TW201226453A

TW201226453A - Prepregs based on a storage-stable reactive or highly reactive polyurethane composition

Info

Publication number: TW201226453A
Application number: TW100133799A
Authority: TW
Inventors: Friedrich Georg Schmidt; Sandra Reemers; Arnim Kraatz
Original assignee: Evonik Degussa Gmbh
Priority date: 2010-09-23
Filing date: 2011-09-20
Publication date: 2012-07-01
Also published as: AU2011304536B2; EP2619256A1; US20130231022A1; JP2013537928A; MX2013003169A; CN103210023A; AU2011304536A1; CA2811063A1; BR112013006846A2; RU2013118433A; ZA201302838B; WO2012038200A1; DE102010041239A1; KR20130109142A

Abstract

The invention relates to prepregs coloured with pigment or dye preparations and based on a storage-stable reactive or highly reactive polyurethane composition.

Description

201226453 六、發明說明：【發明所屬之技術領域】本發明係關於利用顏料或染料製劑著色且建基於貯存安定之反應性或高反應性聚胺基甲酸酯組成物之預浸體。【先前技術】由 DE 102009001793 、 DE 102009001806 ' DE 1 020 1 0293 5 5中獲知建基於貯存安定之反應性或高反〇應性聚胺基甲酸酯組成物的預浸體。【發明內容】本發明之目的是要製造建基於貯存安定的反應性或高反應性聚胺基甲酸酯組成物的經著色預浸體。所述之目的係利用顏料或染料製劑達成，該顏料或染料製劑適合於粉末塗覆應用，且在預浸體製造過程中已包 0 含在該建基於貯存安定的反應性或高反應性聚胺基甲酸酯組成物的基質材料組成物中。本發明之主題是經著色之預浸體，其基本上係由以下物質組成 A)至少一種纖維性載體，及 B )至少一種反應性或高反應性聚胺基甲酸酯組成物作爲基質材料，其中該聚胺基甲酸酯組成物基本上含有下列之混合物：作爲黏合劑之具有對異氰酸酯反應的官能基之聚合物b)，及作爲固化劑a -5- 201226453 )之經內部阻斷或利用阻斷劑阻斷之二或多異氰酸酯，且其中該基質材料另外包含 1. 具有<150奈米之粒子直徑的顏料，及/或 2. 染料。該預浸體之製造原則上可藉由任何方法進行。以合適的方式，藉由粉末浸漬作用（較佳藉由落塵（ dusting )方法）’將包含該染料及/或顏料之粉末狀聚胺基甲酸酯組成物B)施加至該載體。也有可能是流化床燒結方法、拉濟成形方法、或噴霧方法。該粉末（全部或部分）較佳藉由落塵方法施加至該纖維性載體上（例如玻璃、碳或芳醯胺纖維稀洋紗/織物之帶狀物上），然後固定。爲避免粉末損失，在該落塵方法之後，將經粉末處理之纖維性載體較佳直接在經加熱區中加熱（例如利用紅外光 )，以致粒子在其上被燒結，在此期間不應超過 8 0至 1 00 °c之溫度，以防止高反應性基質材料開始反應。這些預浸體視需要可組合成不同型式且切割成合適尺寸。該預浸體之製造也可藉由直接熔體浸漬方法進行。預浸體用之直接溶體浸漬方法的工作方式包括下列：首先，包含該染料及/或該顏料之反應性或高反應性聚胺基甲酸酯組成物B )由其個別成分製成熔體狀態。然後將此包含染料及/或顏料之該反應性聚胺基甲酸酯組成物B )的熔體直接施加至該纖維載體A)，換言之’以該B)之熔體浸漬該纖維性載體A )。在此之後’可將經冷卻之可貯存的預浸體在稍後進一步加工成複合材料。經由本發明之直 -6 - 201226453 接熔體浸漬方法，該纖維性載體進行極良好的浸漬作用，因爲當時液態之低黏度反應性聚胺基甲酸酯組成物極良好地潤濕該載體之纖維。也可以使用溶劑進行該預浸體之製造。製造預浸體之方法的工作方式包含下列：首先，包含該反應性或高反應性聚胺基甲酸酯組成物B )(其包含染料及/或顏料）之溶液或分散液係在合適之普通溶劑中由其個別成分製造。然後將該反應性聚胺基甲酸酯組成物B )之溶液或分散液直接施加至該纖維性載體A)上，因而以此溶液浸泡/浸漬該纖維性載體。其次，移除溶劑。較佳地，該溶劑在低溫下，較佳地<1〇〇 °C，例如藉由熱處理或真空應用而完全移除。在此之後，再次不含溶劑之可貯存的預浸體可另外在稍後被加工成複合材料。經由本發明之方法，纖維性載體進行極良好的浸漬作用，因爲該反應性聚胺基甲酸酯組成物溶液極良好地潤濕該載體之纖維。作爲本發明之方法用的適合溶劑，可以使用所有非質子性液體，其對反應性聚胺基甲酸酯不具反應性，對所用之反應性聚胺基甲酸酯組成物之個別成份顯現出合適溶劑力，且可在溶劑移除處理步驟中從該浸漬過該反應性聚胺基甲酸酯組成物之預浸體移除，除了留下略爲微量溶劑（ <0· 5重量％ )以外，藉此該經分離之溶劑的再循環是有利的。舉例而言，在此可以提及酮類（丙酮、甲基乙基酮、甲基異丁基酮、環己酮）、醚類（四氫呋喃）、酯類（乙 201226453 酸正丙酯、乙酸正丁酯、乙酸異丁酯、碳酸1,2-丙二酯、丙二醇甲基醚乙酸酯）。在冷卻至室溫後，本發明之預浸體在室溫下顯現出極高之貯存安定性，先決條件是該基質材料顯現出至少40 t之Tg。依照所含之反應性聚胺基甲酸酯組成物，這在室溫下是至少數日，但通常該預浸體在4〇t或更低之溫度下貯存安定達數星期。由此所產製之預浸體並非黏性的，且因此是極好處置的且極好另外加工的。依本發明所用之反應性或高反應性聚胺基甲酸酯組成物因此在該纖維性載體上顯現出極良好之黏合性及分布作用。在例如藉由在高溫下加壓以將該預浸體另外加工成複合物（複合材料）期間，該纖維性載體進行極良好的浸漬作用，因以下事實：在因該反應性或高反應性聚胺基甲酸酯組成物在高溫下之交聯反應使凝膠化發生或使全部聚胺基甲酸酯完全固化之前，當時液態之低黏度反應性或高反應性聚胺基甲酸酯組成物在該交聯反應之前極良好地潤濕該載體之纖維。由此所製造之預浸體可視需要地被組合成不同形式且被切割成合適尺寸。爲供該預浸體合倂成單一複合材料及使該基質材料交聯以獲得該基質，該預浸體被切割成合適尺寸，隨意地被縫合，或者在壓力及隨意施用真空下在合適塑膜中固定並壓縮。在本發明之內容中，依照固化時間，由該預浸體製造複合材料之程序係在使用反應性基質材料及在超過約 -8- 201226453 1 60 °C溫度的情況下進行（修正型I )，或在使用高反應性基質材料並有合適觸媒且在超過i 00 溫度的情況下進行（修正型II)。依照所用之反應性或高反應性聚胺基甲酸酯組成物及隨意添加之觸媒的組成，在製造該複合材料組件時之交聯反應的速率及該基質之性質二者可廣泛變化。在本發明之內容中，將製造該預浸體用之反應性或高反應性聚胺基甲酸酯組成物定義爲基質材料，且在該預浸〇體之描述中，仍具反應性或高反應性之聚胺基甲酸酯組成物係藉由本發明之方法施加至該纖維。基質定義爲由複合材料中經交聯之該反應性或高反應性聚胺基甲酸酯組成物所得之基質材料。載體在本發明中之纖維性載體係由纖維性材料（也常稱爲強化纖維）組成。通常，由該等纖維所組成之任何材料是 0 適合的，然而，較佳使用下列纖維材料：玻璃、碳、塑膠 (例如聚醯胺（芳醯胺）或聚酯）、天然纖維或無機纖維材料諸如玄武岩（basalt )纖維或陶瓷纖維（建基於鋁氧化物及/或矽氧化物之氧化物纖維）。可以使用多種纖維類型的混合物，例如芳醯胺及玻璃纖維之織物組合物、或碳及玻璃纖維之織物組合物。同樣地，可以製造具有不同纖維性載體之預浸體的雜合複合材料組件。主要由於其相對低之價格，玻璃纖維是最常用之纖維類型。在此原則上，所有形式之以玻璃爲底質之強化纖維 -9 - 201226453 是合適的（E玻璃、S玻璃、R玻璃、Μ玻璃、C玻璃、 ECR玻璃、D玻璃、AR玻璃、或中空玻璃纖維）。碳纖維通常用在高效能複合材料中，其中與玻璃纖維相比’較低密度與較高強度也是重要因素。碳纖維是由含碳原料其藉由熱解作用轉化成石墨構型的碳而製成之工業製纖維。在等向性與異向性之間做區別：等向性纖維僅具有低的強度及較低之工業重要性，異向性纖維顯現出高強度及剛性，同時具有低的破裂點延長性。在此，由植物及動物材料 (例如木料、纖維素、棉、苧麻、黃麻、亞麻、劍麻、或竹纖維）所得之所有的紡織纖維及纖維材料被描述成天然纖維。對碳纖維也同樣地，芳醯胺纖維顯現出負的熱膨脹係數，亦即在加熱時變短。其之比強度及彈性模數顯著地低於碳纖維之比強度及彈性模數。在與正膨脹係數之基質樹脂結合時，可以製造高尺寸安定之組件。與碳纖維強化之塑膠相比，芳醯胺纖維複合材料之壓縮強度明顯更低。方醯胺纖維之習知的商標名是得自 DuPont之Nomex®及 Kevlar®，或得自 Teijin 之 Teijincinex®、Twaron® 及 Technora®。由玻璃纖維、碳纖維、芳醯胺纖維、或陶瓷纖維所製成之載體是適合且較佳的。纖維材料是平的紡織片。非織造材料之平的紡織片（也稱爲針織物品）諸如針織品或針織織物’以及非針織片諸如紡織織物、非織造織物或編織織物是合適的。此外’在作爲載體之長纖維與短纖維之間做區別=依本發明也適合的是粗紗（r〇ving )及細紗（yarn )。所有之該等材料適合作爲本發明內容中之 -10 - 201226453 纖維性載體。強化纖維之總述揭示於“Composites Technologies, Paolo Ermanni (Version 4), Script for Lecture at ETH Ziirich, August 2007，Chapter 7”。基質材料原則上，所有的反應性或高反應性聚胺基甲酸酯組成物是適合作爲基質材料，即使是其他在室溫下貯存安定者 ^ 。依本發明，適合之聚胺基甲酸酯組成物係由以下物質之〇混合物組成：具有對NCO基團反應之官能基的聚合物b )(黏合劑，也描述爲樹脂），及經暫時鈍化（亦即經內部阻斷或利用阻斷劑阻斷）之二或多異氰酸酯（也描述爲固化劑a )(成分a ))。作爲聚合物b)(黏合劑）之官能基，羥基、胺基、及硫醇基是合適的，這些基團在添加時與該游離之多氰酸酯基反應且因此將該聚胺基甲酸酯交聯且固化。該黏合劑 Q 成分必須具有固態樹脂本質（玻璃轉換溫度高於室溫）。可能之黏合劑是具有20至500毫克KOH/克之OH値及 250至6000克/莫耳之平均分子量的聚酯類、聚醚類、聚丙烯酸酯類、聚碳酸酯類、及聚胺基甲酸酯類。特佳地，使用具有20至150毫克KOH /克之OH値及500至 6000克/莫耳之平均分子量的含羥基的聚酯類或聚丙烯酸酯類。當然，也可以使用此等聚合物之混合物。選擇具有官能基之聚合物b)之量，以使對於成份b)之每一官能基而言，可消耗成分a)之0.6至2個 NCO當量或0.3 -11 - 201226453 至1個脈一·嗣基（uretdione)。作爲固化成分a)，使用二或多異氰酸酯類，其利用阻斷劑阻斷或經內部阻斷（脲二酮）。依本發明所用之二及多異氰酸酯類可以由任何芳族、脂族、環脂族及/或（環）脂族二及/或多異氰酸酯類組成。作爲芳族二或多異氰酸酯類，原則上所有已知的芳族化合物是適合的。特別適合的是二異氰酸1，3-及1,4-苯二酯、二異氰酸1，5-萘二酯、二異氰酸聯甲苯酯（1〇1丨(1丨116 diisocyanate)、二異氰酸2,6-甲苯二酯、二異氰酸2,4-甲苯二酯（2,4-TDI)、二異氰酸2,4’-二苯基甲烷酯（ 2,4’-MDI)、二異氰酸4,4’-二苯基甲烷酯、二異氰酸二苯基甲烷酯（MDI)單體與二異氰酸二苯基甲烷酯寡聚物的混合物（聚合的MDI)、二異氰酸苯二甲酯 '二異氰酸四甲基苯二甲酯及三異氰醯甲苯。適合之脂族二或多異氰酸酯類的直鏈型或支鏈型伸院基殘基有利地具有3至16個碳原子（較佳地4至12個碳原子），且適合之環脂族或（環）脂族二異氰酸酯類的環伸烷基殘基有利地具有4至1 8個碳原子（較佳地6至1 5 個碳原子）。同樣地，精於此技藝之人士充分地了解：（環）脂族二異氰酸酯類是指與環狀且脂族基團鍵結的 NCO基團，如同二異氰酸異佛爾酮酯之情況。相反地’ 環脂族二異氰酸酯類據了解是指那些僅具有與該環脂族環直接鍵結的N C Ο基團者，例如H 12 M D 1 °貫例是二異氰酸環己院醋、二異氰酸甲基環己院醋、一異氰酸乙基丨哀己院 -12- 201226453 酯、二異氰酸丙基環己烷酯、二異氰酸甲基二乙基環己烷酯、二異氰酸丙烷酯、二異氰酸丁烷酯、二異氰酸戊烷酯、二異氰酸己烷酯、二異氰酸庚烷酯、二異氰酸辛烷酯、二異氰酸壬烷酯、三異氰酸壬烷酯’諸如二異氰酸4 -異氰酸甲基-1,8-辛烷酯（TIN)、二及三異氰酸癸烷酯、二及三異氰酸十一烷酯、及二及三異氰酸十二烷酯。二異氰酸異佛爾酮酯（IP DI )、二異氰酸伸己二酯（ HDI )、二異氰酸二環己基甲烷（H12MDI )、二異氰酸2- C) 甲基戊烷酯（MPDI )、二異氰酸2,2,4-三甲基己二酯/ 二異氰酸2,4,4-三甲基己二酯（丁1^01)及/或二異氰酸原冰片烷酯（NBDI )是較佳的。相當特佳地，使用IPDI 、HDI、TMDI及/或H12MDI，且異氰脲酸酯類也是可用的。並且，1,3 -二異氰酸4 -甲基-環己院醋、二異氰酸2-丁基-2-乙基伸戊二酯、異氰酸3 (4)-異氰酸甲基-1-甲基環己酯、異氰酸2-異氰酸丙基環己酯、二異氰酸2,4’-q 伸甲基雙（環己酯）、及1,4-二異氰酸基-4-甲基戊烷是合適的。當然，也可以使用該等二及多異氰酸酯類之混合物。另外，較佳使用寡或聚異氰酸酯類，其可藉由利用脲烷、脲甲酸酯、脲、縮二脲、脲二酮、胺、異氰脲酸酯、碳化二亞胺、脲酮亞胺（uretonimine)、噁二嗪三酮、或亞胺基噁二嗪二酮結構連接而由該等二或多異氰酸酯或其混合物製造。異氰脲酸酯（特別是選自IPDI及/或HDI )是特別適合的。 -13- 201226453 依本發明所用之多異氰酸酯係經阻斷的。可能用於此的是外部阻斷劑諸如乙醯基乙酸乙酯、二異丙胺、甲基乙基酮肟、丙二酸二乙酯、£ -己內醯胺、1,2,4-三唑、酚或經取代之酚類及/或3,5-二甲基吡唑。較佳使用的固化劑是含有異氰脲酸基及經-己內醯胺阻斷之異氰酸酯結構的IPDI加合物。內部阻斷也是可能的，且這是較佳被使用的。經由脲二酮結構形成二聚體以進行內部阻斷，該脲二酮結構在高溫下再次分裂成原先存在之異氰酸酯結構且因此在動態的狀況下與該黏合劑進行交聯。隨意地，該反應性聚胺基甲酸酯組成物可含有另外之觸媒。這些是含量爲0.001至1重量％之有機金屬觸媒（諸如二月桂酸二丁基錫（DBTL)、辛酸錫、新癸酸鉍）、或三級胺（諸如I,4-二氮雜雙環[2.2.2]辛烷）。這些依本發明所用之反應性聚胺基甲酸酯組成物在一般條件下被固化，例如利用DBTL觸媒，在高於l6〇°C，經常在高於約1 8 0 °C的溫度且指明爲修正型I。爲要製造反應性聚胺基甲酸酯組成物，可以添加總量爲0.05至5重量％之在粉末塗覆技術中常用之添加劑，諸如勻染劑（例如聚矽氧烷或丙烯酸酯）、光安定劑（例如位阻胺），或其他添加劑（例如在E P 6 6 9 3 5 3中所述的 )° 在本發明之內容中，反應性（修正型I )意爲：如上述之依本發明所用的反應性聚胺基甲酸酯組成物，視該載 -14- 201226453 體本質而定，在高於160°C的溫度固化。本發明之反應性聚胺基甲酸酯組成物在一般條固化，例如利用DBTL觸媒，在高於16CTC，經常約1 8 0 °c的溫度。依本發明所用之聚胺基甲酸酯組固化時間一般在5至60分鐘內。較佳地，在本發明中，使用由含有脲二酮基之甲酸酯組成物B)製成之基質材料B)，該組成物本上含有 a)至少一種含脲二酮基之固化劑，其建基於、（環）脂族或環脂族脲二酮基之多異氰及含羥基之化合物的加成聚合化合物，其化劑在低於40°C時是固態且在高於125°C 態，且具有少於5重量％之游離NCO含: 25重量％之脲二酮含量， b )至少一種含羥基之聚合物，其在低於4 0 °C 態且在高於1 2 5 °C時是液態，且具有在2 0 毫克KOH/克之間的OH値， c) 隨意地，至少一種觸媒，及 d) 隨意地，聚胺基甲酸酯化學中習知的輔劑劑，以致該二成分a)及b)之含量比率使得對於成分每一個羥基而言消耗成分a)之0.3至1個脲二嗣佳0.45至0.55個。後者相當於〇·9至1.1/1的 OH比率。件下被在高於成物之聚胺基 B)基含脂族酸酯類中該固時是液匱及3 - 時是固至200 及添加 b )之基，較 NCO/ -15- 201226453 含脲二酮基之多異氰酸酯類是習知的，且是例如描述於 US 4,476,054、US 4,912,210、US 4,929,724 及 EP 417 6 03中。關於異氰酸酯類二聚合成爲脲二酮類的工業相關方法的綜合槪述係在J· Prakt. Chem. 336 ( 1 994 ) 185-200中給予。通常，異氰酸酯類轉化成脲二酮類係在可溶性二聚合觸媒諸如二烷基胺基吡啶類、三烷基膦類、磷酸三醯胺類、或咪唑類存在下進行。該反應（其隨意地在溶劑中進行，但較佳無溶劑地進行）在達到所要之轉化程度時係藉由添加觸媒毒物以停止。然後過多之異氰酸酯單體係藉由短路徑蒸發作用移除。若該觸媒是具有足夠揮發性，則在該單體移除過程中該反應混合物可以不含該觸媒。在此情況中，可以省略觸媒毒物之添加。基本上，多種異氰酸酯類適合用於製造含脲二酮基之聚異氰酸酯類。可以使用上述二及多異氰酸酯類。然而，選自任何脂族、環脂族及/或（環）脂族之二及多異氰酸酯類是較佳的。依本發明，使用二異氰酸異佛爾酮酯（IP DI )'二異氰酸伸己二酯（HDI)、二異氰酸基二環己基甲烷（H12MDI) 、二異氰酸2-甲基戊烷酯（MPDI)、二異氰酸2,2,4-三甲基伸己二酯/二異氰酸 2,4,4 -三甲基伸己二酯（TMDI )及/或二異氰酸原冰片烷酯（NBDI )。相當特佳地使用IPDI、HDI、TMDI及/或H12MDI，且異氰脲酸酯類也是可用的。相當特佳地，IPDI及/或HDI係用於該基質材料= 這些含脲二酮基之多異氰酸酯轉化成爲含脲二酮基之固化 -16- 201226453 劑a)的作用係包含該游離NCO基與作爲鏈延長劑之含羥基的單體或聚合物（例如聚酯類、聚硫醚類、聚醚類、聚內醯胺類、聚環氧化物、聚酯醯胺類、聚胺基甲酸酯類、或低分子量之二、三及/或四元醇）及隨意地作爲鏈終止劑之單胺類及/或一元胺類的反應，且已經常被描述（ EP 6 6 9 3 53、EP 6 6 9 3 54、DE 30 30 572 ' EP 6 3 9 5 98 或 EP 803 524 )。較佳之具有脲二酮基的固化劑a)具有少於5重量％之游離NCO含量及3至25重量％之脲二酮基含量（較佳 6至18重量％，以分子量爲84之C2N202計算）。聚酯類及二元醇單體是較佳的。除了該脲二酮基之外，該固化劑也可以具有異氰脲酸酯、縮二脲、脲甲酸酯、胺基甲酸酯及/或脲結構。爲供該含羥基之聚合物b)，較佳使用具有20至200 毫克KOH/克之OH値的聚酯類、聚醚類、聚丙烯酸酯類、聚胺基甲酸酯類及/或聚碳酸酯類。特佳使用具有30 至150毫克KOH/克之OH値及500至6000克/莫耳之平均分子量的聚酯類，其在低於40 °C時爲固態且在高於 1 25 °C時爲液態。此種黏合劑例如已描述於EP 669 354及 EP 254 152中。當然，也可以使用此等聚合物之混合物。選擇含羥基之聚合物b)的量，以致對於成份b)之每一羥基而言，消耗〇.3至1個（較佳至0.5個）成分a )之脲二酮基。隨意地’可將另外的觸媒c)包含在本發明之反應性聚胺基甲酸酯組成物B)中。這些是含量爲 -17- 201226453 0.001至1重量％之有機金屬觸媒（例如二月桂酸二丁基錫、辛酸鋅、新癸酸鉍）、或三級胺類（例如14-二氮雜雙環[2.2.2]辛烷）。這些依本發明所用之反應性聚胺基甲酸酯組成物係在一般條件下被固化，例如利用D B T L觸媒，在超過160 °C ’經常是超過約180。(：的溫度，且命名爲修正型I。爲要製造本發明之反應性或高反應性聚胺基甲酸酯組成物’可以添加總量爲0.05至5重量％之在粉末塗覆技術中常用之添加劑，例如聚矽氧烷或丙烯酸酯類）、光安定劑（例如位阻胺類）、或其他添加劑（例如在 EP 669 353中所述者）。依本發明所用之反應性聚胺基甲酸酯組成物在一般條件下被固化，例如利用DBTL觸媒，在超過160°C，經常是超過約1 8 0 °C的溫度。依本發明所用之反應性聚胺基甲酸酯組成物提供極良好之流動且因此提供良好之浸漬行爲且在固化的狀態時提供優越之抗化學品性。此外，加上使用脂族交聯劑（例如IPDI或H12MDI )，也同時達成良好之耐候性。特佳地在本發明中，使用由以下物質製成之基質材料 B)至少一種高反應性之含脲二酮基的聚胺基甲酸酯組成物，其基本上含有 a )至少一種含脲二酮基之固化劑；及 b )隨意地，至少一種具有對NCO基反應之官能基 -18- 201226453 的聚合物； c) 0.1至5重量％之至少—種觸媒，其選自具有幽素氫氧根、醇根、或有機酸根或無機酸根陰離子作爲平衡離子之四級銨鹽及/或四級鱗鹽 :及 d) 〇.1至5重量％之至少—種輔觸媒，其選自 dl)至少一種環氧化物，及/或 0 d2)至少一種乙醯基丙酮酸金屬鹽及/或乙醯基丙酮酸四級銨鹽及/或乙醯基丙酮酸四級錢鹽；及 e )隨意地’聚胺基甲酸酯化學中習知的輔劑及添加劑。相當特別地’使用由以下物質製成之基質材料B )： B)具有至少一種高反應性粉末狀之含脲二酮基之聚胺基甲酸酯組成物B)作爲基質材料，該組成物b)基本 0 上含有 a) 至少一種含脲二酮基之固化劑，其建基於含脂族、（環）脂族或環脂族脲二酮基之多異氰酸酯類及含羥基之化合物的加成聚合化合物，其中該固化劑在低於40°C時是固態且在高於125 °C時是液態，且具有少於5重量％之游離N C Ο 含量及3-2 5重量％之脲二酮含量， b) 至少一種含羥基之聚合物，其在低於40°C時是固態且在高於125 °C時是液態，且具有在20至 -19- 201226453 200毫克KOH /克之間的〇H値， c) 0.1至5重量％之至少一種觸媒，其選自素、氫氧根、醇根、或有機酸根或無機離子作爲平衡離子之四級銨鹽及/或四 :及 d) 0.1至5重量％之至少一種輔觸媒，其選 d 1 )至少一種環氧化物，及/或 d2)至少一種乙醯基丙酮酸金屬鹽及/或乙酮酸四級銨鹽及/或乙醯基丙酮酸四級及 e )隨意地，聚胺基甲酸酯化學中習知的輔加劑，以致該二成分a)及b)之含量比率使得對於成分每一個羥基而言消耗成分a)之0.3至1個脲二嗣佳0.6至0.9個。後者對應於0.6至2/1或1.2至的NCO/ OH比率。這些依本發明所用之高反應性甲酸酯組成物在100至160°c溫度固化且命名爲修〇本發明之適合的高反應性之含脲二酮基的聚胺酯組成物含有以下物質之混合物：經暫時鈍化的二氰酸酯類，亦即含脲二酮基（經內部阻斷）之二或酸酯類，也描述爲固化劑a ):及依本發明所含之 )及d);且隨意地加上具有對NCO基反應之官聚合物（黏合劑），其也描述爲樹脂b )。該等觸具有鹵酸根陰級鍈鹽白醯基丙錢鹽；劑及添 b )之基，較 1.8/1 聚胺基正型II 基甲酸或多異多異氰觸媒C 能基的媒確保 -20 - 201226453 該含脲二酮基之聚胺基甲酸酯組成物在低溫下固化。含脲二酮基之聚胺基甲酸酯組成物因此是高反應性的。作爲成分a)及b)，使用諸如上述者。作爲c)之觸媒，使用具有鹵素、氫氧根、醇根、或有機酸根或無機酸根陰離子作爲平衡離子的四級銨鹽（較佳是四烷基銨鹽）及/或四級鱗鹽。