201030211 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於製造道路、轨道及其他交通所用 區域之方法，其係藉由製造一包括經研磨路面、礦物材料 及/或玻璃、聚合物反應混合物及若需要之另外添加物之 . 混合物，及將其施用於一基質材料，及使其硬化。本發明 進一步係關於可藉由此類型方法獲得之道路、軌道及其他 交通所用區域。 ® 【先前技術】 本發明進-步之實施例見於中請專利範圍、闡述及實例 中。上述本發明主旨之特徵及將在下文閣釋之特徵當然在 不超出本發明之料下，不僅可以分別閣述之組合並且亦 可以其他組合使用。 道路主要係自瀝青，藉由將礦物混合物（主要係將瀝青 作為黏合劑）(若適宜則分多層）施用於基質而製成。亦知曉 ❹使用塑膠作為點合劑之路面，例如de 196〇5剛及DE 19651749中所述。 以遞青為主之道路—般在約12至18年之後（成品質與負 載之函數），及在少至6至7年之後若頂層具有開孔則應更 新$此，元全或部份移除老舊的遞青。經移除的少量材 料，右適當，可以相同粒度分佈回收高達較佳15重量％之 量。。為此，必須將材料輸送至瀝青混合工廠，在此在約 180 C的溫度下將其與新鮮瀝青以及與礦物材料混合。之 後將所付瀝青依次自瀝青混合工廠輸送至安裳場所。此程 144931.doc 201030211 序會導致嚴重的環培兮迅 的貨車運铨 / 、，、疋因為針對此目的所必須 二=:以及因為瀝青混合工廠中之高能量消耗。另 因：係遞月不可再利用’其黏合劑仍包含一定比例的隹 油，由於焦油有毒，其必須作為特殊廢棄物棄置。’、，、 【發明内容】 本發明之一目標係提供一 道路、執道及其他交 通所用Q域之方法，且其可降低環境污染。 本發明之目標係經由—㈣於製造道路、軌道及其他交 通所用區域之方法而達到，該方法係藉由製造—包括經研 磨路面、礦物材料及/或破璃、聚合物反應混合物及若需 要之另外添加物之混合物，及將其施用於-基質材料，及 使其硬化。 【實施方式】 道路、軌道及其他交通所用區域—般係由多層組成。其 等在表面處具有至少一結合頂層’以及若適宜，另外的經 結合及未結合之更深層。經結合的更深層—般稱為負荷承 載層，以及未結合之更深層一般係由瓦礫及砂石組成之基 體層。用於此等結合頂層及負荷承载層作為黏合劑的一般 材料係水泥、塑膠或遞青。 本發明方法在此係關於結合層之製造。其等可為負荷承 載層或頂層。負荷承載層與頂層之間的主要差異在於所用 礦物材料之平均直徑。本發明方法較佳係關於頂層之製 造。所用基質材料可為任何所需材料，其實例為砂、土 壤、砂壌、混凝土、石。基質材料較佳為基體層及/或負 144931.doc 201030211 荷承載層。 據本發明，經研磨路面意指經研磨或破碎的頂層，或 者經研磨或破碎的負荷承載層，及經研磨的瓦礫層或經研 f的砂石層。經研磨的路面較佳為經研磨的結合層，尤其 ’7<研磨的頂層。用於此處經研磨結合層之黏合劑較佳係 以聚合物為主或以瀝青為主，尤其是以瀝青為主之黏合 d此特佳變型不僅利用遞青之熱塑性或黏彈性性質，還 參 利用聚合物黏合劑之高溫。經研磨路面之粒度分佈在此可 藉由改變研磨條件或移除非所需粒度而以一已知方式進行 調整。根據本發明，亦可使用基於有孔遞青之頂層作為經 研磨路面的基體。 ' 在此所用之礦物材料可包括任何已知的礦物材料。舉例 來說’在此可使用砂或經研磨的石材（稱為破碎材料），其 中石> 具有主要為圓形的表面及破碎材料具有棱邊及斷裂 面。特別佳的係所用礦物材料包括一主要由破碎材料組成 之材料。 所用玻璃較佳包括經研磨或破碎的破璃。破碎玻璃在此 較佳為有色玻璃，其允許（例如）施用標記。破璃在此可與 =玻一 Γ用或替代礦物材料。較佳僅使用礦物材料 由經研磨路面組成及由礦物材料及/或破璃組成之混人 物的粒度分佈㈣㈣基於在含瀝青道路構造t所遇狀 規格其為預期用途之函數，例如對於負荷 層，其實例為經石材填充之膠泥渥青混凝土或排水性遞 14493I.doc 201030211 青。粒度分佈可經由調整經研磨路面之粒度，或者經由利 用具有特定粒度分佈之礦物材料，或經由此二者進行調 整。經研磨路面及礦物材料在此可以任何重量比混人。= 研磨路面之比例基於由經研磨路面及礦物材料組成之混= 物總重量，較佳小於95重量％，特別佳為自5重量％至= 量％及尤其是自10重量％至70重量％。 聚合物反應混合物在此意指能夠反應得到聚合物之混合 物。此等混合物包括含有（例如）能經由鏈增長反應（諸如自 由基聚合、或離子聚合）反應得到聚合物之分子（其實例為 不飽和化合物）、或能夠進入縮聚反應之分子（其實例為多 元醇）、或能夠進入加成聚合反應之分子（其實例為多元醇 及聚異氰酸酯，或彼等諸如環氧化物者）的混合物。本發 明之聚合物反應混合物較佳在4〇°c下為液體。 聚合物反應混合物較佳包括一用於製造環氧樹脂或聚胺 基甲酸醋之混合物。特定言之，纟包括一用於製造聚胺基 甲酸酯之混合物，即聚胺基曱酸酯反應混合物。聚合物反 應混合物在此較佳本質上不含溶劑。 自聚合物反應混合物獲得之聚合物較佳為緊實的，此意 指其等實際上無孔隙。緊實聚合物之一特徵為，與多孔聚 合物相比具有更強的機械穩定性。在聚合物内可能會出現 氣泡且其一般不重要。但其等應盡可能小。此外，所得聚 合物較佳為疏水性。此可抑制聚合物被水降解。 本發明之聚合物反應混合物較佳包括用於改良對回收材 料以及對礦物材料的黏合力之化合物。舉例而言，其等係 144931.doc 201030211 通式（i)之羥基胺基矽烷化合物或烷氧基胺基矽烷化合物201030211 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing roads, tracks and other areas used for transportation, which comprises manufacturing a surface comprising a ground surface, a mineral material and/or glass, Mixing the polymer reaction mixture and, if desired, additional additives, and applying it to a matrix material and allowing it to harden. The invention further relates to roads, tracks and other areas of traffic that can be obtained by this type of method. ® [Prior Art] Examples of further developments of the present invention are found in the scope, description, and examples of the patent application. The features of the gist of the present invention and the features which will be explained hereinafter are of course not limited to the scope of the present invention, and may be used in combination not only separately but also in other combinations. The road is mainly made of asphalt, which is prepared by applying a mineral mixture (mainly using asphalt as a binder), if appropriate in multiple layers, to the substrate. It is also known that 塑胶 uses plastic as a paving agent, as described in DE 196〇5 and DE 19651749. The road based on diversion is generally about 12 to 18 years later (as a function of quality and load), and if there is an opening in the top layer as little as 6 to 7 years later, it should be updated to $, full or partial Remove the old divorce. The removed small amount of material, right right, can be recovered up to preferably 15% by weight with the same particle size distribution. . To this end, the material must be transported to an asphalt mixing plant where it is mixed with fresh bitumen and with mineral materials at a temperature of about 180 °C. The bitumen is then transported from the asphalt mixing plant to the Anchang site. This process 144931.doc 201030211 The order will lead to serious 兮 兮 的 的 货车 铨 / /, 疋 because it is necessary for this purpose two =: and because of the high energy consumption in the asphalt mixing plant. Another reason: the monthly delivery is not reusable. 'The adhesive still contains a certain proportion of eucalyptus oil. Since tar is toxic, it must be disposed of as special waste. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> One of the objects of the present invention is to provide a method for roads, roads, and other Q domains used for transportation, and which can reduce environmental pollution. The object of the present invention is achieved by - (d) in the manufacture of roads, tracks and other areas used for transportation by manufacturing - including ground pavement, mineral materials and / or glass, polymer reaction mixtures and if desired A mixture of additional additives is applied to the matrix material and allowed to harden. [Embodiment] Roads, tracks, and other areas used for transportation are generally composed of multiple layers. They have at least one bonded top layer' at the surface and, if appropriate, additional bonded and unbonded deeper layers. The deeper layers that are combined are generally referred to as load carrying layers, and the deeper layers that are not combined are generally the base layers of rubble and sand. The general materials used for these combined top layers and load bearing layers as binders are cement, plastic or fairing. The method of the invention is here related to the manufacture of the bonding layer. They can be load bearing layers or top layers. The main difference between the load bearing layer and the top layer is the average diameter of the