種這樣的應用是它們作為交聯劑；該交聯能力在例如杓 脂中、黏合劑組成物中或塗層組成物中是有利的。由於裙 據本發明引起的可能性，烷化胺基塑膠樹脂具有—高的 Tg(位於例如室溫附近或之上），它們尤其適合於作為粉末涂 層組成物中的交聯劑。本發明因此是進一步關於塗層組成 物，尤其是粉末塗層組成物，包含根據本發明的烷化胺基 塑膠樹脂。被包含在該粉末塗層組成物中的烷化胺基塑膠 樹脂的量可在廣闊的限度内變化；較佳地，以作為一整體 的粉末塗層組成物計，該量是位於lwt%至3〇wt%之間。在 本發明的一經選擇的具體例中，該烧化胺基塑膠樹脂不但 被使用作為交聯劑而且作為在一塗層組成物中的不可缺少 的塗層組成部分。在這樣一情況中，如被包含在一塗層組 成物中的烷化胺基塑膠樹脂的量可一直到4〇wt%、6〇wt%、 70wt%、80wt%、90wt% 或甚至 95wt%、99wt% 或本質上 21 200808847 lOOwt% 〇 正如所瞭解的，一粉末塗層組成物通常含有一催化 劑，該催化劑的作用是促進該交聯劑的交聯活性。常常並 且較佳地是一酸以一有效的量被選擇作為催化劑；這些有 5 效的量常常是位於O.lwt%至2wt%的範圍内。常常在交聯操 作中被選擇的一酸的一例子是對甲苯磺酸(PTSA)。可是， 這樣做該酸的催化官能基應被考慮該溫度的功能。在實踐 中，包含一交聯劑和一催化劑的一粉末塗層組成物是在稍 微提升的溫度下被製備的，例如約5(rcs8(rc。重要的是 10 一催化劑在這樣的溫度下不應是非常活性的。另一方面， 非常有利的是如果一催化劑在僅僅稍微高於此的溫度下變 得非常活潑，例如在約100_12(rc。為了找到在稍微提升的 溫度下的非活性和在稍高於此溫度下的高活性之間的一折 衷辦法，忒催化劑通常包含一酸和一堵劑之一組合。這樣 15的組合就其本身而論是已知的。常常被選擇作為堵劑的一 類組分的-例子是環氧化合物種類。本發明的一較佳具體 例因此是關於-粉末塗層組成物，該粉末塗層組成物包含 根據本發明的一燒化胺基塑膠樹脂並且還包含作為催化劑 的酸和-壞氧化合物，其中該酸和該環氧化合物之間的 2〇重ΐ比例是在1〇:9〇至7〇:3〇之間。尤其較佳的是包含作為酸 的對甲苯橫酸和一脂環族環氧化物的-催化劑，較佳地Γ 3,4·環氧環己基甲基_3,4_環氧環己烧缓酸醋。 疋 【貧施方式;J 較佳實施例之詳細說明 22 200808847 本發明會透過如下所顯示的該等實施例的方式被說 明’沒有被限制在該等實施例中。 實施例1 實施例是根據本發明的該第一主要具體例而被進行 5的’其中該胺基化合物是三聚氰胺，三聚甲醛被用作甲醛 並且該C5_C30醇是四氫糠醇。 步驟a)和b)如下被組合操作··裝配有一蒸餾裝備的一經 油加熱的丨.5升玻璃反應器被進料106.7克三聚氰胺、171.3 克三聚甲醛(91-92%純度)和1037.0克四氫糠醇，並且使其處 10於氮氣之下。油溫被設置在ll〇°C。55分鐘之後該反應混合 物的溫度是94°C並且該反應混合物變得清澈。該油溫被設 置在115。〇 10分鐘之後21.7克的2莫爾的溶於四氫糠醇中甲 酸溶液被加入並且一4〇〇mBar的真空被施加。 ^而進行後面的步驟c)的操作。在95分鐘的過程中該 I5 >£力逐漸降低至26mBar。60分鐘之後該真空被停止。然後， 經由加入68.5g的一 5%的熔於四氫糠醇的氫氧化鈉溶液步 驟d)被進行。在下面的步驟e)和θ中，首先一全部*⑽克的 液體被除去。該的反應產物仍含有大量溶劑。在一旋轉蒸 發器中該溶劑在真空下被除去；在12〇。〇下起始，在一 1〇〇 20分鐘的時間段内該溫度被逐漸增加至17(TC，並且繼而在 170C下被保持15分鐘。最終，31〇克烷化胺基塑膠樹脂被 收回。 該烷化胺基塑膠樹脂的接下來的測試產生該等如下性質： -經由D S C測量的玻璃轉移溫度T g是2 2它 23 200808847 -數量平均分子量(Μη)是1478 ;重量平均分子量(Mw) 是7490(使用聚苯乙烯標準物在GPC中測量） -該烷化胺基塑膠樹脂的莫爾比例D/(NH2)3(也就是，等 於當被併入該樹脂中時的甲醛與三聚氰胺結構單元的比例) 5 是3.6 ;這是經由有關該烷化胺基塑膠樹脂的一 13〇NMR測 量而被測量的。 -該烷化胺基塑膠樹脂的莫爾比例l/(nh2)3(也就是，等 於當被併入該樹脂中時的環己醇與三聚氰胺結構單元的比 例）是2·1 ;這是經由有關該烷化胺基塑膠樹脂的一 13〇NMR 10 測量而被測量的。 實施例2 根據本發明的第二主要具體例進行實施例2,其中該胺 基化合物疋二聚鼠胺以及該C5-C3G醉是環己醇。 一胺基塑膠樹脂的製備： 15 裝配有一回流冷凝器的一經油加熱的1.5升玻璃反應 器被進料100.8克三聚氰胺、335.2克50.14%的溶於水的甲醛 和53克水。在被加入到該反應器之前使用一2莫爾的氫氧化 鈉溶液該甲醛溶液的pH被調節到9.0。該反應系統的溫度被 設置到60°C。只要該反應系統變得清激，該反應器被卸下。 20 該反應系統在室溫下保留16個小時。 該烷化胺基塑膠樹脂的製備'回收和性質測量： 裝配有'Dean-St ark裝備的 經*油加熱的1.5升破璃反 應器被進料被進料206克該反應系統（包含該胺基塑膠樹 脂）。向該反應系統中加入592克環己醇；該反應系統繼而 24 200808847 處於氮氣氛圍之下。該油溫被設置為84°C。70分鐘之後， δ亥反應混合物變得清澈並且使用發煙鹽酸該pjj被降至 4.6(步驟(iv))。該油溫被設置為l〇9°C。10分鐘之後該反應 混合物的溫度是92°C。140分鐘之後一600mBar的真空被施 5 加並且在50分鐘内被降至7〇mBar。80分鐘之後該真空被停 止並且使用一飽和的氫氧化鈉甲醇溶液該pH被設置為 12.5(步驟(vi))。經由該Dean-strak，130克水被除去。 在一旋轉蒸發器中在真空、120°C下任何過量的溶劑或 揮發性組分被除去並且在1〇〇分鐘内該溫度逐漸增加至 10 150°C，使其在150°C下保持15分鐘。該烷化胺基塑膠樹脂 因此被回收。 該烧化胺基塑膠樹脂的接下來的測試產生該等如下性質·· -玻璃轉移溫度Tg是48°C (在DSC中被測量） -數量平均分子量(Μη)是1193 ;重量平均分子量(Mw) 15 是2511(使用聚苯乙烯標準物在GPC中測量） -該烷化胺基塑膠樹脂的莫爾比例D/(NH2)3(也就是，等 於當被併入該樹脂中時的甲醛與三聚氰胺結構單元的比例) 是4.7 ;這是經由有關該烧化胺基塑膠樹脂的一 13c_]sjMR測 量而被測量的。 20 •該烷化胺基塑膠樹脂的莫爾比例L/(NH2)3(也就是，等 於當被併入該樹脂中時的環己醇與三聚氰胺結構單元的比 例）是2·1，这疋經由有關該烧化胺基塑膠樹脂的一 13c_NMR 測量而被測量的。 實施例3 25 200808847 如實施例2 —樣操作實施例3，然而下面不同的是： -代替步驟(iv)中使該pH降至4.6，它被降至2.9 ; -在步驟(viii)中該烷化胺基塑膠樹脂的最終回收是經 由在_20°C下從並同中沉澱之後在真空下過濾並且乾燥而 5 被進行。 該烷化胺基塑膠樹脂的接下來的測試產生該等如下性質： -玻璃轉移溫度1^是47。