這些觸媒的實例是：甲酸四甲基銨、乙酸四甲基銨、丙酸四甲基銨、丁酸四甲基銨、苯甲酸四甲基銨、甲酸四乙基銨、乙酸四乙基銨、丙酸四乙基銨、丁酸四乙基銨、苯甲酸四乙基銨、甲酸四丙基銨、乙酸四丙基銨、丙酸四丙基銨、丁酸四丙基銨、苯甲酸四丙基銨、甲酸四丁基銨、乙酸四丁基銨、丙酸四丁基銨、丁酸四丁基銨、及苯甲酸四丁基銨以及乙酸四丁基鐵、甲酸四丁基錢及乙酸乙基三苯基錢、苯並三唑化四丁基鍈（tetrabytylphosphonium benzotriazolate )、酣化四苯基鱗、及癸酸三己基十四基鱗、氫氧化甲基三丁基銨、氫氧化甲基三乙基銨、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化四戊基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化四癸基銨、氫氧化十四烷基三己基銨、氫氧化四-十八烷基銨、氫氧化苄基三甲基銨、氫氧化苄基三乙基銨、氫氧化三甲基苯基銨、氫氧化三乙基甲基銨、氫氧化三甲基乙烯基銨、甲醇化甲基三丁基銨、甲醇化甲基三乙基銨、甲醇化四甲基銨、甲醇化四乙基敍、甲醇化四丙基銨、申醇化四丁基銨、甲醇化四戊基銨、甲醇化四己基銨、甲醇化四辛基銨、 -21 - 201226453 甲醇化四癸基銨、甲醇化十四烷基三己基銨、甲醇化四-十八烷基銨、甲醇化苄基三甲基銨、甲醇化苄基三乙基敍、甲醇化三甲基苯基銨、甲醇化三乙基甲基銨、甲醇化三甲基乙烯基銨、乙醇化甲基三丁基銨、乙醇化甲基三乙基銨、乙醇化四甲基銨、乙醇化四乙基銨、乙醇化四丙基銨、乙醇化四丁基銨、乙醇化四戊基銨、乙醇化四己基銨、乙醇化四辛基銨、乙醇化四癸基銨、乙醇化十四烷基三己基銨、乙醇化四-十八烷基銨、乙醇化苄基三甲基銨、乙醇化苄基三乙基敍、乙醇化三甲基苯基銨、乙醇化三乙基甲基銨、乙醇化三甲基乙烯基銨、苄基化甲基三丁基銨、苄基化甲基三乙基銨、苄基化四甲基銨、苄基化四乙基銨、苄基化四丙基銨、苄基化四丁基銨、苄基化四戊基銨、苄基化四己基銨、苄基化四辛基銨、苄基化四癸基銨、苄基化十四基三己基銨、苄基化四-十八烷基敍、苄基化苄基三甲基銨、苄基化苄基三乙基銨、苄基化三甲基苯基銨、苄基化三乙基甲基銨、苄基化三甲基乙烯基銨、氟化四甲基錶'氟化四乙基銨、氟化四丁基銨、氟化四辛基銨、氟化苄基三甲基銨、氫氧化四丁基鱗、氟化四丁基錢、氯化四丁基銨、溴化四丁基銨、碘化四丁基銨、氯化四乙基銨、溴化四乙基銨、碘化四乙基銨、氯化四甲基銨、溴化四甲基銨、碘化四甲基銨、氯化苄基三甲基銨、氯化苄基三乙基銨、氯化苄基三丙基銨、氯化苄基三丁基銨、氯化甲基三丁基銨、氯化甲基三丙基銨、氯化甲基三乙基銨、氯化甲基三苯基銨、氯化苯基三甲基銨、溴化苄基三甲基 -22- 201226453 銨、溴化苄基三乙基銨、溴化苄基三丙基銨、溴丁基銨、溴化甲基三丁基銨、溴化甲基三丙基銨基三乙基銨、溴化甲基三苯基銨、溴化苯基三甲化苄基三甲基銨、碘化苄基三乙基銨、碘化苄基、碘化苄基三丁基鉸、碘化甲基三丁基銨、碘化基銨、碘化甲基三乙基銨、碘化甲基三苯基銨及三甲基銨、氫氧化甲基三丁基銨、氫氧化甲基三 ^ 氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙〇氧化四丁基銨、氫氧化四戊基銨、氫氧化四己基化四辛基銨、氫氧化四癸基銨、氫氧化十四烷基、氫氧化四-十八烷基銨、氫氧化苄基三甲基銨苄基三乙基銨、氫氧化三甲基苯基銨、氫氧化三銨、氫氧化三甲基乙烯基銨、氟化四甲基銨、氟銨、氟化四丁基銨、氟化四辛基銨及氟化苄基三這些觸媒可以單獨添加或以混合物形式添加。較 Q 甲酸四乙基銨及/或氫氧化四丁基銨。觸媒C)之含量以該基質材料之總調和物爲以是0.1至5重量％，較佳是0.3至2重量％。依本發明之一修正型也包括此種觸媒c )結合物b )之官能基。除此之外，這些觸媒可被惰環繞且藉此被包覆。使用環氧化物作爲輔觸媒d 1 )。在此可能水甘油基醚類及縮水甘油基酯類、脂族環氧化物雙酚A及甲基丙烯酸縮水甘油基酯之二縮水甘化苄基三、溴化甲基錶、确三丙基銨甲基三丙碘化苯基乙基銨、基錢、氫銨、氫氧三己基銨、氫氧化乙基甲基化四乙基甲基銨。佳使用苯基準計可合至該聚性外層所是例如縮、建基於油基醚類 -23- 201226453 。此種環氧化物之實例是異氰脲酸三縮水甘油基酯（ TGIC，商品名 ARALDIT 810，Huntsman)、對苯二甲酸二縮水甘油基酯與苯偏三酸三縮水甘油基酯之混合物（商品名 ARALDIT 910 及 912，Huntsman)、維沙酸（ versatic acid)之縮水甘油基酯類（商品名 KARDURA E10，Shell) 、3’，4’-環氧基環己烷羧酸3,4-環氧基環己基甲酯（ECC )、建基於雙酚A之二縮水甘油基醚類（商品名 EPIKOTE 828，Shell )、乙基己基縮水甘油基醚、丁基縮水甘油基醚、季戊四醇四縮水甘油基醚（商品名 POLYPOX R16，UP PC AG)及其他具有游離環氧基之波利波克斯（polyp οχ )型。也可以使用混合物。較佳使用 ARALDIT PT910 及 9 1 2。作爲輔觸媒d2)，乙醯基丙酮酸金屬鹽是可能的。這些的實例是單獨或混合之乙醯基丙酮酸鋅、乙醯基丙酮酸鋰及乙醯基丙酮酸錫。較佳使用乙醯基丙嗣酸鋅。作爲輔觸媒d2)，乙醯基丙酮酸四級銨鹽類或乙醯基丙酮酸四級鱗鹽類也是可能的。此種觸媒之實例是乙醯基丙酮酸四甲基銨、乙醯基丙酮酸四乙基銨、乙醯基丙酮酸四丙基銨、乙醯基丙酮酸四丁基銨、乙醯基丙酮酸苄基三甲基銨、乙醯基丙酮酸苄基三乙基銨、乙醯基丙酮酸四甲基鱗、乙醯基丙酮酸四乙基鱗、乙醯基丙酮酸四丙基鳞、乙醯基丙酮酸四丁基鱗、乙醯基丙酮酸苄基三甲基鎸、及乙醯基丙酮酸苄基三乙基錢。特佳地’也可以使用乙醯基丙酮酸四乙基銨及/或乙醯 -24- 201226453 基丙酮酸四丁基銨。當然，也可以使甩此等觸媒之混合物〇輔觸媒d 1 )及/或d2 )之量以該基質材料之總調和物爲基準計，可以是0.1至5重量％，較佳是0.3至2重量％。利用依本發明所用之高反應性且因此低溫固化之聚胺基甲酸酯組成物B )，在1 0 0至1 6 0 °C之固化溫度，不僅可以節省能量及固化時間，也可以使用很多對溫度敏感的 C) 載體。在本發明之內容中，高反應性（修正型II )意爲：依本發明所用之含脲二酮基之聚胺基甲酸酯組成物，依照載體本質而定’在100至160 °c之溫度固化。該固化溫度較佳是120至150°C，特佳是130至140°C。依本發明所用之聚胺基甲酸酯組成物的固化時間在5至60分鐘之間。依本發明所用之高反應性之含脲二酮基的聚胺基甲酸 Q 酯組成物B)提供極良好之流動行爲，且因此提供良好之浸漬行爲’且在固化的狀態時提供優越之抗化學品性。此外，加上使用脂族交聯劑（例如I p D I或Η ! 2 M D I )，也同時取得良好之耐候性。適合之顏料原則上是所有已知之顏料。利用選自已知種類之天然及合成無機顏料的顏料。有用的天然顏料包括土色料例如綠土、黃赭石或赭土，及礦物色料例如鐵氧化物、孔雀石或硃砂。並且適合的是無機合成顏料例如碳黑、鉻顏料、鈷顏料、鐵顏料、群青藍色 -25- 201226453 、或白顔料例如二氧化鈦。同樣適合的是天然有機顏料及合成有機顏料諸如偶氮顏料（亮黃、永久紅）、多環顏料 (酞花青藍、海利綠（heliogen ))、或二酮基吡咯並吡咯顏料。同樣亦適合的是金屬效果顏料或珠光顏料。此種顏料之實例是：普魯士藍（顏料藍2 7 C . 1.7 7 5 1 〇 )、亮黃（顏料黃 74 C.I. 1 1741 )、鎘黃（顏料黃35 C.I. 77205 )、鎘紅（顏料紅 108 C.I.772 02 )、氧化鉻綠（顏料綠 17 C.I. 77288)、鈷藍（顏料藍 28 C.I. 77346) '鈷藍綠松石光（顏料藍36 c.I. 77343)、鈷紫光（顏料紫49 C.I. 7 73 62 )、氧化鐵黑（顏料黑11 c.i 77499 )、伊爾加勤（irgazine )紅（顏料紅 254 C.I. 56110)、錳紫（顏料紫 16 C.I. 77742)、酞花青藍（ org )(顏料藍15 C.I. 74 1 60 )、鈦白（顏料白 C.I. 77891)、群青藍（顏料藍29 C.I. 77007)、群青紅A ( 顏料紅 259 C.I. 77007)、赭土（顏料棕 7 C.I. 77491) 〇適合之染料是所有已知的染料，特別是反應性染料、分散性染料、顏料染料' 酸染料、顯色（deveI〇ping )染料、IW離子或鹼性染料 '偶合染料、媒染染料、鹽染料、金屬錯合染料、直接染料。在本發明內容中可用之重要的染料類型是蒽醌染料、偶氮染料、一噁嗪染料、靛藍染料、硝基染料、亞硝基染料、酞花青染料、硫染料、三苯基甲烷染料。 k別適合於粉末塗覆應用之染料及顏料係例如在 -26- 201226453201226453 VI. Description of the Invention: [Technical Field] The present invention relates to a prepreg which is colored by a pigment or dye preparation and which is based on a storage-reactive or highly reactive polyurethane composition. [Previously] A prepreg based on a storage-stabilized or highly reactive urethane composition is known from DE 102009001793, DE 102009001806 ' DE 1 020 1 0293 5 5 . SUMMARY OF THE INVENTION It is an object of the present invention to produce a colored prepreg based on a storage stable or highly reactive polyurethane composition. The object is achieved by a pigment or dye formulation suitable for powder coating applications and which has been included in the prepreg manufacturing process in the storage-based stable or highly reactive poly-polymer. A matrix material composition of a urethane composition. The subject of the invention is a pigmented prepreg consisting essentially of A) at least one fibrous carrier, and B) at least one reactive or highly reactive polyurethane composition as matrix material Wherein the polyurethane composition substantially comprises a mixture of the polymer b) having an isocyanate-reactive functional group as a binder, and the internal blocking as a curing agent a-5-201226453) Or blocking the di- or polyisocyanate with a blocking agent, and wherein the matrix material additionally comprises 1. <150 nm particle diameter pigment, and / or 2. Dyes. The manufacture of the prepreg can in principle be carried out by any method. In a suitable manner, the powdered polyurethane composition B) comprising the dye and/or pigment is applied to the carrier by powder impregnation (preferably by dusting method). It may also be a fluidized bed sintering method, a Lazi forming method, or a spraying method. The powder (in whole or in part) is preferably applied to the fibrous carrier by a dusting method (e.g., glass, carbon or linoleum fiber ray/fabric tape) and then fixed. In order to avoid powder loss, after the dusting method, the powder-treated fibrous carrier is preferably heated directly in the heated zone (for example using infrared light) so that the particles are sintered thereon, during which time it should not exceed 8 A temperature of 0 to 100 ° C to prevent the highly reactive matrix material from starting to react. These prepregs can be combined into different types and cut to size as needed. The manufacture of the prepreg can also be carried out by a direct melt impregnation method. The working mode of the direct solution impregnation method for the prepreg includes the following: First, the reactive or highly reactive polyurethane composition comprising the dye and/or the pigment B) is melted from its individual components. Body state. The melt of the reactive polyurethane coating B) containing the dye and/or pigment is then applied directly to the fiber carrier A), in other words the fiber carrier A is impregnated with the melt of the B ). Thereafter, the cooled storable prepreg can be further processed into a composite later. The fibrous carrier is subjected to a very good impregnation via the direct -6 - 201226453 melt impregnation method of the present invention, since the liquid low viscosity reactive polyurethane composition is then very well wetted by the carrier. fiber. The manufacture of the prepreg can also be carried out using a solvent. The method of producing the prepreg comprises the following: First, a solution or dispersion comprising the reactive or highly reactive polyurethane composition B), which comprises a dye and/or a pigment, is suitable Common solvents are made from their individual components. The solution or dispersion of the reactive polyurethane composition B) is then applied directly to the fibrous carrier A), thereby soaking/impregnating the fibrous carrier with the solution. Second, remove the solvent. Preferably, the solvent is at a low temperature, preferably <1 ° ° C, completely removed by heat treatment or vacuum application, for example. After this, the solvable prepreg which is again free of solvent can be additionally processed into a composite material later. By means of the process of the invention, the fibrous carrier undergoes a very good impregnation because the reactive polyurethane composition solution wets the fibers of the carrier very well. As suitable solvents for the process of the invention, it is possible to use all aprotic liquids which are not reactive towards reactive polyurethanes and which exhibit the individual components of the reactive polyurethane compositions used. Suitable solvent strength, and can be removed from the prepreg impregnated with the reactive polyurethane composition in a solvent removal treatment step, except that a slight trace of solvent is left ( In addition to <0·5 wt%), recycling of the separated solvent is advantageous. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (tetrahydrofuran), esters (ethyl 201226453 n-propyl acetate, acetic acid) can be mentioned here. Butyl ester, isobutyl acetate, 1,2-propylene diester, propylene glycol methyl ether acetate). After cooling to room temperature, the prepreg of the present invention exhibits extremely high storage stability at room temperature, provided that the matrix material exhibits a Tg of at least 40 t. Depending on the reactive polyurethane composition contained, this is at room temperature for at least several days, but typically the prepreg is stored at a temperature of 4 Torr or less for several weeks. The prepreg thus produced is not viscous and is therefore extremely well handled and extremely well processed. The reactive or highly reactive polyurethane composition used in accordance with the present invention thus exhibits excellent adhesion and distribution on the fibrous carrier. During the additional processing of the prepreg into a composite (composite), for example by pressurization at elevated temperatures, the fibrous carrier undergoes a very good impregnation due to the fact that due to the reactivity or high reactivity A low viscosity or highly reactive polyurethane in the liquid state prior to the cross-linking reaction of the polyurethane composition at high temperatures to allow gelation to occur or to fully cure the entire polyurethane. The composition wets the fibers of the carrier very well before the crosslinking reaction. The prepregs thus produced can be combined into different forms as needed and cut into suitable sizes. In order to combine the prepreg into a single composite material and crosslink the matrix material to obtain the substrate, the prepreg is cut into suitable sizes, randomly sewed, or suitably molded under pressure and under vacuum. The film is fixed and compressed. In the context of the present invention, the procedure for making a composite from the prepreg is carried out using a reactive matrix material and at a temperature in excess of about -8 to 201226453 1 60 °C (corrected type I), depending on the curing time. Or