mineral material used. The method of the invention is preferably directed to the manufacture of the top layer. The matrix material used may be any desired material, examples of which are sand, soil, mortar, concrete, stone. The matrix material is preferably a matrix layer and/or a negative 144931.doc 201030211 load bearing layer. According to the invention, the ground surface means a ground or ground top layer, or a ground or crushed load bearing layer, and a ground rubble layer or a ground sand layer. The ground surface is preferably a ground bonded layer, especially a '7<grinded top layer. The adhesive used for the abrasive bonding layer here is preferably polymer-based or asphalt-based, especially asphalt-based bonding. This special modification not only utilizes the thermoplastic or viscoelastic properties of the greening, but also The high temperature of the polymer binder is used. The particle size distribution of the ground surface can be adjusted in a known manner by changing the grinding conditions or removing the undesired particle size. According to the present invention, a top layer based on a perforated green can also be used as the base of the ground surface. 'The mineral material used herein may include any known mineral material. For example, sand or ground stone (referred to as crushing material) may be used herein, wherein the stone > has a predominantly circular surface and the fractured material has edges and fracture surfaces. Mineral materials used in particularly preferred systems include a material consisting primarily of crushed materials. The glass used preferably comprises ground or broken glass. The broken glass is here preferably colored glass which allows, for example, the application of markings. In this case, the broken glass can be used with or instead of mineral materials. Preferably, only the mineral material is composed of a ground surface composed of a ground surface and a mixed material composed of a mineral material and/or a glass. (4) (4) Based on a function of the intended use of the asphalt-containing road structure t, for example, for a load layer An example of this is a stone-filled mortar, concrete, or drainage, 14493I.doc 201030211. The particle size distribution can be adjusted by adjusting the particle size of the ground surface, or by using a mineral material having a particular particle size distribution, or both. The ground surface and mineral material can be mixed in any weight ratio. = the proportion of the ground pavement is based on the total weight of the mixture composed of the ground pavement and the mineral material, preferably less than 95% by weight, particularly preferably from 5% by weight to 9% by weight and especially from 10% by weight to 70% by weight . By polymer reaction mixture is meant herein a mixture of polymers which are capable of reacting. Such mixtures include molecules containing, for example, a polymer which can be obtained by a chain extension reaction such as a radical polymerization or ion polymerization, examples of which are unsaturated compounds, or molecules capable of entering a polycondensation reaction (examples thereof are plural Alcohol), or a mixture of molecules capable of entering an addition polymerization reaction, examples of which are polyols and polyisocyanates, or such as epoxides. The polymer reaction mixture of the present invention is preferably liquid at 4 ° C. The polymer reaction mixture preferably comprises a mixture for the manufacture of an epoxy resin or a polyurethane carboxylic acid. In particular, 纟 includes a mixture for the manufacture of polyurethanes, i.e., polyamine phthalate reaction mixtures. The polymer reaction mixture is preferably free of solvent in this context. The polymer obtained from the polymer reaction mixture is preferably compact, which means that it is virtually void free. One of the compact polymers is characterized by greater mechanical stability than porous polymers. Air bubbles may appear in the polymer and are generally not important. But it should be as small as possible. Further, the obtained polymer is preferably hydrophobic. This inhibits degradation of the polymer by water. The polymer reaction mixture of the present invention preferably comprises a compound for improving the adhesion to the recycled material and to the mineral material. For example, it is 144931.doc 201030211 Hydroxylaminodecane compound or alkoxyaminodecane compound of formula (i)
R —siH~Y—ν\ ο) L Jn L \ Jm w R1 · 其中 X 彼此獨立地為OH、CH3、0[CH2]pCH3 ; Y 為 [CH2]t 、 [(CH2)rNH(CH2)s] [(CH2)rNH(CH2)sNH(CH2)z]b ； R，R· 為 H、[CH2]tCH3 ; t 為0至10 ; η 為1至3 ; Ρ 為0至5 ; m 為4至η ; r、s、b及z彼此獨立地為1至i〇。 此烧氧基胺基矽烷化合物⑴一般為三經基_、二烧氧基_ 或二烷氧基胺基矽烷化合物。較佳的烷氧基X為甲氧基及 • 乙氧基。胺基必須為對異氰酸酯基具有反應性之胺基，亦 即第一胺基或第二胺基。較佳的烷基R為氫、甲基及乙 基。 烷氧基胺基矽烷化合物⑴較佳包括三羥基胺基矽烷化合 物或三烷氧基胺基矽烷化合物，其中在式⑴中，或 0[CH2]PCH3 及 ρ=〇、1。 烷氧基胺基矽烷化合物⑴更佳包括烷氧基二胺基矽烷化 合物，其中在式（I)中，Y=[CH2]rNH[CH2]s，及_ S可相同 144931.doc 201030211 或不同，其等為1或2。其實例為[CH2]3NH[CH2]2、 [CH2]2NH[CH2]2、[CH2]NH[CH2]、[ch2]3nh[ch2]3、 [CH2CH(CH3)CH2]NH[CH2]2及[CH2]2NH[CH2]3。 烧氧基胺基矽烷化合物（I)尤其包括三烷氧基二胺基矽烷 化合物’其中在式⑴中，x=〇[CH2]pCH3，其中p = 〇、1， 及Y=[CH2]rNH[CH2]s，其中I^s可相同或不同，其等為1或 特佳之院氧基胺基矽烷化合物⑴為3_三乙氧基矽烷基丙 胺、N-(3-三羥基矽烷基丙基）乙二胺、n_(3_三曱氧基矽烷❹ 基丙基）乙二胺及Ν·(3_曱基二曱氧基甲基矽烷基_2甲基丙 基）乙二胺。 聚合物反應混合物在此一般包含基於聚合物反應混合物 之總重量’自0.01重量％至10重量％，較佳為〇」重量。如 重量。/。濃度之用於改良黏合之化合物。此用於改良黏合之 化&物在此亦可先刚已與聚合⑯反應昆合物之另外成份反 應’例如藉由任何存在的ΟΗ基。 就本發明之目的而言，用於製造環氧樹脂之混 ❹ 了、…/抑汴匕口柳思孑曰 包括含環氧基的化合物及適合的硬化社混合物。此等混 合物在此能夠自含環氧基之化合物開始，利用適合的硬化 劑，错由該等環氧基經由加聚而形成環氧樹脂。本發明當 :反：中之轉化率利用表述語「用於製造環氧樹脂之混合 於製造環氧樹脂之環氧基，其較佳少於 〇特佳少於75%，以及尤其是少於5〇%。 所利用之含環氧基之化合物較佳為具有至少兩個環氧基 144931.doc 201030211 並且在室溫下為液體之化合物。此處亦可利用含環氧基之 不同化合物之混合物。該等化合物較佳係疏水性或該等混 合物包括至少一種疏水性及含環氧基之化合物。此類型之 疏水性化合物可舉例為經由雙酚A或雙酚？與表氯醇之縮合 反應所獲得得。該等化合物可單獨使用或以混合物之形式 使用。 在一實施例中，使用由上述包含環氧基之疏水性化合物 瘳肖包含環氧基之可自乳化親水性化合物組成之混合物。此 等親水性化合物在此係藉由將親水性基團引入含環氧基之 化0物的主鏈中而獲得。