(：(在DSC中被測量） -數量平均分子量(Μη)是2784;重量平均分子量(Mw) 是5833(使用聚苯乙烯標準物在GPC中測量） 10 -該烷化胺基塑膠樹脂的莫爾比例D/(NH2)3(也就是，等 於當被併入該樹脂中時的曱醛與三聚氰胺結構單元的比例) 是5.0 ;這是經由有關該烷化胺基塑膠樹脂的一 測 量而被測量的。 -該烷化胺基塑膠樹脂的莫爾比例l/(nh2)3(也就是，等 15 於當被併入該樹脂中時的環己醇與三聚氰胺結構單元的比 例）是3·0;這是經由有關該烷化胺基塑膠樹脂的一 13C_NMr 測量而被測量的。 實施例4 作為交聯劑的一烷化胺基塑膠樹脂的用途 20 如在實施例1中製備的20份該烷化胺基塑膠樹脂、80 份UralacTM P1580粉末（一 OH-官能飽和羧化聚酯塗層樹 脂；供應商：DSM® Resins)、由1份對甲苯磺酸和3份AEPD(2-胺基-2-乙基-1，3-丙二醇）構成的0.5份一催化混合杨、0.75 份作為消泡劑的安息香、50份鈦白（Kronos™ 2160)和1.5份 26 200808847 作為流動劑的Resifl〇w™ PV5(供應商：w〇ri‘Chemie)被進 料至、雙螺擠壓機並且在85。〇下被擠壓。該擠出物被研 磨’並且接下來被篩選以便得到具有不大於90μιη的顆粒的 一粉末塗層組成物。 5 具有位於室溫之上的—Tg的一層該粉末塗層組成物在 一鋁薄片上被靜電喷灑。該層具有約52μιη的的一厚度。為 了調查在什麼溫度下該塗層的固化可被達到（包括如透過 根據本發明的烷化胺基塑膠樹脂而被達到的交聯），經該粉 末覆盍的鋁薄片在4〇分鐘之内被放在一梯度烘箱内。該烘 10箱具有從100°C至15(TC的一梯度。 、 從該梯度烘箱中取出的該鋁薄片被進行丙酮雙摩擦測 试。在這個測試中，一織物被浸透在丙酮中並且然後在該 塗層之上來回被摩擦。一次來回的運動計數為一雙摩擦。 在執行該測試中，計算了直到該塗層溶解在該塗層之上該 15織物被擦過的次數，藉此如果該塗層禁得起至少100次雙摩 擦，令人滿意的性能的要求被達到。這個要求符合在120它 或更高的溫度下的固化，因此證明了充分的該粉末塗層組 成物的固化確實在那些溫度下被達到。 實施例5 20 實施例5如實施例4被進行，除了如在實施例2中被製備 的20份該烧化胺基塑膠樹脂被使用外。 具有位於室溫之上的一Tg的一層該粉末塗層組成物在 一鋁薄片上被靜電噴灑。該層具有約45μηι的的一厚度。經 該粉末覆蓋的鋁薄片在2〇分鐘的時間内被放在一梯度烘箱 27 200808847 内。該煤箱具有從100乞至15〇。(：的一梯度。 從該梯度烘箱中取出的該鋁薄片被進行丙酮雙摩擦_ 試’藉此對於禁得住至少100次雙摩擦所要求是符合在 14〇°C或更高的溫度下的固化，因此證明了充分的該粉末塗 5層組成物的固化確實在那些溫度下被達到。 實施例6 實施例6如實施例4被進行，除了如在實施例3中被製備 的20份該烷化胺基塑膠樹脂被使用外。 具有位於室溫之上的一Tg的一層該粉末塗層組成物在 10 —鋁薄片上被靜電喷灑。該層具有約37μηι的的一厚度。辨 5亥物末覆盖的铭缚片在20分鐘的時間内被放在一梯度力址箱 内。該烘箱具有從loot：至200°c的一梯度。 從該梯度烘箱中取出的該鋁薄片被進行丙g同雙摩擦測 試，藉此對於禁得住至少1〇〇次雙摩擦所要求是符合在 15 18(TC或更高的溫度下的固化，因此證明了充分的該粉末塗 層組成物的固化確實在那些溫度下被達到。 I：圖式簡單說明；] (無） 【主要元件符號說明】 (無） 2820 200808847 By this: at least 30% or 40%, preferably 50%, 60%, or even 7〇% or all B groups of the 疋CH2〇Ri 'R〗 is minus one-OH group Each of the "A1" of the resin as a whole as a whole contains a portion of ～5 10 15 20 1.5 1.5 or 1.3, preferably at most ΐ·〇, 〇·8, 〇·7 or even at most 〇6 〇5〇〇-ΝΗ group; · The weight average molecular weight of the resin is between 200 and 1 〇, between 〇〇〇; the weight average molecular weight of the resin above the 隹 ground is located at 3〇〇 to 9,5〇〇 Between the two, the content is preferably between 400 or 500 or 1, between 〇〇〇 and 9, 〇〇〇. The alkylated amine-based plastic resin according to the invention is suitable for a wide range of applications. One such application is that they serve Crosslinking agent; the crosslinking ability is advantageous in, for example, blush, binder composition or coating composition. The alkylated amine based plastic resin has a high Tg due to the possibility of the present invention. (located, for example, near or above room temperature), they are especially suitable as crosslinkers in powder coating compositions. The invention is therefore further closed a coating composition, in particular a powder coating composition, comprising an alkylated amine-based plastic resin according to the invention. The amount of alkylated amine-based plastic resin contained in the powder coating composition can be within a wide range Preferably, the amount is between 1% by weight and 3% by weight based on the powder coating composition as a whole. In a selected specific embodiment of the invention, the burnt amine-based plastic resin is not only It is used as a