using a highly reactive matrix material with a suitable catalyst and at temperatures in excess of i 00 (correction II). Depending on the reactive or highly reactive polyurethane composition used and the composition of the catalyst which is optionally added, both the rate of crosslinking reaction and the nature of the substrate in the manufacture of the composite component can vary widely. In the context of the present invention, a reactive or highly reactive polyurethane composition for making the prepreg is defined as a matrix material and, in the description of the prepreg, remains reactive or The highly reactive polyurethane composition is applied to the fiber by the method of the present invention. A matrix is defined as a matrix material derived from the reactive or highly reactive polyurethane composition crosslinked in a composite. Carrier The fibrous carrier in the present invention is composed of a fibrous material (also often referred to as a reinforcing fiber). Generally, any material composed of such fibers is suitable for 0. However, it is preferred to use the following fibrous materials: glass, carbon, plastic (for example, polyamine (arylamine) or polyester), natural or inorganic fibers. Materials such as basalt fibers or ceramic fibers (based on oxide oxides of aluminum oxide and/or niobium oxide). Mixtures of various fiber types can be used, such as fabric compositions of linaloamine and glass fibers, or fabric compositions of carbon and glass fibers. Likewise, hybrid composite components having prepregs of different fibrous carriers can be made. Fiberglass is the most commonly used fiber type, mainly due to its relatively low price. In principle, all forms of glass-based reinforced fiber -9 - 201226453 are suitable (E glass, S glass, R glass, bismuth glass, C glass, ECR glass, D glass, AR glass, or hollow) glass fiber). Carbon fibers are commonly used in high performance composites where lower density and higher strength are also important factors. Carbon fiber is an industrial fiber made from a carbonaceous material which is converted into a graphite configuration by pyrolysis. The distinction between isotropic and anisotropic: isotropic fibers have only low strength and low industrial importance, and anisotropic fibers exhibit high strength and rigidity, while having low elongation at break. Here, all of the textile fibers and fibrous materials obtained from plant and animal materials such as wood, cellulose, cotton, ramie, jute, linen, sisal, or bamboo fibers are described as natural fibers. Similarly for carbon fibers, the linalin fibers exhibit a negative coefficient of thermal expansion, i.e., become shorter upon heating. Its specific strength and modulus of elasticity are significantly lower than the specific strength and modulus of elasticity of carbon fibers. When combined with a matrix resin having a positive expansion coefficient, it is possible to manufacture a high-size stable component. Compared to carbon fiber reinforced plastics, melamine fiber composites have significantly lower compressive strength. The well-known trade names for the chitosan fibers are Nomex® and Kevlar® from DuPont, or Teijincinex®, Twaron® and Technora® from Teijin. A carrier made of glass fiber, carbon fiber, linalin fiber, or ceramic fiber is suitable and preferred. The fibrous material is a flat textile sheet. Flat woven sheets of nonwoven material (also referred to as knit items) such as woven or knitted fabrics and non-woven sheets such as woven fabrics, nonwoven fabrics or woven fabrics are suitable. Further, the difference between the long fibers and the short fibers as the carrier is also suitable for the roving and the yarn according to the present invention. All of these materials are suitable as a fibrous carrier of the present invention -10 - 201226453. A general overview of reinforced fibers is disclosed in "Composites Technologies, Paolo Ermanni (Version 4), Script for Lecture at ETH Ziirich, August 2007, Chapter 7". Matrix Materials In principle, all reactive or highly reactive polyurethane compositions are suitable as matrix materials, even if others are stored at room temperature for stability. According to the invention, a suitable polyurethane composition consists of a ruthenium mixture of the following: a polymer b) having a functional group reactive with an NCO group (adhesive, also described as a resin), and temporarily Di- or polyisocyanate (also described as curing agent a) (ingredient a)) which is passivated (ie blocked by internal blocking or blocked with a blocking agent). As functional groups of the polymer b) (binder), a hydroxyl group, an amine group, and a thiol group are suitable, and these groups are reacted with the free polycyanate group upon addition and thus the polyamino group The acid ester crosslinks and cures. The binder Q component must have a solid resin nature (glass transition temperature above room temperature). Possible binders are polyesters, polyethers, polyacrylates, polycarbonates, and polyaminocarboxylic acids having an OH oxime of from 20 to 500 mg KOH/g and an average molecular weight of from 250 to 6000 g/mol. Esters. Particularly preferably, a hydroxyl group-containing polyester or polyacrylate having an OH oxime of 20 to 150 mg KOH / gram and an average molecular weight of 500 to 6000 g / mol is used. Of course, mixtures of such polymers can also be used. The amount of polymer b) having a functional group is selected such that for each functional group of component b), 0.6 to 2 NCO equivalents of the consumable component a) or 0.3 -11 - 201226453 to 1 pulse are included. Ure di (uretdione). As curing component a), di- or polyisocyanates are used, which are blocked by a blocking agent or internally blocked (uretdione). The di- and polyisocyanates used in accordance with the invention may be composed of any of aromatic, aliphatic, cycloaliphatic and/or (cyclo)aliphatic di- and/or polyisocyanates. As aromatic di- or polyisocyanates, in principle all known aromatic compounds are suitable. Particularly suitable are 1,3- and 1,4-phenylenediester diisocyanate, 1,5-naphthalene diisocyanate, and creyl diisocyanate (1〇1丨1丨(1丨116 diisocyanate) 2,6-toluene diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2, 4'-MDI), a mixture of 4,4'-diphenylmethane diisocyanate, diphenylmethane diisocyanate (MDI) monomer and diphenylmethane diisocyanate oligomer (Polymerized MDI), Benzene diisocyanate 'tetramethylphenyl dimethyl diisocyanate and triisocyanato toluene. Linear or branched type suitable for aliphatic di- or polyisocyanates The excipient-based residue advantageously has from 3 to 16 carbon atoms (preferably from 4 to 12 carbon atoms), and that the cycloaliphatic alkyl group of a cycloaliphatic or (cyclo)aliphatic diisocyanate is advantageously It has 4 to 18 carbon atoms (preferably 6 to 15 carbon atoms). Likewise, those skilled in the art are well aware that: (cyclo)aliphatic diisocyanates are referred to as cyclic and aliphatic. The group-bound NCO group, as in the case of isophorone diisocyanate Conversely, 'cycloaliphatic diisocyanates are understood to mean those having only an NC hydrazine group directly bonded to the cycloaliphatic ring, for example, H 12 MD 1 ° is a diisocyanate cyclohexanil vinegar, Diisocyanatomethylcyclohexanin vinegar, monoisocyanatoethyl 丨己院 -12- 201226453 ester, propyl cyclohexane diisocyanate, methyl diethyl cyclohexane diisocyanate Ester, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptyl diisocyanate, octyl diisocyanate, diiso Cetyl cyanate, decyl triisocyanate such as 4-isocyanato-methyl isocyanate-1,8-octyl ester (TIN), di- and tri-ocyanurate, and Undecyl triisocyanate and dodecyl di- and triisocyanate. Isophorone diisocyanate (IP DI ), diisocyanate diisocyanate (HDI ), diisocyanate Acid dicyclohexylmethane (H12MDI), 2-C) methyl pentane diisocyanate (MPDI), 2,2,4-trimethylhexyl diisocyanate / diisocyanate 2,4 , 4-trimethylhexyl diester (butyl 1 ^ 01) and / or dibornyl diisocyanate (NBDI) is preferred of. Quite particularly well, IPDI, HDI, TMDI and/or H12MDI are used, and isocyanurates are also available. Also, 1,3 -diisocyanate 4-methyl-cyclohexanin vinegar, 2-butyl-2-ethyl pentanyl diisocyanate, isocyanic acid 3 (4)-isocyanatomethyl -1-methylcyclohexyl ester, isocyanate 2-isocyanatopropyl cyclohexyl ester, diisocyanate 2,4'-q methyl bis(cyclohexyl), and 1,4-diiso Cyanate-4-methylpentane is suitable. Of course, mixtures of such di- and polyisocyanates can also be used. Further, it is preferred to use oligo or polyisocyanates which can utilize urethane, urea, urea, biuret, uretdione, amine, isocyanurate, carbodiimide, ureton The uretonimine, oxadiazinetrione, or iminooxadiazinedione is structurally linked to be produced from the di- or polyisocyanates or mixtures thereof. Isocyanurates, especially selected from IPDI and/or HDI, are particularly suitable. -13- 201226453 The polyisocyanate used in accordance with the invention is blocked. Possible for this is an external blocking agent such as ethyl acetoxyacetate, diisopropylamine, methyl ethyl ketone oxime, diethyl malonate, £-caprolactam, 1,2,4-tri An azole, a phenol or a substituted phenol and/or 3,5-dimethylpyrazole. The curing agent preferably used is an IPDI adduct having an isocyanuric acid group and an isocyanate structure blocked by caprolactam. Internal blocking is also possible and this is preferred. The dimer is formed via the uretdione structure for internal blocking, and the uretdione structure is again split at a high temperature into the originally existing isocyanate structure and thus crosslinked with the binder under dynamic conditions. Optionally, the reactive polyurethane composition may contain additional catalyst. These are organometallic catalysts (such as dibutyltin dilaurate (DBTL), tin octoate, neodymium neodecanoate) or tertiary amines (such as I,4-diazabicyclo[2.2] in an amount of 0.001 to 1% by weight. .2] octane). These reactive polyurethane coatings for use in accordance with the present invention are cured under typical conditions, for example, using DBTL catalysts, at temperatures above 16 ° C, often at temperatures above about 180 ° C and Indicated as modified I. In order to produce a reactive polyurethane composition, a total of 0.05 to 5% by weight of additives commonly used in powder coating techniques, such as leveling agents (eg polyoxyalkylene or acrylate), may be