此類型之化合物及用於製造其等 之方法以貫例的方式揭示於JP-A-7-206982及Jp_A-7_ 304853 中 〇 所用之硬化劑包括可催化含環氧基化合物之均聚合反 應，或者可與環氧基或第二羥基共價反應之化合物，其實 例為聚胺、聚胺基酿胺、嗣亞胺、叛酸野及三聚氣胺-尿 鲁素苯酚加合物及甲醛加合物。較佳使用酮亞胺，其可藉 由將含第一胺基或第二胺基之化合物（例如二伸乙基三 胺、三伸乙基四胺、丙二胺或二曱苯二胺)與羰基化合物 (諸如丙酮、甲基乙基_或異丁基甲基_)反應而獲得，或 者使用脂族、脂環族及芳族聚胺化合物及聚醯胺化合物。 特佳使用的硬化劑為_亞胺或包括酮亞胺之相容混合物。 硬化劑中之反應性基團對環氧基之比例較佳為0.7:1至 1·5:1，特佳為 1.1:1至！ 4:1。 在製造環氧樹脂期間，亦可連同含環氧基之化合物及所 144931.doc 201030211 用之硬^齊j添加另外的添力σ劑，諸如溶劑、反應性稀釋 劑、填充劑及顏料。此類型添加劑已為熟悉此項技術者所 知。 聚胺基曱酸醋反應混合物係一由含異氛酸醋基之化合物 及含對異氰酸酯具有反應性之基團的化合物組成之混合 物，其中基於用於製造聚胺基曱酸酯反應混合物之異氰酸 酯基之反應轉化率較佳少於9〇%，特佳少於75%，以及尤 其是少於50%。含對異氰酸酯具有反應性之基團之化合物 在此不僅包括高分子量化合物，諸如聚醚_及聚酯醇，並 _ 且亦包括低分子量化合物’諸如丙三醇、二醇，以及水。 若基於異氰酸酯基計的反應轉化率大於9〇%，則以下使用 術語聚胺基甲酸酯。聚胺基甲酸酯反應混合物在此亦可包 括用於製造聚合物之另外的反應混合物。可用於製造聚合 物之另外反應混合物之實例為用於製造環氧化物、用於製 造丙烯酸酯或用於製造聚酯樹脂之反應混合物。用於製造 聚合物之另外反應混合物之比例，在此基於聚胺基甲酸醋 反應混合物之總重量’較佳少於5 0重量％。特佳的係聚胺 © 基甲酸酯反應混合物不含用於製造聚合物之另外的反應混 合物。 5^胺基曱酸s曰反應混合物可包括稱為濕固化系統者。此 等包括經由加成水或經由濕氣，主要藉由形成脲基，而形 成聚胺基曱酸酯或聚脲之異氰酸酯預聚合物。 較佳使用用於製造聚胺基甲酸酯反應混合物之稱為兩組 分系統者。為此’將包括含異氰酸酯基之化合物之異氰酸 144931.doc -10- 201030211 酯組分’及包括含對異氰酸酯具有反應性的基團的化合物 之多元醇組分，以定量比例混合，使得異氰酸酯指數在4〇 至300，較佳60至200 ’及特佳80至150的範圍内。· 就本發明之目的而言，異氰酸酯指數在此意指異氰酸酯 基除以對異氰酸酯具有反應性的基團之化學計量比乘以 100。對異氰酸酯具有反應性的基團在此意指任何包含於 反應混合物中並且對異氰酸酯具有反應性之基團，其包括 化學發泡劑，但不包括異氰酸酯基本身。 聚胺基甲酸酯反應混合物較佳係藉由使a)異氰酸酯與b) 含至少兩個對異氰酸酯具有反應性的氫原子之相對高分子 量化合物混合，以及若需要則與c)鏈延長劑及/或交聯劑， d)觸媒，及e)其他添加劑混合而獲得。使用作為組分a)及 b)，以及若需要之c)至e)之特佳化合物係彼等可得到疏水 性聚胺基甲酸酯反應混合物及疏水性聚胺基▼酸酯者。 可利用的#氰酸醋a)大體上為任何含至少兩個異氰酸醋 φ 基之室溫下為液體之異氰酸酯。較佳使用芳族異氰酸酯， 特佳使用F苯二異氰酸酯（TDI)之異構體及二苯基甲烷二 異氰酸酯（MDI)之異構體，尤其是由Mm及聚伸苯基聚亞 甲基聚異氰酸Θ旨（粗MDI)組成之混合物。此等異氣酸醋亦 可經改質，例如藉由併入異三聚氰酸醋基及碳二醢亞胺 基二及尤其是藉由併入胺基甲酸醋基。最後提及之化合物 係藉甴將異氰酸酯與低於化學計量的含至少兩個活性氫原 子之化合物反應而製造，且一般稱為狀〇預聚合物。其等 之NCO含量主要係在2重量％至32重量％的範圍内。異氛酸 144931.doc 201030211 醋a)較佳包括粗Mm，以致增加所獲得聚胺基甲酸酯之穩 定性。 在本發明方法之應用中，當高染色牢固性係重要時，較 佳使用包括脂族異氰酸酯及芳族異氰酸酯之混合物。特佳 兀全使用脂族異氰酸酯。在一特定實施例中，可使用由基 於脂族異氰酸酯之聚胺基甲酸酯組成之覆蓋層，以保護基 於芳族異氰酸酯的頂層不黃化。此覆蓋層在此亦可包括礦 物材料。較佳代表性的脂族異氰酸酯係六亞甲基二異氰酸 酯（HDI)及異佛爾酮二異氰酸酯（IpDI)。由於脂族異氰酸酯 # 具有高揮發性，因而其主要係以其等之反應產物形式使 用，尤其係以二縮脲、脲基甲酸酯、脲酮亞胺或異三聚氰 酸酯之形式。 異氰酸酯a)亦可以其預聚合物形式使用。為此，使異氰 酸酯a)以一已知方式且過量地與對異氰酸酯具有反應性之 化合物反應，例如與列於b)之相對高分子量化合物（其具有 至少2個對異氰酸醋具有反應性的基團）反應、，以得到預聚 合物。 所使用之具有至少兩個對異氰酸醋具有反應性的氫原子 之相對高分子量化合物b)較佳包括含經基或胺基作為對異 氰酸醋具有反應性的基團之化合物。以胺基作為對異氰酸 醋具有反應性的基團導致形成腺基，其依次經硬化得到通 常易碎的聚胺基甲酸g旨，但复且a - /、具有相當好的对水解性及耐 化學劑性。所使用的含至少兩個 网调對異氰酸酯具有反應性的 風原子之相對局分子量化人私1 U \ ± Λ 化〇物W較佳包括多羥基醇，因為 144931.doc 201030211 其等一般比含胺基化合物反應更慢及因此允許更長的加工 時間。若具適合的高莫耳質量（例如大於15〇〇 g/m〇l)，則 利用多經基醇會另外生成相當彈性的材料。 所利用的此相對高分子量、多羥基醇可舉例為包括聚醚 或聚酯。含至少兩個對異氰酸酯基具有反應性的氫原子之 另外的化合物可與所提及化合物一起使用。 由於其等的高耐水解性，聚醚醇較佳作為含至少兩個對 異氰酸酯具有反應性之氫原子的相對高分子量化合物b)。 此等係藉由慣用且已知之方法，主要係藉由環氧烷的加成 反應至H-官能性起始物質上而製造。伴隨使用之聚醚醇之 官能度較佳至少為2,其等羥值為至少1〇mgK〇H/g，較佳 為至少15 mg KOH/g，尤其是在20至600 mg KOH/g的範圍 内。其等係以習知方式經由至少雙官能性起始物質與環氧 烷之反應而製造。所用起始物質較佳可包括於分子中含至 少兩個羥基之醇，其實例為丙二酵、單乙二酵、二甘醇、 二丙二醇、三丙二醇。相對高官能度之起始物質較佳可為 丙三醇、三羥甲基丙烷、新戊四酵、山梨酵及蔗糖。所用 環氧烷較佳包括環氧乙烷及環氧丙烷，尤其是環氧丙烷。 本發明之反應混合物較佳包括含疏水基之化合物。其等 特佳包括含疏水基的羥基官能化化合物。此等含疏水基之 化合物具有較佳含大於6，特佳大於8及小於2〇〇，以及尤 其是大於10且小於100個碳原子之烴基。此等含疏水基之 化合物可作為個別的組分或作為組分勾至幻之一成份，用 於製造反應混合物《此等羥基官能化疏水性化合物較佳包 14493】.doc 201030211 括遵循含至少兩個對異氰酸酯具有反應性的氫原子之相對 高分子量化合物b)之定義的化合物。組分b)在此可包括羥 基官能化疏水性化合物或可較佳由其等組成。 所用羥基官能化疏水性化合物較佳包括自油化學中得知 之包基官能化化合物或自油化學中得知之多元醇。 許多可利用的羥基官能性化合物係於油化學中所知曉。 其實例為：蓖麻油、經羥基改質之油（例如葡萄籽油）、黑 種草油、南瓜籽油、琉璃苣籽油、大豆油、小麥胚芽油、 φ 菜籽油、葵花油、花生油、杏仁籽油、開心果油、杏仁 ’由、橄欖油、澳洲胡桃果仁油、酪梨油、沙棘油、芝麻 油、榛子油、月見草油、野玫瑰油、大麻油、刻油、胡桃 油、經羥基改質且基於肉豆蔻油酸、棕櫚油酸、油酸、反 11-十八烯酸、序子酸、鱈油酸、芥子酸、二十四碳烯 酸、亞麻油酸、次亞麻油酸、十人碳四稀酸、花生四稀 酸、二十碳五烯酸'綠油酸或二十二碳六稀酸之脂肪酸 醋。在此較佳使用萬麻油及其與環氧燒或與綱-甲酸樹脂R —siH~Y—ν\ ο) L Jn L \ Jm w R1 · where X is independently of each other OH, CH3, 0[CH2]pCH3; Y is [CH2]t, [(CH2)rNH(CH2)s ][(CH2)rNH(CH2)sNH(CH2)z]b ; R,R· is H,[CH2]tCH3; t is 0 to 10; η is 1 to 3; Ρ is 0 to 5; m is 4 To η ; r, s, b, and z are independently from 1 to i 〇. The alkoxyaminodecane compound (1) is generally a trisyl-, di-oxo- or di-alkoxyaminodecane compound. Preferred alkoxy groups X are methoxy and • ethoxy. The amine group must be an amine group reactive toward isocyanate groups, i.e., a first amine group or a second amine group. Preferred alkyl groups R are hydrogen, methyl and ethyl. The alkoxyaminodecane compound (1) preferably comprises a trihydroxyaminodecane compound or a trialkoxyaminodecane compound, wherein in the formula (1), or 0[CH2]PCH3 and ρ=〇, 1. The alkoxyaminodecane compound (1) more preferably comprises an alkoxydiamine decane compound, wherein in the formula (I), Y = [CH2]rNH[CH2]s, and _S may be the same as 144931.doc 201030211 or different , which is equal to 1 or 2. Examples thereof are [CH2]3NH[CH2]2, [CH2]2NH[CH2]2, [CH2]NH[CH2], [ch2]3nh[ch2]3, [CH2CH(CH3)CH2]NH[CH2]2 And [CH2]2NH[CH2]3. The alkoxyaminodecane compound (I) includes, in particular, a trialkoxydiaminodecane compound, wherein in the formula (1), x = 〇[CH2]pCH3, wherein p = 〇, 1, and Y = [CH2]rNH [CH2]s, wherein I^s may be the same or different, and the equivalent of 1 or a preferred oxyamino decane compound (1) is 3-triethoxydecylpropylamine, N-(3-trihydroxydecylpropylidene Ethylenediamine, n_(3_tridecyloxydecylmercaptopropyl)ethylenediamine and Ν·(3_fluorenyldimethoxymethyldecyl-2-methylpropyl)ethylenediamine. The polymer reaction mixture here generally comprises from 0.01% to 10% by weight, based on the total weight of the polymer reaction mixture, preferably 〇" by weight. Such as weight. /. Concentration of compounds used to improve adhesion. The <RTIgt; </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; For the purposes of the present invention, the use of a mixture of epoxy resins for the production of epoxy resins, etc., includes an epoxy group-containing compound and a suitable hardening compound mixture. These mixtures can hereby start with an epoxy group-containing compound and, by means of a suitable hardener, the epoxy groups are formed by addition polymerization. The present invention: when: the conversion rate in the reverse: using the expression "the epoxy group used to make the epoxy resin mixed in the epoxy resin, preferably less than 75%, and especially less than The epoxy group-containing compound to be used is preferably a compound having at