crosslinking agent and as an indispensable coating component in a coating composition. In such a case, the amount of the alkylated amine-based plastic resin, such as contained in a coating composition, can be used. Up to 4 〇 wt%, 6 〇 wt%, 70 wt%, 80 wt%, 90 wt% or even 95 wt%, 99 wt% or essentially 21 200808847 lOOwt% 〇 As is known, a powder coating composition usually contains a catalyst The effect of the catalyst is to promote the crosslinking activity of the crosslinking agent. It is often and preferably that an acid is selected as a catalyst in an effective amount; these 5 effective amounts are often from 0.1% by weight to 2% by weight. Within the scope of the cross-linking operation An example of a selected monoacid is p-toluenesulfonic acid (PTSA). However, the catalytic functional group of the acid should be considered to function at this temperature. In practice, a powder comprising a crosslinking agent and a catalyst is coated. The layer composition is prepared at a slightly elevated temperature, for example about 5 (rcs8 (rc. It is important that 10 a catalyst should not be very active at such temperatures. On the other hand, it is very advantageous if one The catalyst becomes very active at temperatures just slightly above this, for example at about 100-12 (rc. in order to find a compromise between inactivity at slightly elevated temperatures and high activity at slightly above this temperature). The rhodium catalyst typically comprises a combination of an acid and a blocking agent. Such a combination of 15 is known per se. An example of a component that is often chosen as a blocking agent is the class of epoxy compounds. A preferred embodiment of the present invention is therefore directed to a powder coating composition comprising a burnt amine-based plastic resin according to the present invention and further comprising an acid and a bad oxygen compound as a catalyst, wherein The 2〇 heavy enthalpy ratio between the acid and the epoxy compound is between 1 〇:9 〇 to 7 〇:3 。. Particularly preferred is a catalyst comprising p-toluic acid as an acid and an alicyclic epoxide, preferably Γ 3,4·epoxycyclohexylmethyl_3,4_epoxycyclohexene Sour vinegar.疋 [Last mode]; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 22 200808847 The present invention will be described by way of the embodiments shown below, which are not limited to the embodiments. EXAMPLE 1 An example is carried out according to this first main embodiment of the invention wherein the amine compound is melamine, the paraformaldehyde is used as formaldehyde and the C5_C30 alcohol is tetrahydrofurfuryl alcohol. Steps a) and b) were combined as follows. • An oil-heated 丨.5 liter glass reactor equipped with a distillation apparatus was charged with 106.7 g of melamine, 171.3 g of trioxane (91-92% purity) and 1037.0 g. Tetrahydrofurfuryl alcohol and placed at 10 under nitrogen. The oil temperature is set at ll 〇 °C. The temperature of the reaction mixture after 55 minutes was 94 ° C and the reaction mixture became clear. The oil temperature is set at 115. After 10 minutes, 21.7 g of 2 mol