added, a light stabilizer (for example a hindered amine), or other additive (for example as described in EP 6 6 9 3 5 3). In the context of the present invention, the reactivity (correction I) means: The reactive polyurethane coating used in the present invention is cured at a temperature higher than 160 ° C depending on the nature of the carrier. The reactive polyurethane compositions of the present invention are cured in a conventional strip, for example, using a DBTL catalyst, at temperatures above 16 CTC, often at about 180 °C. The polyurethane group used in the present invention has a curing time of usually 5 to 60 minutes. Preferably, in the present invention, a matrix material B) made of a formic acid ester composition B) containing a uretdione group is used, which composition contains a) at least one uretdione-containing curing agent. An addition polymerization compound based on a (cyclo)aliphatic or cycloaliphatic uretdione-based polyisocyanate and a hydroxyl-containing compound, the agent being solid at less than 40 ° C and above 125 °C state, and having less than 5% by weight of free NCO content: 25% by weight of uretdione content, b) at least one hydroxyl group-containing polymer, which is below 40 ° C and above 1 2 Liquid at 5 ° C and having an OH 在 between 20 mg KOH/g, c) optionally, at least one catalyst, and d) optionally, a conventional adjuvant in the urethane chemistry The ratio of the content of the two components a) and b) is such that 0.3 to 1 urea bismuth of the component a) is preferably 0.45 to 0.55 for each hydroxyl group of the component. The latter corresponds to an OH ratio of 〇·9 to 1.1/1. In the case of a polyamine-based B)-containing aliphatic acid ester, the solid is a liquid helium and 3 - when it is solid to 200 and b), compared to NCO/ -15- 201226453 Polyisocyanates containing uretdione groups are known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929, 724, and EP 417 6 03. A comprehensive description of the industrially relevant methods for the isocyanate dimerization to uretdiones is given in J. Prakt. Chem. 336 (1 994) 185-200. In general, the conversion of isocyanates to uretdiones is carried out in the presence of soluble dimerization catalysts such as dialkylaminopyridines, trialkylphosphines, triammonium phosphates, or imidazoles. The reaction, which is optionally carried out in a solvent, but preferably in the absence of a solvent, is stopped by the addition of a catalytic poison when the desired degree of conversion is achieved. Excess isocyanate single system is then removed by short path evaporation. If the catalyst is sufficiently volatile, the reaction mixture may be free of the catalyst during the monomer removal process. In this case, the addition of the poison of the catalyst can be omitted. Basically, various isocyanates are suitable for the production of polyisocyanates containing uretdione groups. The above di- and polyisocyanates can be used. However, di- and polyisocyanates selected from any of aliphatic, cycloaliphatic and/or (cyclo)aliphatic are preferred. According to the invention, isophorone diisocyanate (IP DI ) 'HDI diisocyanate (HDI), diisocyanatodicyclohexylmethane (H12MDI), diisocyanate 2 - Methyl pentane ester (MPDI), 2,2,4-trimethylhexylene diisocyanate / 2,4,4-trimethylhexylene diester (TMDI) and/or diisocyanate Borane diisocyanate (NBDI). It is quite preferable to use IPDI, HDI, TMDI and/or H12MDI, and isocyanurates are also available. Quite well, IPDI and/or HDI is used for the matrix material = the conversion of these uretdione-containing polyisocyanates to uretdione-containing curing-16-201226453 agent a) comprises the free NCO group And a hydroxyl group-containing monomer or polymer as a chain extender (for example, polyesters, polythioethers, polyethers, polydecylamines, polyepoxides, polyesteramines, polyaminocarboxylic acids) The reaction of esters, or low molecular weight di-, tri- and/or tetrahydric alcohols) and monoamines and/or monoamines optionally as chain terminators, and has been frequently described (EP 6 6 9 3 53, EP 6 6 9 3 54, DE 30 30 572 'EP 6 3 9 5 98 or EP 803 524 ). Preferably, the curing agent having a uretdione group a) has a free NCO content of less than 5% by weight and a uretdione group content of 3 to 25% by weight (preferably 6 to 18% by weight, calculated as C2N202 having a molecular weight of 84) ). Polyesters and glycol monomers are preferred. In addition to the uretdione group, the curing agent may have an isocyanurate, biuret, ureaformate, urethane and/or urea structure. For the hydroxyl group-containing polymer b), polyesters, polyethers, polyacrylates, polyurethanes and/or polycarbonates having an OH oxime of 20 to 200 mg KOH/g are preferably used. class. Particularly preferred are polyesters having an OH oxime of 30 to 150 mg KOH/g and an average molecular weight of 500 to 6000 g/mol, which is solid at temperatures below 40 ° C and liquid at temperatures above 15 ° C . Such adhesives are described, for example, in EP 669 354 and EP 254 152. Of course, mixtures of such polymers can also be used. The amount of the hydroxyl group-containing polymer b) is selected such that for each of the hydroxyl groups of the component b), from 3,000 to 1 (preferably to 0.5) of the uretdione group of the component a) is consumed. Optionally, additional catalyst c) may be included in the reactive polyurethane composition B) of the present invention. These are organometallic catalysts (e.g., dibutyltin dilaurate, zinc octoate, neodymium neodecanoate) or tertiary amines (e.g., 14-diazabicyclo[2.2] in an amount of from -17 to 201226453 0.001 to 1% by weight. .2] octane). These reactive polyurethane compositions used in accordance with the present invention are cured under typical conditions, e.g., using D B T L catalyst, often exceeding about 180 at over 160 °C. (The temperature of: and is named Modified I. To make the reactive or highly reactive polyurethane composition of the present invention' can be added in a total amount of 0.05 to 5% by weight in the powder coating technique Commonly used additives, such as polyoxyalkylene or acrylates, light stabilizers (such as hindered amines), or other additives (for example as described in EP 669 353). The reactive polyurethane compositions used in accordance with the present invention are cured under typical conditions, for example, using DBTL catalysts, at temperatures in excess of 160 ° C, often in excess of about 180 ° C. The reactive polyurethane coatings used in accordance with the present invention provide excellent flow and thus provide good impregnation behavior and provide superior chemical resistance in the cured state. In addition, the use of an aliphatic crosslinking agent (e.g., IPDI or H12MDI) also achieves good weatherability. Particularly preferred in the present invention is the use of a matrix material B) at least one highly reactive uretdione-containing polyurethane composition substantially comprising a) at least one urea-containing material a diketone-based curing agent; and b) optionally, at least one polymer having a functional group -18-201226453 reactive with an NCO group; c) 0.1 to 5% by weight of at least a species of a catalyst selected from the group consisting of a hydroxide, an alcohol radical, or an organic acid or inorganic acid anion as a quaternary ammonium salt and/or a quaternary phosphonium salt of a counter ion: and d) at least 1 to 5% by weight of a secondary catalyst, Selecting from dl) at least one epoxide, and/or 0 d2) at least one metal acetyl phthalate and/or quaternary ammonium acetyl phthalate and/or quaternary ammonium acetyl acetonate; And e) arbitrarily 'adjuncts and additives in the urethane chemistry. Quite specifically 'using a matrix material B made of the following substances: B) as a matrix material having at least one highly reactive powdered uretdione-containing polyurethane coating B) b) Basic 0 contains a) at least one uretdione-containing curing agent based on a polyisocyanate containing an aliphatic, (cyclo)aliphatic or cycloaliphatic uretdione group and a hydroxyl group-containing compound a polymeric compound wherein the curing agent is solid at less than 40 ° C and liquid at temperatures above 125 ° C and has a free NC Ο content of less than 5% by weight and a urea 2 of 5% to 5% by weight Ketone content, b) at least one hydroxyl-containing polymer which is solid at temperatures below 40 ° C and liquid at temperatures above 125 ° C and has a relationship between 20 and -19 - 201226453 200 mg KOH / gram 〇H値, c) 0.1 to 5% by weight of at least one catalyst selected from the group consisting of a phosphine, a hydroxide, an alcohol radical, or an organic acid or inorganic ion as a quaternary ammonium salt of a counter ion and/or four: and d And 0.1 to 5% by weight of at least one auxiliary catalyst, which is selected to be d 1 ) at least one epoxide, and/or d2) at least one Acetylpyruvate metal salt and / or keto acid quaternary ammonium salt and / or acetyl phthalic acid quaternary ammonium and e) optionally, a secondary additive in the polyurethane chemistry, such that The content ratio of the two components a) and b) is such that from 0.3 to 1 urea bismuth of the component a) is preferably 0.6 to 0.9 for each hydroxy group of the component. The latter corresponds to an NCO/OH ratio of 0.6 to 2/1 or 1.2 to. These highly reactive formate compositions for use in accordance with the present invention are cured at a temperature of from 100 to 160 ° C and are designated as suitable high reactivity uretdione-containing polyurethane compositions of the present invention containing a mixture of the following: : temporarily passivated dicyanates, ie urethanedione-containing (internally blocked) di or acid esters, also described as curing agents a): and according to the invention) and d) And optionally an official polymer (adhesive) having a reaction to the NCO group, which is also described as resin b). These contacts have a halogenated sulfonium salt, a sulfonium salt, and a base of the addition of b), which is more effective than the 1.8/1 polyamine-based di-formic acid or polyiso-isocyanic catalyst C-energy- 20 - 201226453 The uretdione-containing polyurethane composition is cured at a low temperature. The polyurethane-containing composition of the urea-containing diketone group is therefore highly reactive. As the components a) and b), those such as those