least two epoxy groups 144931.doc 201030211 and being liquid at room temperature. Different compounds containing an epoxy group may also be used herein. Mixtures. The compounds are preferably hydrophobic or the mixtures comprise at least one hydrophobic and epoxy-containing compound. Hydrophobic compounds of this type may be exemplified by condensation of bisphenol A or bisphenol? with epichlorohydrin. The compound can be used alone or in the form of a mixture. In one embodiment, a self-emulsifiable hydrophilic compound comprising an epoxy group-containing hydrophobic compound and an epoxy group is used. Mixtures. These hydrophilic compounds are hereby obtained by introducing a hydrophilic group into the main chain of the epoxy group-containing compound. The compounds of this type and the methods for producing the same are conventional. The hardeners disclosed in JP-A-7-206982 and Jp_A-7_304853 include compounds which catalyze the homopolymerization of an epoxy-containing compound or which are covalently reactive with an epoxy group or a second hydroxyl group. Examples thereof are polyamines, polyamine-based amines, quinones, tarenic acid and trisamine-uranyl phenol adducts and formaldehyde adducts. Preferably, ketimines are used, which can be a compound containing a first amine group or a second amine group (for example, di-ethyltriamine, tri-ethylidene tetraamine, propylenediamine or dinonylbenzenediamine) and a carbonyl compound (such as acetone, methylethyl group) Or isobutylmethyl-) can be obtained by reaction, or aliphatic, alicyclic and aromatic polyamine compounds and polyamine compounds can be used. Particularly preferred hardeners are imines or compatible mixtures including ketimines. The ratio of the reactive group to the epoxy group in the hardener is preferably from 0.7:1 to 1.5:1, particularly preferably from 1:1:1 to 4:1. The compound of the epoxy group and the 144931.doc 201030211 are used to add another additive force, such as a solvent, a reactive diluent, and a filling agent. Charges and pigments. This type of additive is known to those skilled in the art. The polyamine phthalic acid vinegar reaction mixture consists of a compound containing an oleic acid acetate group and a compound having a reactivity with an isocyanate group. a mixture wherein the conversion based on the isocyanate groups used to make the polyamine phthalate reaction mixture is preferably less than 9%, particularly preferably less than 75%, and especially less than 50%. Containing p-isocyanate The reactive group compounds herein include not only high molecular weight compounds such as polyethers and polyesterols, but also low molecular weight compounds such as glycerol, diols, and water, if based on isocyanate groups. The reaction conversion is greater than 9%, and the term polyurethane is used below. The polyurethane reaction mixture may also comprise an additional reaction mixture for the manufacture of the polymer. Examples of additional reaction mixtures which can be used in the manufacture of polymers are the reaction mixtures for the manufacture of epoxides, for the manufacture of acrylates or for the manufacture of polyester resins. The proportion of the additional reaction mixture used to make the polymer is preferably less than 50% by weight based on the total weight of the polyurethane reaction mixture. A particularly preferred polyamine © carbamate reaction mixture does not contain an additional reaction mixture for the manufacture of the polymer. The 5 胺 曱 曱 曰 曰 曰 reaction mixture can include a person known as a moisture curing system. These include the formation of polyamino phthalate or polyurea isocyanate prepolymers via addition water or via moisture, primarily by the formation of urea groups. It is preferred to use a system called a two-component system for producing a polyurethane reaction mixture. For this purpose, the isocyanate group 144931.doc -10- 201030211 ester component comprising an isocyanate group-containing compound and a polyol component comprising a compound having a group reactive with isocyanate are mixed in a quantitative ratio such that The isocyanate index is in the range of 4 to 300, preferably 60 to 200' and particularly preferably 80 to 150. For the purposes of the present invention, the isocyanate index here means the stoichiometric ratio of the isocyanate group divided by the isocyanate-reactive group multiplied by 100. The group reactive toward isocyanate means herein any group which is included in the reaction mixture and is reactive toward isocyanate, and includes a chemical blowing agent, but does not include an isocyanate. The polyurethane reaction mixture is preferably prepared by mixing a) an isocyanate with b) a relatively high molecular weight compound containing at least two hydrogen atoms reactive toward isocyanate, and if necessary, with c) a chain extender and / or cross-linking agent, d) catalyst, and e) other additives are obtained by mixing. The use of the hydrophobic aramid reaction mixture and the hydrophobic polyamine-based acid ester can be obtained by using the particularly preferred compounds as components a) and b), and if desired, c) to e). Useful #Cyanate vinegar a) is generally any isocyanate which is liquid at room temperature containing at least two isocyanate φ groups. It is preferred to use an aromatic isocyanate, particularly preferably an isomer of F phenyl diisocyanate (TDI) and an isomer of diphenylmethane diisocyanate (MDI), especially from Mm and polyphenylene polymethylene. A mixture of isocyanate (crude MDI). These isogastric vinegars may also be modified, for example by incorporation of iso-cyanuric acid and carbodiimide di- and especially by incorporation of urethane carboxylic acid groups. The last-mentioned compounds are made by reacting isocyanates with substoichiometric compounds containing at least two