of a solution of formic acid dissolved in tetrahydrofurfuryl alcohol was added and a vacuum of 4 〇〇 mBar was applied. ^ and proceed to the operation of the following step c). The I5 > force gradually decreased to 26 mBar during the 95 minute process. The vacuum was stopped after 60 minutes. Then, it was carried out by adding 68.5 g of a 5% sodium hydroxide solution in tetrahydrofurfuryl alcohol to the step d). In the following steps e) and θ, first all *(10) grams of liquid are removed. The reaction product still contains a large amount of solvent. The solvent was removed under vacuum in a rotary evaporator; at 12 Torr. Starting at the beginning of the sputum, the temperature was gradually increased to 17 (TC, and then held at 170 C for 15 minutes in a period of 1 〇〇 20 minutes. Finally, 31 gram of the alkylated amine-based plastic resin was withdrawn. The subsequent testing of the alkylated amine-based plastic resin produced the following properties: - The glass transition temperature Tg measured by DSC was 2 2 it 23 200808847 - The number average molecular weight (Μη) was 1478; the weight average molecular weight (Mw) Is 7490 (measured in GPC using polystyrene standards) - Moiré ratio D/(NH2)3 of the alkylated amine-based plastic resin (that is, equivalent to formaldehyde and melamine structure when incorporated into the resin) The ratio of the unit) 5 is 3.6; this is measured by a 13 NMR measurement of the alkylated amine-based plastic resin. - The molar ratio of the alkylated amine-based plastic resin is l/(nh2)3 (also That is, the ratio of cyclohexanol to melamine structural unit when incorporated into the resin is 2.1; this is measured by a 13 NMR 10 measurement of the alkylated amine-based plastic resin. Embodiment 2 Embodiment 2 is carried out according to a second main embodiment of the present invention, Wherein the amine compound bismuthimamine and the C5-C3G drunk are cyclohexanol. Preparation of an amine-based plastic resin: 15 An oil-heated 1.5 liter glass reactor equipped with a reflux condenser is fed 100.8 g. Melamine, 335.2 g of 50.14% of water-soluble formaldehyde and 53 g of water. The pH of the formaldehyde solution was adjusted to 9.0 using a 2 mol sodium hydroxide solution before being added to the reactor. It was set to 60 ° C. The reactor was removed as long as the reaction system became clear. 20 The reaction system was kept at room temperature for 16 hours. Preparation of the alkylated amine-based plastic resin 'recovery and property measurement : An oil-heated 1.5 liter glass reactor equipped with 'Dean-Stark equipment was fed to feed 206 grams of the reaction system (containing the amine-based plastic resin). 592 grams of ring was added to the reaction system. Hexanol; the reaction system was then under a nitrogen atmosphere at 24 200808847. The oil temperature was set to 84 ° C. After 70 minutes, the δ hai reaction mixture became clear and the pjj was reduced to 4.6 using fuming hydrochloric acid (step ( Iv)). The oil temperature is set l 〇 9 ° C. The temperature of the reaction mixture after 10 minutes was 92 ° C. After 140 minutes, a vacuum of 600 mBar was applied 5 and was lowered to 7 〇 m Bar in 50 minutes. After 80 minutes the vacuum was stopped and The pH was set to 12.5 using a saturated sodium hydroxide methanol solution (step (vi)). 