described above are used. As the catalyst of c), a quaternary ammonium salt (preferably a tetraalkylammonium salt) having a halogen, a hydroxide, an alcohol radical, or an organic acid or inorganic acid anion as a counter ion, and/or a quaternary phosphonium salt is used. . Examples of such catalysts are: tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethyl acetate Ammonium, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, benzene Tetrapropylammonium formate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, and tetrabutylammonium benzoate, and tetrabutyl iron acetate, tetrabutyl formate Money and ethyl triphenylacetate, tetrabendylphosphonium benzotriazolate, tetraphenylphosphonium tetrachloride scale, and trihexyltetradecyl phthalate scale, methyltributylammonium hydroxide, Methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraammonium hydroxide, tetrahexylammonium hydroxide, Tetramethylammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetra-octadecylammonium hydroxide, hydrogen peroxide Benzyltrimethylammonium, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide, methylated methyltributyl Ammonium, methanolic methyltriethylammonium, methanolic tetramethylammonium, methanolic tetraethyl sulphate, methanolic tetrapropylammonium, tetraethylammonium hydride, tetraamylammonium methoxide, tetrahexyl methoxide Ammonium, methanolic tetraoctyl ammonium, -21 - 201226453 Methanolated tetradecyl ammonium, methanolic tetradecyltrihexyl ammonium, methanolized tetra-octadecyl ammonium, methanolated benzyltrimethylammonium, methanol Benzyltriethyl sulphate, methanolic trimethylphenylammonium, methanolic triethylmethylammonium, methanolized trimethylvinylammonium, ethanolated methyltributylammonium, ethanolated methyltriethylamine Ammonium, ethanolic tetramethylammonium, ethanolic tetraethylammonium, ethanolic tetrapropylammonium, ethanolic tetrabutylammonium, ethanolic tetraamylammonium, ethanolic tetrahexylammonium, ethanolic tetraoctylammonium , ethanolic tetradecyl ammonium, ethanolic tetradecyl trihexylammonium, ethanolated tetra-octadecyl ammonium, ethanolated benzyl trimethyl ammonium, B Benzyltriethyl sulphate, ethanolic trimethylphenylammonium, ethanolic triethylmethylammonium, ethanolated trimethylvinylammonium, benzylated methyltributylammonium, benzylated methyl Triethylammonium, benzylated tetramethylammonium, benzylated tetraethylammonium, benzylated tetrapropylammonium, benzylated tetrabutylammonium, benzylated tetraamylammonium, benzylated tetrahexyl Ammonium, benzylated tetraoctyl ammonium, benzylated tetradecylammonium, benzylated tetradecyltrihexylammonium, benzylated tetra-octadecylsulfonate, benzylated benzyltrimethylammonium, benzyl Benzylbenzyltriethylammonium, benzylated trimethylphenylammonium, benzylated triethylmethylammonium, benzylated trimethylvinylammonium, fluorinated tetramethyl-perfluorinated tetraethyl Ammonium, tetrabutylammonium fluoride, tetraoctyl ammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, bromide Butyl ammonium, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide Base ammonium, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, chlorine Benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenyl chloride Ammonium, phenyltrimethylammonium chloride, benzyltrimethyl-22-201226453 ammonium, benzyltriethylammonium bromide, benzyltripropylammonium bromide, bromobutylammonium, bromination Methyltributylammonium, methyltripropylammonium triethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, benzyltriethylammonium iodide Ammonium, benzyl iodide, benzyltributylammonium iodide, methyltributylammonium iodide, ammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide and trimethyl Alkyl ammonium, methyltributylammonium hydroxide, methyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide tetrabutylammonium hydroxide, tetraamylammonium hydroxide, Tetrahexyl tetraoctyl ammonium hydroxide, tetradecylammonium hydroxide, tetradecyl hydroxide, tetra-octadecyl ammonium hydroxide, benzyltrimethylammonium benzyl triethylammonium hydroxide, hydrogen Trimethylphenylammonium oxide, triammonium hydroxide The catalysts of trimethylvinylammonium hydroxide, tetramethylammonium fluoride, ammonium fluoride, tetrabutylammonium fluoride, tetraoctyl ammonium fluoride and benzyltrifluoride may be added separately or as a mixture. . More Q tetraethylammonium formate and / or tetrabutylammonium hydroxide. The catalyst C) is present in an amount of from 0.1 to 5% by weight, preferably from 0.3 to 2% by weight, based on the total mass of the matrix material. A modification according to the invention also comprises a functional group of such a catalyst c) compound b). In addition to these, these catalysts can be surrounded by inertia and thereby coated. An epoxide is used as a secondary catalyst d 1 ). Here, it is possible that the glycidyl ethers and glycidyl esters, the aliphatic epoxide bisphenol A and the glycidyl methacrylate are dihydrated benzyl tris, the brominated methyl group, and the tripropyl group. Ammonium methyl tripropion iodide phenylethylammonium, base money, ammonium hydrogen hydride, hydrogen hexyl ammonium hexoxide, ethyl methyl hydride tetraethyl methyl ammonium. The best use of the benzene benchmark can be incorporated into the polymeric outer layer, such as shrinking, based on oleyl ether -23- 201226453. Examples of such epoxides are triglycidyl isocyanurate (TGIC, trade name ARALDIT 810, Huntsman), a mixture of diglycidyl terephthalate and triglycidyl trimellitate ( Trade names ARALDIT 910 and 912, Huntsman), vaginal acid glycidyl esters (trade name KARDURA E10, Shell), 3', 4'-epoxycyclohexanecarboxylic acid 3,4- Epoxycyclohexylmethyl ester (ECC), diglycidyl ether based on bisphenol A (trade name EPIKOTE 828, Shell), ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythritol tetrahydrate Glyceryl ether (trade name POLYPOX R16, UP PC AG) and other polyp οχ types with free epoxy groups. Mixtures can also be used. It is better to use ARALDIT PT910 and 9 1 2 . As the secondary catalyst d2), a metal salt of acetylpyruvate is possible. Examples of these are zinc acetylacetonate, lithium acetylacetonate and tin acetylacetonate alone or in combination. Preferably, zinc acetyl phthalate is used. As the secondary catalyst d2), quaternary ammonium acetyl phthalate or a quaternary phosphonium acetylate is also possible. Examples of such a catalyst are tetramethylammonium acetoxypyruvate, tetraethylammonium acetoxypyruvate, tetrapropylammonium acetoxypyruvate, tetrabutylammonium acetylacetonate, and ethyl hydrazino. Benzyl trimethylammonium pyruvate, benzyltriethylammonium acetoxypyruvate, tetramethyl sulphate acetate, tetraethyl sulphate, tetrapropyl sulphate , tetrabutyl sulfonate acetylacetonate, benzyl trimethyl hydrazine acetoacetate, and benzyl triethyl acetoxyacetate. Particularly preferably, tetraethylammonium acetylacetonate and/or acetoin-24-201226453 tetrabutylammonium pyruvate may also be used. Of course, the amount of the mixture of the catalysts, the auxiliary catalysts d 1 ) and/or d2 ) may be 0.1 to 5% by weight, preferably 0.3, based on the total blend of the matrix materials. Up to 2% by weight. By using the highly reactive and thus low-temperature curing polyurethane composition B) according to the invention, the curing temperature at 100 to 160 ° C can save energy and curing time, and can also be used. Many temperature sensitive C) carriers. In the context of the present invention, high reactivity (modified type II) means that the uretdione-containing polyurethane composition used in accordance with the present invention is in the range of 100 to 160 ° C depending on the nature of the carrier. The temperature is solidified. The curing temperature is preferably from 120 to 150 ° C, particularly preferably from 130 to 140 ° C. The polyurethane composition used in accordance with the invention has a cure time of between 5 and 60 minutes. The highly reactive uretdione-containing polycarbamic acid Q ester composition B) used in accordance with the present invention provides excellent flow behavior and thus provides good impregnation behavior and provides superior resistance in the cured state. Chemical. In addition, the use of an aliphatic crosslinking agent (e.g., I p D I or Η 2 M D I ) also achieves good weatherability. Suitable pigments are in principle all known pigments. A pigment selected from natural and synthetic inorganic pigments of known species is utilized. Useful natural pigments include earth color materials such as smectite, sassafras or alumina, and mineral pigments such as iron oxide, malachite or cinnabar. Also suitable are inorganic synthetic pigments such as carbon black, chromium pigments, cobalt pigments, iron pigments, ultramarine blue -25-201226453, or white pigments such as titanium dioxide. Also suitable are natural organic pigments and synthetic organic pigments such as azo pigments (bright yellow, permanent red), polycyclic pigments (indigo blue, heliogen), or diketopyrrolopyrrole pigments. Also suitable are metallic effect pigments or pearlescent pigments. Examples of such pigments are: Prussian blue (pigment blue 2 7 C. 1.7 7 5 1 〇), bright yellow (pigment yellow 74 CI 1 1741 ), cadmium yellow (pigment yellow 35 CI 77205 ), cadmium red (pigment red 108) CI772 02 ), chrome oxide green (pigment green 17 CI 77288), cobalt blue (pigment blue 28 CI 77346) 'cobalt blue turquoise light (pigment blue 36 cI 77343), cobalt violet (pigment violet 49 CI 7 73 62 ) , iron oxide black (pigment black 11 ci 77499), irgazine red (pigment red 254 CI 56110), manganese purple (pigment purple 16 CI 77742), phthalocyanine blue ( org ) (pigment blue 15 CI 74 1 60 ), titanium white (pigment white CI 77891), ultramarine blue (pigment blue 29 CI 77007), ultramarine blue A (pigment red 259 CI 77007), bauxite (pigment brown 7 CI 77491) 〇 suitable dyes are all Known dyes, in particular reactive dyes, disperse dyes, pigment dyes 'acid dyes, deeve I ping dyes, IW ions or basic dyes 'coupling dyes, mordant dyes, salt dyes, metal-missing dyes Direct dyes. Important dye types that can be used in the context of the present invention are anthraquinone dyes, azo dyes, monooxazine dyes, indigo dyes, nitro dyes, nitroso dyes, phthalocyanine dyes, sulfur dyes, triphenylmethane dyes. . k Other dyes and pigments suitable for powder coating applications, for example, at -26-201226453