active hydrogen atoms and are generally referred to as ruthenium prepolymers. The NCO content thereof is mainly in the range of 2% by weight to 32% by weight. Ioric acid 144931.doc 201030211 Vinegar a) preferably comprises crude Mm so as to increase the stability of the obtained polyurethane. In the application of the process of the invention, when high dye fastness is important, it is preferred to use a mixture comprising an aliphatic isocyanate and an aromatic isocyanate. It is a good use of aliphatic isocyanates. In a particular embodiment, a cover layer composed of an aliphatic isocyanate-based polyurethane can be used to protect the top layer of the aromatic isocyanate from yellowing. This cover layer may also include mineral materials herein. A preferred representative aliphatic isocyanate is hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IpDI). Since aliphatic isocyanate # has high volatility, it is mainly used in the form of its reaction product, especially in the form of a biuret, allophanate, uretonimine or meta- lysate. The isocyanate a) can also be used in its prepolymer form. For this purpose, the isocyanate a) is reacted in a known manner and in excess with a compound which is reactive toward isocyanates, for example with a relatively high molecular weight compound listed in b) which has at least 2 reactivity with isocyanic acid The group) reacts to obtain a prepolymer. The relatively high molecular weight compound b) having at least two hydrogen atoms which are reactive toward isocyanate is preferably a compound containing a trans group or an amine group as a group reactive toward isocyanate. The use of an amine group as a group reactive toward isocyanic acid vines results in the formation of a glandular group which is sequentially hardened to give a generally brittle polyglycolic acid, but a & / has a relatively good hydrolyzability And chemical resistance. The relative molecular weight of the wind atom containing at least two nets which are reactive toward isocyanate is preferably a polyhydric alcohol, since 144931.doc 201030211 Amino compounds react more slowly and thus allow for longer processing times. If a suitable high molar mass is present (e.g., greater than 15 〇〇 g/m 〇l), the use of polyhydric alcohol will additionally result in a relatively elastic material. The relatively high molecular weight, polyhydric alcohol utilized may be exemplified by polyethers or polyesters. Further compounds containing at least two hydrogen atoms which are reactive toward isocyanate groups can be used together with the compounds mentioned. Due to their high hydrolysis resistance, polyether alcohols are preferred as relatively high molecular weight compounds b) which contain at least two hydrogen atoms which are reactive toward isocyanates. These are produced by a conventional and known method, mainly by addition reaction of an alkylene oxide onto an H-functional starting material. The polyether alcohol used in combination preferably has a functionality of at least 2 and an equivalent hydroxyl number of at least 1 〇 mg K 〇 H / g, preferably at least 15 mg KOH / g, especially from 20 to 600 mg KOH / g. Within the scope. These are produced in a conventional manner by reaction of at least a bifunctional starting material with an alkylene oxide. The starting material used may preferably comprise an alcohol having at least two hydroxyl groups in the molecule, examples of which are malondialdehyde, monoethylidene, diethylene glycol, dipropylene glycol, tripropylene glycol. Preferably, the relatively high functionality starting material is glycerol, trimethylolpropane, neopentyl fermentation, sorbitan and sucrose. The alkylene oxide used preferably comprises ethylene oxide and propylene oxide, especially propylene oxide. The reaction mixture of the present invention preferably comprises a compound containing a hydrophobic group. It is particularly preferred to include a hydroxyl functional compound containing a hydrophobic group. These hydrophobic group-containing compounds have a hydrocarbon group preferably having more than 6, particularly preferably more than 8, and less than 2, and especially more than 10 and less than 100 carbon atoms. These hydrophobic group-containing compounds can be used as individual components or as a component to the phantom component for the preparation of the reaction mixture. "The hydroxy-functionalized hydrophobic compounds are preferably packaged 14493." doc 201030211 A compound of the definition of a relatively high molecular weight compound b) which is a reactive hydrogen atom to an isocyanate. Component b) may here comprise or may consist essentially of a hydroxy-functionalized hydrophobic compound. The hydroxy-functionalized hydrophobic compound used preferably comprises a urethane functionalized compound known from oleochemistry or a polyol known from oleochemistry. Many available hydroxy functional compounds are known in oil chemistry. Examples are: castor oil, hydroxy modified oil (eg grape seed oil), black grass oil, pumpkin seed oil, borage seed oil, soybean oil, wheat germ oil, φ rapeseed oil, sunflower oil, peanut oil Almond seed oil, pistachio oil, almond's, olive oil, Australian walnut nut oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil, hemp oil, engraved oil, walnut oil, Modified by hydroxyl group and based on myristic acid, palmitoleic acid, oleic acid, trans 11-octadecenoic acid, protonic acid, oleic acid, sinapic acid, tetracosenoic acid, linoleic acid, sub-Asia Sesic acid, ten carbon tetrabasic acid, peanut tetrabasic acid, eicosapentaenoic acid 'green oleic acid or docosahexaenoic acid fatty acid vinegar. It is preferred to use the sesame oil and its epoxy or bismuth-formic acid resin