130 g of water was removed via the Dean-strak. Any excess in vacuum, 120 ° C in a rotary evaporator The solvent or volatile components were removed and the temperature was gradually increased to 10 150 ° C in 1 min, which was maintained at 150 ° C for 15 minutes. The alkylated amine-based plastic resin is thus recovered. The subsequent test of the burnt amine-based plastic resin produced the following properties: - The glass transition temperature Tg was 48 ° C (measured in DSC) - The number average molecular weight (Μη) was 1193; the weight average molecular weight (Mw) 15 is 2511 (measured in GPC using polystyrene standards) - Moiré ratio of the alkylated amine-based plastic resin D/(NH2)3 (that is, equal to formaldehyde and melamine when incorporated into the resin) The ratio of the structural unit is 4.7; this is measured by a 13c_]sjMR measurement of the burnt amine-based plastic resin. 20 • The moiré ratio L/(NH 2 ) 3 of the alkylated amine-based plastic resin (that is, the ratio of the cyclohexanol to the melamine structural unit when incorporated into the resin) is 2.1, which is It was measured by a 13c_NMR measurement on the burned amine-based plastic resin. Example 3 25 200808847 Example 3 was operated as in Example 2, except that the following is different: - instead of lowering the pH to 4.6 in step (iv), it is lowered to 2.9; - in step (viii) The final recovery of the alkylated amine-based plastic resin was carried out by filtration under vacuum at -20 ° C, followed by filtration under vacuum and drying. Subsequent testing of the alkylated amine-based plastic resin produced the following properties: - The glass transition temperature was 47. (: (measured in DSC) - the number average molecular weight (?n) is 2784; the weight average molecular weight (Mw) is 5833 (measured in GPC using polystyrene standards) 10 - the alkylated amine based plastic resin The ratio D/(NH2)3 (that is, the ratio of furfural to melamine structural unit when incorporated into the resin) is 5.0; this is determined by a measurement relating to the alkylated amine-based plastic resin. The molar ratio of the alkylated amine-based plastic resin is 1/(nh2)3 (that is, the ratio of cyclohexanol to melamine structural unit when incorporated into the resin) is 3· 0; This was measured by a 13C_NMr measurement of the alkylated amine-based plastic resin. Example 4 Use of an alkylated amine-based plastic resin as a crosslinking agent 20 20 parts as prepared in Example 1. The alkylated amine based plastic resin, 80 parts of UralacTM P1580 powder (an OH-functional saturated carboxylated polyester coating resin; supplier: DSM® Resins), 1 part p-toluenesulfonic acid and 3 parts AEPD (2-amine) 0.5 parts of a catalytically mixed poplar composed of keto-2-ethyl-1,3-propanediol, and 0.75 parts of benzoin as a defoaming agent 50 parts of titanium white (KronosTM 