Clariant “Colorants for Powder Coatings”（2005)及 BASF “Colorants and additives from BASF for coatings” (2008) 之文件中詳述。整體而言，較佳是顏料調和物，因爲染料具有一至少受限之光安定性或氣候安定性，此限制由本發明之對應的著色預浸體所製造之複合組件的直接戶外用途〇染料在該基質材料B)中的含量是15重量％以上。 _ 顏料在該基質材料B)中的含量是〇.5至20重量％〇基質材料之製造可進行如下：用於製造聚胺基甲酸酯組成物B)之所有成分的均質化可以在合適單元（例如可加熱之攪拌槽、捏合機或甚至是擠出機）中進行，其間不應超過120至130°C的溫度上限。個別成份之混合較佳是在擠出機中在高於該個別成份之熔化溫度但低於交聯反應開始之溫度下進行。直接使用熔體或在粉末冷卻及製造之 Q 後使用是可能的。該聚胺基甲酸酯組成物B )之製造也可以藉由在上述單元中的混合在溶劑中進行。其次，決定於製程，該基質材料B)與該載體A)被加工成預浸體。本發明之預浸體及複合物組件具有按體積計大於5 0 %，較佳地大於50至70%，特佳地50至65%之纖維含量。作爲基質材料之本發明的反應性或高反應性聚胺基甲酸酯組成物基本上係由反應性樹脂及固化劑之混合物組成 -27- 201226453 。在熔體均質化之後，此混合物具有至少40°C之Tg ,且一般在該反應性聚胺基甲酸酯組成物之情況下僅在高於 1 60 °C時反應，或在該高反應性聚胺基甲酸酯組成物之情況下在高於1 〇〇°C時反應，以獲得經交聯之聚胺基甲酸酯且因此形成該複合材料之基質。此意爲：本發明之預浸體在其製造後係由該載體及所施加之作爲基質材料的反應性聚胺基甲酸酯組成物（其呈未經交聯但爲反應性）製成。該預浸體因此是貯存安定的，一般是數日且甚至是數週，且因此可隨時被進一步加工成複合材料。這就是與已於以上描述之具反應性且無貯存安定性之2成份系統的基本差異’因爲在施加之後，這些立即開始反應且交聯以獲得聚胺基甲酸酯類。本發明之預浸體之製造可以利用已知之工廠及設備，藉由以下方法進行：反應噴射成形（RIM )、強化之反應噴射成形（RRIM )、拉擠方法、藉由在圓柱磨機中施加該溶液或利用熱刮刀、或其他方法。並且’本發明之主題是該預浸體之用途，特別是其與玻璃、碳或芳醯胺之纖維性載體之用途。並且’本發明之主題是依本發明所製造之預浸體的用途’其係用於製造供船舶結構、航空技術、汽車製造、二輪車輛（較佳是機車及腳踏車）、汽車、建築、醫藥技術及運動領域、電器及電子工業及發電廠（諸如風力發電廠中的轉動葉片）用之複合材料。並且，本發明之主題是由依本發明所製造之預浸體 -28- 201226453 所製造之複合組件。【實施方式】反應性聚胺基甲酸酯組成物使用具有以下組成之反應性聚胺基甲酸酯組成物以製造預浸體及複合材料。實例1 調合物[修正型丨] (依本發明）單位:重量％ VESTAGON BF 1321 (含脲二酮基之固化齊喊份a)), Evonik Degussa 32.02 Reafree 17014 (官能之聚酯樹脂成份，得自Cray Valley) 46.86 Reafree 17091 (官能之聚酯樹脂成份，得自Cray Valley) 15.62 Resiflow PV 88 (句染劑，得自WoH6e) 1.00 Benzoin, (除氣助劑，得自Aldrich) 0.50 Colortherm Yellow 10 (供塑料應用之微米化顏料，得自Lanxess) 4.00 NCO:OH比率 0.9:1Details of Clariant “Colorants for Powder Coatings” (2005) and BASF “Colorants and recommendations from BASF for coatings” (2008). In general, pigment blends are preferred because the dyes have an at least limited light stability or climate stability, which limits the direct outdoor use of the composite components produced by the corresponding colored prepregs of the present invention. The content in the matrix material B) is 15% by weight or more. _ The content of the pigment in the matrix material B) is 〇5 to 20% by weight. The ruthenium matrix material can be produced as follows: homogenization of all the components for the production of the polyurethane composition B) can be suitable The unit is carried out, for example, in a heated stirred tank, kneader or even an extruder, and should not exceed an upper temperature limit of 120 to 130 °C. The mixing of the individual components is preferably carried out in an extruder at a temperature above the melting temperature of the individual components but below the onset of the crosslinking reaction. It is possible to use the melt directly or after the powder is cooled and manufactured. The production of the polyurethane composition B) can also be carried out in a solvent by mixing in the above unit. Secondly, depending on the process, the matrix material B) and the carrier A) are processed into a prepreg. The prepreg and composite component of the present invention has a fiber content of more than 50% by volume, preferably more than 50 to 70%, particularly preferably 50 to 65% by volume. The reactive or highly reactive polyurethane composition of the present invention as a matrix material consists essentially of a mixture of a reactive resin and a curing agent -27-201226453. After the homogenization of the melt, the mixture has a Tg of at least 40 ° C, and generally only reacts above 1 60 ° C in the case of the reactive polyurethane composition, or in the high reaction In the case of a polyurethane composition, the reaction is carried out above 1 ° C to obtain a crosslinked polyurethane and thus a matrix of the composite. This means that the prepreg of the present invention is made of the carrier and the reactive polyurethane composition applied as a matrix material (which is uncrosslinked but reactive) after its manufacture. . The prepreg is therefore shelf stable, typically for days and even weeks, and thus can be further processed into a composite at any time. This is the basic difference from the two-component system which has been described above and has no storage stability. As these are immediately reacted after crosslinking and cross-linked to obtain polyurethanes. The prepreg of the present invention can be produced by known processes and equipment by reactive spray forming (RIM), enhanced reactive spray forming (RRIM), pultrusion, by application in a cylindrical mill. The solution is either hot scraped or otherwise. And the subject matter of the invention is the use of the prepreg, in particular its use with a fibrous carrier of glass, carbon or linaloamine. And 'the subject of the invention is the use of prepregs made in accordance with the invention' which are used in the manufacture of marine structures, aerospace technology, automobile manufacturing, two-wheeled vehicles (preferably locomotives and bicycles), automobiles, construction, medicine Composite materials for the technical and sports sectors, the electrical and electronic industries and power plants, such as rotating blades in wind power plants. Further, the subject of the present invention is a composite component manufactured by the prepreg -28-201226453 manufactured according to the present invention. [Embodiment] Reactive Polyurethane Composition A reactive polyurethane coating having the following composition was used to produce a prepreg and a composite. Example 1 Blend [Correction type 丨] (according to the invention) Unit: % by weight VESTAGON BF 1321 (urea diketone-containing curing screaming a)), Evonik Degussa 32.02 Reafree 17014 (functional polyester resin component, From Cray Valley) 46.86 Reafree 17091 (functional polyester resin from Cray Valley) 15.62 Resiflow PV 88 (sentence dye from WoH6e) 1.00 Benzoin, (degassing aid from Aldrich) 0.50 Colortherm Yellow 10 (Micronized pigments for plastic applications, available from Lanxess) 4.00 NCO: OH ratio 0.9:1