Q 之反應產&。最後提到的化合物例如由Μ以 Desmophen® 1150上市。 於油化學中知曉且其你用兔4。 使用&較佳之另—群多元醇可藉由 脂肪酸㈣環，同時與醇反應，及若需要，則隨 主要係經由包含於此苯…/基併入油及脂肪中 所雙鍵環氧化，隨後將 所得環乳基與單·或多㈣醇反應而進行。 產物為羥I，或|多羥基醇的情 ^ 月凡下為含相對高OU基值 144931.do. -14 - 201030211 的結構。由於油及脂肪主 應同時發生酯交換反應。 5〇〇至1500 g/mol的範圍内 供。 要為丙三醇酯，因而伴隨上述反 所得化合物之莫耳質量較佳在 。此等產物係（例如）由Henkel提 在本發明方法之-特佳實施例中，含至少兩個對異氛酸 醋具有反應性的氫原子之相對高分子量化合物b)包括至少 -種於油化學中知曉之多元醇及至少一種經酚改質之芳族 烴樹脂，特別是一種茚-香豆酮樹脂。以該組分…為主之聚 胺基曱酸酯反應混合物具有一定程度的疏水性質，其足夠 高以使得其等大體上甚至能夠在有水的條件下硬化，或在 降雨時裝設。 所用具有末端酚基之經酚改質之芳族烴樹脂較佳包括經 酚改質之茚·香豆酮樹脂’以及特佳包括芳族烴樹脂之工 業混合物。此等產物可於市面購得及（例如）由厌肘#。 AG以 NOVARES®提供。 φ 經紛改質之芳族烴樹脂，尤其是經酚改質之茚-香豆酮 樹脂的ΟΗ含量一般係自〇_5重量％至5.0重量％。 自油化學中得知之多元醇及經酚改質之芳族烴樹脂，尤 其是茚-香豆酮樹脂，較佳係以100:1至100:50的重量比使 用0 可利用鏈延長劑c)製造本發明之聚胺基甲酸酯反應混合 物。然而，在此亦可省略鏈延長劑c)。然而，添加鏈延長 劑、交聯劑或者若需要則添加其等之混合物可成功地改善 機械性質，例如硬度。 H4931.doc -15· 201030211 若使用低分子量鏈延長劑及/或交聯劑c),則可利用已知 的鏈延長劑製造聚胺基甲酸酯。此等較佳為含對異氰酸酯 具有反應性的基團且莫耳質量為62至400 g/m〇1之低分子量 化合物，其實例為丙三醇、三羥甲基丙烷、已知的二醇衍 生物、丁二醇及二胺。其他可能的低分子量鏈延長劑及/ 或交聯劑例示於「Kunststoffhandbuch，Band 7，聚胺基甲 酸 δθ (Polyurethane)」[Plastics Handbook’ 第 7卷，聚胺美 甲酸醋（Polyurethanes)]，Carl Hanser Verlag，！ 993 年第 3 版，第3.2及3·3·2章中。 所用的聚胺基甲酸酯大體上可在無觸媒d)的存在下製 造。可同時使用觸媒d)以改良硬化。所選之觸媒d)較佳應 為可使反應時間最大化者。因此，聚胺基甲酸酯反應混 物可長時間保持液態。此等觸媒為熟悉此項技術者所知。 其亦可大體上如所述在完全無觸媒的條件下進行。 可將其他習知成份添加至聚胺基甲酸酯反應混合物中， 其實例為習知添加劑e)。其等包括（例如）習知的填料。所 用填料較佳為習知、有機及無機填料、增強劑及本身已知 的增重劑。可提及的個別實例為：無機填料（例如頁石夕酸 鹽，諸如葉蛇紋石、蛇紋岩、角閃石、閃石、溫石棉）、 金屬氧化物（諸如高嶺土、氧化鋁、氧化鈦及氧化鐵”金 屬鹽（諸如白堊、重晶石）及無機顏料（諸如硫化鎘、硫化 鋅）以及玻璃。較佳使用高嶺土（i 土）、㈣缺由硫酸鋇 及石組成之共沉澱物 '以及天然及合成纖維碌石（諸 如矽灰石）、不同長度的金屬纖維及尤其是不同長度的玻 144931.doc -16- 201030211 璃纖維，#需要，則其可經膝料塗覆。可利用的有機填料 實例為··碳黑、三聚氰胺、松香、環戊二烯基樹脂及接枝 聚合物’以及纖維素纖維、聚醯胺纖維、聚丙婦腈纖維、 聚胺基甲酸酯纖維、以芳族二幾酸醋及/或脂族二緩酸醋 為主之聚酯纖維’及尤其是碳纖維。Q reaction production & The last mentioned compounds are marketed, for example, by Desmophen® 1150. Known in oil chemistry and you use rabbit 4 . The use of & preferably another group of polyols can be carried out by the fatty acid (tetra) ring while reacting with the alcohol, and if desired, with the primary linkage via the incorporation of the benzene .../ group into the oil and fat by double bond epoxidation, The resulting cyclic lactide is then reacted with a mono- or poly(tetra)ol. The product is a hydroxy I, or | polyhydric alcohol. The structure is a structure containing a relatively high OU base value of 144931.do. -14 - 201030211. Since the oil and fat mainly undergo a transesterification reaction. Available in the range of 5 〇〇 to 1500 g/mol. It is preferably a glycerol ester, and thus the molar mass of the compound obtained by the above reaction is preferred. Such products are, for example, those raised by Henkel in a preferred embodiment of the process of the invention, the relatively high molecular weight compound b) comprising at least two hydrogen atoms reactive toward the oleic acid vinegar, including at least one of the oils A polyol known in the chemical and at least one phenol-modified aromatic hydrocarbon resin, particularly a quinone-coumarin resin. The polyaminophthalate reaction mixture based on this component has a degree of hydrophobic property which is sufficiently high that it can be hardened even in the presence of water, or in rain. The phenol-modified aromatic hydrocarbon resin having a terminal phenol group preferably comprises a phenol-modified oxime-coumarin resin and an industrial mixture particularly preferably comprising an aromatic hydrocarbon resin. These products are commercially available and, for example, from the elbow #. AG is supplied by NOVARES®. The rhodium content of the φ modified aromatic hydrocarbon resin, especially the phenol-modified rhodium-coumarin resin, is generally from 〇5 wt% to 5.0 wt%. The polyol and the phenol-modified aromatic hydrocarbon resin, especially the quinone-coumarin resin, which are known from the oil chemistry, are preferably used in a weight ratio of 100:1 to 100:50. 0 can be used as a chain extender c. The polyurethane reaction mixture of the invention is produced. However, the chain extender c) can also be omitted here. However, the addition of a chain extender, a crosslinking agent or, if desired, the addition of a mixture thereof or the like can successfully improve mechanical properties such as hardness. H4931.doc -15· 201030211 If a low molecular weight chain extender and/or crosslinker c) is used, a known chain extender can be used to produce the polyurethane. These are preferably low molecular weight compounds having a group reactive toward isocyanate and having a molar mass of from 62 to 400 g/m , 1, examples of which are glycerol, trimethylolpropane, known diols. Derivatives, butylene glycol and diamines. Other possible low molecular weight chain extenders and/or crosslinkers are exemplified in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics Handbook 'Vol. 7, Polyurethanes], Carl Hanser Verlag,! Third edition of 993, chapters 3.2 and 3.3.2. The polyurethane used can be produced substantially in the absence of catalyst d). Catalyst d) can be used simultaneously to improve hardening. The selected catalyst d) should preferably be such that the reaction time is maximized. Therefore, the polyurethane reaction mixture can remain in a liquid state for a long period of time. Such catalysts are known to those skilled in the art. It can also be carried out substantially as described above under completely catalyst-free conditions. Other conventional ingredients may be added to the polyurethane reaction mixture, an example of which is the conventional additive e). They include, for example, conventional fillers. The fillers used are preferably conventional, organic and inorganic fillers, reinforcing agents and weighting agents known per se. Specific examples which may be mentioned are: inorganic fillers (such as sulphate, such as serpentine, serpentine, hornblende, amphibole, chrysotile), metal oxides (such as kaolin, alumina, titania and iron oxide) "Metal salts (such as chalk, barite) and inorganic pigments (such as cadmium sulfide, zinc sulfide) and glass. It is preferred to use kaolin (i soil), (4) coprecipitate composed of barium sulfate and stone, and natural and Synthetic fiber (such as ash stone), metal fibers of different lengths and especially glass of different lengths 144931.doc -16- 201030211 glass fiber, if needed, it can be coated by the knee. Available organic filler Examples are carbon black, melamine, rosin, cyclopentadienyl resin and graft polymer', as well as cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, and aromatic two. A few kinds of acid vinegar and / or aliphatic acid vinegar-based polyester fiber 'and especially carbon fiber.