2160) and 1.5 parts of 26 200808847 Resifl〇wTM PV5 (supplier: w〇ri'Chemie) as a flow agent was fed to the twin screw extruder and at 85. The extrudate is milled' and subsequently screened to obtain a powder coating composition having particles of no more than 90 μη. 5 a layer of the powder coating composition having a -Tg above room temperature Electrostatically sprayed on an aluminum foil. The layer has a thickness of about 52 μm. In order to investigate at what temperature the curing of the coating can be achieved (including, for example, by the alkylated amine-based plastic resin according to the present invention) The cross-linking achieved, the powder-coated aluminum flakes were placed in a gradient oven within 4 min. The bake 10 bins had a gradient from 100 ° C to 15 (TC). From the gradient oven The aluminum flakes taken out were subjected to an acetone double rub test. In this test, a fabric was soaked in acetone and then rubbed back and forth over the coating. One back and forth movement count was a pair of rubs. In this test, it was calculated until The coating dissolves the number of times the 15 fabric is wiped over the coating, whereby if the coating is resistant to at least 100 double rubs, satisfactory performance requirements are met. This requirement is consistent with 120 or higher. Curing at temperature, thus demonstrating that sufficient curing of the powder coating composition is indeed achieved at those temperatures. Example 5 20 Example 5 was carried out as in Example 4 except that as prepared in Example 2. 20 parts of the burnt amine-based plastic resin were used. A layer of the powder coating having a Tg above room temperature was electrostatically sprayed on an aluminum foil. The layer has a thickness of about 45 μm. The powder-covered aluminum flakes were placed in a gradient oven 27 200808847 over a period of 2 minutes. The coal box has a range from 100 乞 to 15 〇. (A gradient of: The aluminum flakes taken from the gradient oven were subjected to acetone double rubbing _ test' thereby curing for at least 100 double rubs required to meet the curing at 14 ° C or higher Thus, it was demonstrated that sufficient curing of the powder coated 5-layer composition was indeed achieved at those temperatures. Example 6 Example 6 was carried out as in Example 4 except for 20 parts of the alkane prepared as in Example 3. The amine-based plastic resin is used. A layer of Tg having a Tg above room temperature is electrostatically sprayed on a 10-aluminum sheet. The layer has a thickness of about 37 μm. The inscribed sheet attached to the material was placed in a gradient force box for 20 minutes. The oven had a gradient from loot: to 200 ° C. The aluminum sheet taken from the gradient oven was subjected to a C g with the double rub test, whereby the requirement for a double rub of at least 1 禁 is consistent with the cure at 15 18 (TC or higher, thus demonstrating that sufficient curing of the powder coating composition is indeed Those temperatures are reached. I: Figure Brief description; (n) [Main component symbol description] (none) 28