得自上表之經硏磨的成分在預混機中緊密地混合，然後在最高達1 3 0°C擠出機中均質化。然後此反應性聚胺基甲酸酯組成物在硏磨後藉由粉末浸漬方法被用於製造該預浸體。爲供直接熔體浸漬方法，在該擠出機中所製造之均質化的熔體混合物可直接被使用。爲供建基於溶劑之方法 -29- 201226453 ，不需要上游熔體均質化作用。 D S C測量The honed ingredients from the above table are intimately mixed in a premixer and then homogenized in an extruder up to 130 °C. This reactive polyurethane composition is then used to make the prepreg by pulverization after honing. For direct melt impregnation, the homogenized melt mixture produced in the extruder can be used directly. For solvent-based methods -29- 201226453, upstream melt homogenization is not required. D S C measurement

遵照 DIN 53765，利用 Mettler Toledo DSC 進行 DSC 測試（玻璃轉化溫度測定及反應焓測量）。擠出體之玻璃轉化溫度經測定爲6 2 t ;用於新製狀態之交聯反應的反應焓是65.5焦耳/克。在該預浸體之基質交聯之後，玻璃轉化溫度升至80 t且不再能偵測到交聯用之熱流。對於此結果，請參見圖所用之玻璃纖維稀洋紗及玻璃纖維織物：在實例中使用以下玻璃纖維稀洋紗及玻璃纖維織物，且在以下稱爲型I及型II。型I是得自“Schl6sser & Cramer”之亞麻E玻璃織物 281 L Art. No. 3103。該織物具有280克/平方公尺之面積重量。型 II GBX 600 Art. No. 1023 是一種得自 “Schl0sser & C r a m e r，，之經縫製的雙軸E玻璃稀洋紗（_ 4 5 / + 4 5 )。此應被了解成二層纖維束，其中一層置放在另一層上且呈90 ° 角互相固定。此結構藉由其他纖維（但其不由玻璃組成）保持在一起。該玻璃纖維之表面利用經胺基矽烷改質之標準膠液處理。該稀洋紗具有600克/平方公尺之面積重® -30- 201226453 預浸體之製造預浸體之製造係藉由依DE 102010029355之直接熔體浸漬方法進行。預浸體之貯存安定性預浸體之貯存安定性，係利用D S C硏究，由玻璃轉化溫度及交聯反應之反應焓決定。 Ό PU預浸體之交聯容量不因在室溫下貯存5週時間而破壞。時間（貯存日） Tg [°〇] 2 62 14 64 28 62 35 63 時間（貯存曰）固化焓μ/g] 2 65 14 67 28 67 35 66DSC testing (glass transition temperature measurement and reaction enthalpy measurement) was performed using a Mettler Toledo DSC in accordance with DIN 53765. The glass transition temperature of the extrudate was determined to be 6 2 t; the reaction enthalpy for the crosslinking reaction of the fresh state was 65.5 joules/g. After the matrix of the prepreg is crosslinked, the glass transition temperature is raised to 80 t and the heat flux for crosslinking is no longer detectable. For the results, please refer to the glass fiber scrim and glass fiber fabric used in the drawings: The following glass fiber scrim and glass fiber fabric are used in the examples, and are referred to below as Type I and Type II. Type I is a linen E glass fabric 281 L Art. No. 3103 available from "Schl6sser & Cramer". The fabric has an area weight of 280 g/m 2 . Type II GBX 600 Art. No. 1023 is a sewn biaxial E-glass scrim (_ 4 5 / + 4 5 ) from Schl0sser & C Ramer. This should be understood as a two-layer fiber. The bundle, one of which is placed on the other and fixed to each other at an angle of 90. This structure is held together by other fibers (but not composed of glass). The surface of the glass fiber is modified with a standard rubber modified with amino decane. Liquid processing. The scrim has an area of 600 g/m 2 . Weight -30 - 201226453 Prepreg manufacturing of the prepreg is carried out by direct melt impregnation according to DE 102010029355. Prepreg storage The storage stability of the stability prepreg is determined by the DSC study, which is determined by the glass transition temperature and the reaction enthalpy of the crosslinking reaction. 交 The cross-linking capacity of the PU prepreg is not destroyed by storage at room temperature for 5 weeks. Time (storage day) Tg [°〇] 2 62 14 64 28 62 35 63 Time (storage 曰) Curing 焓μ/g] 2 65 14 67 28 67 35 66