若將上述無機材料用作添加劑e)，則其等之礦物物質成 份較佳不同於礦物材料之絲物質成份，且在測量㈣材 料的粒度分佈時將其忽略。 無機及有機填料可單獨使用或以混合物的形式使用，並 且其於反應混合物中之含量基於組分a)h)之重量較佳為 0-5重量％至50重量％，特別佳為】重量％至4〇重量％。 聚胺基甲酸酯反應混合物亦應包括乾燥劑，諸如沸石。 較佳將其等在製造本發明反應混合物之前，添加至含至少 兩個對異氰酸酯具有反應性的氫原子之化合物…中，或添 加至包括含至少兩個對異氰酸醋具有反應性的氫原子的化 合物b)之組分中。乾燥劑的添加可避免組分中或反應混合 物中任何水濃度的增加，以及因此避免泡沫狀聚胺基甲酸 酯之形成。就吸水性而言較佳添加鋁矽酸鹽，其選自以下 組成之群：鋁矽酸鈉、鋁矽酸鉀、鋁矽酸鈣、鋁矽酸鉋' 鋁矽酸鋇、鋁矽酸鎂、鋁矽酸鋰、鋁磷酸鈉、鋁磷酸鉀、 鋁磷酸鈣及其混合物。特佳使用存於作為載體物質之蓖麻 油中的鋁矽酸鈉、鋁矽酸鉀及鋁矽酸鈣之混合物。 為改良本發明頂層之長期穩定性，另外可有利地添加對抗 微生物攻擊的試劑。添MUV穩定劑亦有利於避免模製品脆 144931.doc •17· 201030211 化。此等添加劑係已知，且其實例於「以她祕―， 7 聚胺基甲酸酯（Polyurethane)」[Plastics Handbook，第7卷，聚胺基f酸酯（卩叫咖加廳）]，If the above inorganic material is used as the additive e), the mineral material component thereof is preferably different from the silk material component of the mineral material, and is ignored when measuring the particle size distribution of the (4) material. The inorganic and organic fillers may be used singly or in the form of a mixture, and the content thereof in the reaction mixture is preferably from 0 to 5% by weight to 50% by weight, particularly preferably 5% by weight, based on the weight of the component a) h). Up to 4% by weight. The polyurethane reaction mixture should also include a desiccant such as a zeolite. Preferably, it is added to a compound containing at least two hydrogen atoms reactive with isocyanate, or added to a hydrogen comprising at least two isocyanate-reactive hydrides before the reaction mixture of the present invention is produced. In the component of compound b) of the atom. The addition of the desiccant avoids any increase in the concentration of water in the component or in the reaction mixture, and thus avoids the formation of foamy polyurethane. In terms of water absorption, it is preferred to add an aluminosilicate which is selected from the group consisting of sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, aluminosilicate, aluminum bismuth citrate, magnesium alumininate Lithium aluminum niobate, sodium aluminophosphate, potassium aluminophosphate, calcium aluminophosphate and mixtures thereof. It is particularly preferable to use a mixture of sodium aluminosilicate, potassium aluminosilicate and calcium aluminosilicate in castor oil as a carrier material. In order to improve the long-term stability of the top layer of the present invention, it is additionally advantageous to add an agent against microbial attack. Adding MUV stabilizers is also beneficial to avoid the embrittlement of molded parts. 144931.doc •17· 201030211. These additives are known, and examples thereof are in "My Secrets, 7 Polyurethane" [Plastics Handbook, Vol. 7, Polyaminof-Acrylate (卩叫咖加厅)] ,
Hanser Veriag，1993年第3版，第3 4章中給出。 較佳將組分c)、d)及e)添加至含至少兩個對異氰酸酯基 具有反應性的氫原子之化合物中。此混合物在工業中一般 稱為多元醇組分。 異氰酸酯與含至少兩個對異氰酸酯基具有反應性的氫原 子之化合物組合的比例較佳係使得所存在的異氰酸酯基超 出化學計量。 在本發明的一較佳實施例中，使用可產生疏水性、實質 上緊實之聚胺基甲酸酯的聚胺基甲酸酯反應混合物。若聚 胺基曱酸酯實質上無氣體夾雜物，則其稱為緊實的聚胺基 曱酸醋。緊實聚胺基甲酸酯之密度較佳大於〇 8 g/cm3，特 佳大於0.9 g/cm ’及尤其是大於]_.〇 g/cm3。 可利用作為另外添加物的材料實例係彼等可防止黏合劑 自礦物材料中流失者。可添加的此類型添加物之實例為有 機纖維，諸如纖維素纖維。另外’可添加目前用於以瀝青 為主的系統中之聚合物。其等尤其是氯丁二烯橡膠、苯乙 烯-丁二烯-苯乙烯、嵌段共聚物或此等之混合物，或者任 何其他已知之橡膠或此等之混合物。此等添加物可以粉末 或顆粒形式直接加入礦物混合物中’或者可分散於聚胺基 曱酸酯組分之一者中。 對於包括經研磨路面、礦物材料及聚合物反應混合物、 144931.doc 201030211 、及右使用之另外添加物之本發明混合物的製造並無任何 限制。其等可（例如）在混合器中製造，將經研磨的路面及 礦物材料引入其中’及將用於製造聚胺基甲酸酯反應混合 . &之起始組分引人（例如經由噴壤）。待於此處添加之添加 ， 4匆，若需要’較佳係在各自有利的接合點處添加至混合物 中。因此，舉例而言，可使其等在反應混合物組分之一者 中（例如在組分a)至e)令之—者中）呈溶液或分散液形式， _卩及可將此等添加至混合物中。亦可分別將添加物添加至 混合物中。舉例而言，可在某一接合點添加纖維素纖維， 使得此等存在於用於製造頂層之混合物之均質分散液中， 但不會被混合程序不可逆性損壞。本發明混合物在此可 (例如）藉由DE 196 32 638中所述方法而製造。同樣地，例 如可以製造聚胺基甲酸酯反應混合物開始，然後將其與礦 物材料，及若使用之另外的添加物混合。在另一實施例 中，若需要，可先將礦物材料與某些反應混合物組分，例 φ 如與組分15)及若存在之勾至e)混合，然後可在混合器中加 入尚未存在的組分（例如組分a))。包括經研磨路面的本發 明混合物可藉由可移動方法在安裝場所製造。不需要將其 .輸送至中心工廠。 . 可較佳使用之疏水性聚胺基甲酸酯反應混合物的特徵為 特別佳的加工性。舉例而言，該等聚胺基甲酸酯反應混合 物及自其獲得的聚胺基甲酸酯之特徵為特別佳的黏合性。 由於此系統的疏水性，此聚胺基曱酸酯反應混合物即使係 在存在水（例如雨水）的情況下亦可硬化，而得到實際上緊 144931.doc -19- 201030211 實的產物。 在將本發明混合物施用於基質材料時，並不需要基質材 料係乾燥的。令人驚訝的是’甚至在基質材料係濕潤時， 亦可在負荷承載層或頂層與基質材料之間獲得良好的黏合 性。 本明混合物在此基於包括經研磨路面、礦物材料及聚 σ物反應混合物以及若需要之另外添加物之本發明混合物 之總重量，較佳包括1重量％至2〇重量％，特佳2重量％至 15重量％，及尤其是4重量％至1〇重量％的聚合物反應混合 物。 礦物材料與本發明黏合劑之間的黏合相當牢固。此外， 特別是若使用含疏水性基團之羥基官能性化合物，則實際 上不存在聚胺基曱酸酯的水解降解，因此，由本發明方法 所製造的頂層之耐久性極高。本發明之頂層具有特別佳的 負荷承載性質，因此適用於所有的道路、軌道及交通所用 區域，尤其適用於跑道及用於承受相對高負荷的構造等級 V至I，尤其是111至1及跑道之道路，其中構造等級V之道路錄 係通路，及構造等級I之道路係高速公路及公路。此處所 用之礦物材料較佳包括對各別構造等級所建議之材料。 令人驚訝地，且特別是當使用疏水性反應混合物時僅 存在極小的霜害。本發明頂層之另一優勢為低修理成本。 其（例如）在不加熱的情況下於原位製造少量用於製造頂層 之混合物，及將其施用於受損部位並將其壓緊即足夠。此 外，本發明頂層之機械性質可經歷若干年而不會變化。 144931.d〇) •20- 201030211 發明頂層之另一優勢為改良的抗濕滑性，尤其是在與具高 瀝青含量之頂層相比，頂層具有高聚胺基甲酸酯含量的情 況下。Hanser Veriag, 3rd edition, 1993, given in Chapter 34. Preferably, components c), d) and e) are added to a compound containing at least two hydrogen atoms which are reactive toward isocyanate groups. This mixture is generally referred to in the industry as a polyol component. The ratio of the isocyanate combination with the compound containing at least two hydrogen atoms which are reactive toward isocyanate groups is preferably such that the isocyanate groups present are out of stoichiometry. In a preferred embodiment of the invention, a polyurethane reaction mixture which produces a hydrophobic, substantially compact polyurethane is used. If the polyamino phthalate is substantially free of gaseous inclusions, it is referred to as a compact polyamino phthalic acid vinegar. The density of the compact polyurethane is preferably greater than 〇 8 g/cm 3 , particularly preferably greater than 0.9 g/cm ‘ and especially greater than _.