複合材料組件的g胃在複合材料壓機上，藉由精於此技藝者已知的壓縮技術製造複合材料組件。藉由直接浸漬作用所製造之均質的 -31 - 201226453 預浸體在工作台壓機上被壓縮成複合材料。此是得自 Schwabenthan 公司之 Polystat 200T，，在120至2 00°C之溫度間將該預浸體壓縮成材料片。壓力是在常壓及450巴之間變化。依、厚度及聚胺基甲酸酯組成物及因此在處理溫設定，動力壓縮（亦即壓力的交替應用）可以聯之優點。在一實例中，該壓機之溫度在熔化期間ί 1 10°c，壓力在熔化3分鐘後增至440巴，然 44〇巴之間動力地變化（每分鐘變化7次），度連續地增至140t。其次，溫度升至18 0。〇維持在3 5 0巴之下直至3 0分鐘後複合材料組移除。測試具有> 50%之纖維體積含量的硬質化學品及耐衝擊的複合材料組件（片產品）之藉由D S C測定）。經固化之基質的玻璃轉化指明在不同固化溫度下之父聯進程。利用所用酸酯組成物，在約2 5分鐘後完成交聯，然後到交聯反應之反應焓。【圖式簡單說明】圖 1 :遵循 DIN 53 765，利用 Mettler 8 2 1 e所進行之D S C測試（玻璃轉化溫度測定測量）。工作台壓機利用該壓機對應之複合照組件大小度下之黏度保證纖維交 έ 9 0 °C升至後在1 5 0至在此期間溫，同時壓力件由該壓機、剛性、耐固化程度（溫度的測定之聚胺基甲不再能偵測The g-stom of the composite component The composite component is fabricated on a composite press by compression techniques known to those skilled in the art. The homogeneous -31 - 201226453 prepreg produced by direct impregnation is compressed into a composite on a bench press. This is a Polystat 200T from Schwabenthan, which compresses the prepreg into a sheet of material at a temperature between 120 and 200 °C. The pressure varies between atmospheric pressure and 450 bar. Depending on the thickness and the polyurethane composition and therefore the temperature setting, the dynamic compression (i.e., the alternating application of pressure) can be combined. In one example, the temperature of the press is during the melting period ί 1 10 ° C, the pressure is increased to 440 bar after melting for 3 minutes, and the power is dynamically changed between 44 〇 (changes 7 times per minute), continuously Increased to 140t. Second, the temperature rose to 18 0.复合 Maintain the composite group below 305 bar until 30 minutes. Hard chemicals and impact resistant composite components (sheet products) having a fiber volume content of > 50% were tested by D S C). Glass conversion of the cured matrix indicates the parent process at different cure temperatures. With the use of the acid ester composition used, the crosslinking is completed after about 25 minutes, and then the reaction enthalpy of the crosslinking reaction is carried out. [Simple description of the diagram] Figure 1: D S C test (glass transition temperature measurement) using Mettler 8 2 1 e in accordance with DIN 53 765. The workbench press uses the viscosity of the composite photo assembly corresponding to the size of the press to ensure that the fiber crosses at 90 °C and then rises to 150° during this period, while the pressure member is made of the press, rigid and resistant. Degree of cure (the determination of the temperature of the polyamine base can no longer be detected

Toledo DSC 及反應焓之 -32-Toledo DSC and reaction -32-

Claims

201226453 VII. Patent application scope: 1 · ~ kinds of prepreg, which basically consists of A) at least one fibrous carrier, and B) less one reactive or highly reactive polyurethane composition As a matrix material, wherein the polyurethane composition substantially contains a mixture of a lower layer of J: a polymer having an isocyanate-reactive functional group as a binder, b), and a curing agent a) The internal blocking and/or the blocking of the di- or polyisocyanate with a blocking agent, and wherein the matrix material additionally comprises 1 a pigment having a particle diameter of < 150 nm, and/or a dye. 2. The prepreg of claim 1, wherein the matrix material B) has a Tg of at least 40 °C. 3. The prepreg according to claim 1, wherein the prepreg has a fiber content of more than 5% by volume, preferably more than 50 to 70%, particularly preferably more than ◎50 to 65% by volume. 4. The prepreg according to claim 1, wherein the pigment is a natural and/or synthetic inorganic pigment. 5) The prepreg according to claim 1 of the patent scope, which contains a reactive dye selected from reactive dyes, disperse dyes, pigment dyes, acid dyes, developing dyes, cationic or basic dyes, coupling dyes, mordants , anthraquinone dyes, metal mismatch dyes, direct dyes. 6. The prepreg according to claim 1, wherein a polymer having a hydroxyl group, an amine group and a thiol group b) is used, particularly having a 20H値 of from 20 to 500 -33 to 201226453 mg / 克 / gram Polyesters, polyethers, polyacrylates, polycarbonates, and polyurethanes having an average molecular weight of from 250 to 60,000 g/mole. 7. The prepreg according to claim 1, wherein a di- or polyisocyanate selected from the group consisting of the following starting compounds of component a): isophorone diisocyanate (IPDI), diisocyanate Acid dihexyl hexaester (HDI), diisocyanatodicyclohexylmethane (H12MDI), 2-methylammonium diisocyanate (MPDI), 2,2,4-trimethyl diisocyanate Hexadiester / / diisocyanate 2,4,4 - trimethyl hexane diester (TMDI) and / or dibornyl diisocyanate (NBDI), especially IPDI, HDI, TMDI and / or Hi zMDI' can also be used with isocyanurates. 8) The prepreg according to claim 1 of the patent application, wherein an external blocking agent selected from the group consisting of a) is blocked by ethyl acetate, diisopropylamine, methyl ethyl ketone oxime, Diethyl malonate, ε-caprolactam, 1,2,4-triazole, phenol or substituted phenols and/or 3,5-dimethylpyrazole. 9. The prepreg according to claim 1, wherein an I P D I adduct, an isocyanuric acid group, and an isocyanate structure blocked by ε-caprolactam are used as the component a). 1 〇 a prepreg according to claim 1, wherein the reactive polyurethane composition B) contains an additional catalyst in an amount of from 0.001 to 1% by weight, preferably dibutyltin dilaurate, Zinc octoate, neodymium neodecanoate, and/or secondary amines are preferably I,4-diazabicyclo[2·2·2] xinyuan. A prepreg according to claim 1, which has at least one polyurethane composition comprising uretdione Β) -34-

基质 201226453 The matrix material, the composition 基本上) basically contains a) at least one uretdione-containing curing agent based on the sale, (cyclo)aliphatic or cycloaliphatic uretdione polyisocyanide And an addition polymerizable compound of a hydroxyl group-containing compound, wherein the oxidizing agent is solid at less than 40 ° C and in a state above 125 ° C ffi, and has less than 5% by weight of free NCO content of 25% by weight of urea II Ketone content, b) at least one hydroxyl-containing polymer which is liquid at temperatures below 40 ° C and above 125 ° C and has an OH 在 between 20 3 mg KOH / cc, c) optionally , at least one catalyst, and d) optionally, adjuvants and agents conventionally used in polyurethane chemistry, such that the ratio of the contents of the two components a) and b) is such that each hydroxyl group is consumed for the component From 0.3 to 1 uretdione 3 of the component a) is preferably from 0.45 to 0.55. The composition of the uretdione-containing poly(acid ester composition B) having at least one highly reactive powder as the matrix material, as claimed in any one of claims 1 to 9 β) substantially a) at least one uretdione-containing curing agent; and b) optionally, at least one having a reactive polymer reactive with NCO groups; c) 〇_1 to 5% by weight of at least one species of catalyst , which is selected from the group consisting of having hydroxide, alkoxide, alcoholic acid or organic acid radicals or inorganic acid radicals, an aliphatic group: esters, solids, liquids, and 3-solids, 200 additions. A dentate ion-35-201226453 as a quaternary ammonium salt and/or a quaternary rust salt of a counter ion; and d) 0.1 to 5% by weight of at least one auxiliary catalyst selected from the group consisting of d 1 ) at least one epoxide And/or d2) at least one metal salt of acetyl acetonate and/or quaternary ammonium acetyl phthalate and/or quaternary phosphonium acetonate; and e) optionally, polyamine Auxiliary adjuvants and additives in acid chemistry. 1 3 - A prepreg according to claim 12, which has at least one highly reactive powdered uretdione-containing polyurethane composition B) as a matrix material, the composition B Basically comprising a) at least one uretdione-containing curing agent based on addition polymerization of polyisocyanates containing aliphatic '(cyclo)aliphatic or cycloaliphatic uretdione groups and hydroxyl group-containing compounds a compound, wherein the curing agent is solid at less than 4 (TC) and liquid at temperatures above 125 ° C, and has a free NCO content of less than 5% by weight and a uretdione content of from 3 to 25% by weight; b At least one hydroxyl group-containing polymer which is solid at less than 4 ° C and liquid at temperatures above 125 ° C and has an OH 在 between 20 and 200 mg KOH / gram; c) 0.1 to 5 wt% of at least one catalyst selected from the group consisting of halogen, hydroxide, alcohol, or organic acid or inorganic acid anion as a quaternary ammonium salt of a counter ion and/or a quaternary phosphonium salt; and d) 0.1 to 5% by weight of at least one auxiliary catalyst selected from the group consisting of d 1 ) at least one epoxide, and/or -36-201226453 d 2) at least one metal salt of acetyl acetylacetonate and/or quaternary ammonium salt of acetyl phthalate and/or quaternary phosphonium acetonate; and e) optionally, urethane chemistry Conventional adjuvants and additives, such that the ratio of the contents of the two components a) and b) is such that from 0 to 3 to 1 uretdione of component a) is consumed for each of the hydroxyl groups of component b), preferably 0.6 to 0.9. 1 4 . Use of a prepreg according to any one of claims 1 to 3, in particular a fibrous support having glass, carbon or linalin fibers. The use of a prepreg as claimed in any one of claims 1 to 13 is for the manufacture of marine structures, aerospace technology, automobile manufacturing, two-wheeled vehicles (preferably locomotives and Composites for bicycles, automobiles, construction, medical technology and sports, electrical and electronics industries, and power plants, such as rotating blades in wind power plants. A composite component produced by a prepreg according to at least one of claims 1 to 13. -37-