〇 g/cm 3 . Examples of materials that can be utilized as additional additives are those that prevent the binder from escaping from the mineral material. An example of this type of additive that can be added is organic fibers, such as cellulosic fibers. In addition, polymers currently used in asphalt-based systems can be added. These are, in particular, chloroprene rubber, styrene-butadiene-styrene, block copolymers or mixtures of these, or any other known rubber or mixtures thereof. These additives may be added directly to the mineral mixture in powder or granules' or may be dispersed in one of the polyaminophthalate components. There are no restrictions on the manufacture of the inventive mixtures including ground pavement, mineral materials and polymer reaction mixtures, 144931.doc 201030211, and other additives for use right. They can be made, for example, in a mixer, incorporating the ground pavement and mineral material into it, and the starting components used to make the polyurethane reaction mixture. & Soil). Additions to be added here, 4 hurried, if desired, are preferably added to the mixture at their respective advantageous joints. Thus, for example, it may be in the form of a solution or dispersion in one of the components of the reaction mixture (for example, in components a) to e), _卩 and may be added Into the mixture. Additives can also be added to the mixture separately. For example, cellulosic fibers can be added at a joint such that they are present in a homogeneous dispersion of the mixture used to make the top layer, but are not irreversibly damaged by the mixing procedure. The inventive mixtures can be produced here, for example, by the method described in DE 196 32 638. Similarly, for example, the polyurethane reaction mixture can be made to begin with, and then mixed with the mineral material, and if additional additives are used. In another embodiment, if desired, the mineral material may be first mixed with certain reaction mixture components, such as component 15) and if present, to e), and then may be added to the mixer. a component (for example component a)). The inventive mixture including the ground pavement can be manufactured at a mounting location by a movable method. It does not need to be transported to the central factory. The hydrophobic polyurethane reaction mixture which can be preferably used is characterized by particularly good processability. For example, the polyurethane reaction mixtures and the polyurethanes obtained therefrom are characterized by particularly good adhesion. Due to the hydrophobic nature of this system, the polyaminophthalate reaction mixture can be hardened even in the presence of water (e.g., rain), resulting in a product that is actually compacted from 144931.doc -19 to 201030211. When the mixture of the invention is applied to a matrix material, the matrix material is not required to be dry. Surprisingly, even when the matrix material is wet, good adhesion can be obtained between the load bearing layer or the top layer and the matrix material. The mixture herein is based on the total weight of the mixture of the invention comprising the ground pavement, the mineral material and the poly-sigma reaction mixture and, if desired, additional additives, preferably from 1% to 2% by weight, particularly preferably 2% by weight. From 0.01 to 15% by weight, and especially from 4% to 1% by weight of the polymer reaction mixture. The bond between the mineral material and the adhesive of the invention is quite strong. Further, in particular, if a hydroxy functional group containing a hydrophobic group is used, hydrolytic degradation of the polyamino phthalate is practically absent, and therefore, the durability of the top layer produced by the method of the present invention is extremely high. The top layer of the invention has particularly good load carrying properties and is therefore suitable for all road, rail and traffic areas, especially for runways and structural grades V to I for relatively high loads, especially 111 to 1 and runways. The roads in which the roads of the class V are constructed, and the roads of the construction class I are highways and highways. The mineral materials used herein preferably include materials suggested for the respective structural grades. Surprisingly, and especially when using hydrophobic reaction mixtures there is only minimal frosting. Another advantage of the top layer of the present invention is the low repair cost. It is sufficient, for example, to produce a small amount of the mixture for the manufacture of the top layer in situ without heating, and applying it to the damaged portion and compacting it. Moreover, the mechanical properties of the top layer of the present invention can be experienced for several years without change. 144931.d〇) • 20- 201030211 Another advantage of the inventive top layer is improved wet skid resistance, especially when the top layer has a high polyurethane content compared to a top layer with a high bitumen content.
包括經研磨路面、礦物材料及聚合物反應混合物、以及 右需要之另外添加物的混合物較佳係在施用於基質材料之 後再壓緊。壓緊之密度在此係取決於所需應用，舉例而 吕，對於製造可散失水分之排水性瀝青僅使用極少的壓 緊，但對於製造可承受高負荷的瀝青則使用較高程度的麼 緊°所需的壓緊程度亦取決於岩石之組成。 本發明方法較佳用於修復道路。經研磨路面在此較佳係 直接在使用場所藉由表面研磨以自需要修復的道路移除材 料而獲得。藉由研磨方法所獲得之材料較佳經破碎、研磨 及/或過篩’以獲得較佳的粒度分佈。將此回收材料與黏 合劑及與另外的礦物材料混合，且較佳於原位重置於道路 上，作為負荷承载層或頂層。為此，較佳用熟悉的黏著促 進劑系統，例如用以聚胺基甲酸自旨為主的喷霧黏著劑預處 理適合的基質。此可得到該等層之間之黏著力之甚至更佳 的改良，及用來補償任何由高負荷（例如嚴重交通負荷）所 引起，或由基質與負荷承制或頂層之間之熱膨脹係數差 異所引起的應力。此等材料在此係使用道路構造中習知之 設備裝設。此處使用之裝設設備較佳具有—抗黏塗層，或 經一較佳基於生物學的釋離劑潤濕。然後，經裝設之頂層 較佳具有經分散細粒礦物材料(例如砂)之塗層，以得到良 好抗濕滑性質之甚至更佳的改良。 144931.doc -21 - 201030211 與其中僅在固定瀝青工廠獲得新鮮瀝青的習知方法相 比，本發明方法可藉由省略在其他情況所需的貨車運輸而目 Μ時間及能量。本發明軌道、道路及交通所用區域:另 —特徵為極高的耐久性（尤其是在經受霜凍-溶解循環時）， 及高彈性以及極高的強度。因此’本發明之頂層結合瀝青 為！的制與基於聚合物反應混合物(諸如聚胺基甲酸醋 或環氧化物）之頂層的有利性質。 本發明藉由以下實例闡釋： 聚胺基甲酸酯反應混合物i : 將100重量份的Elastan 655 1/101系統之多元醇組分及5〇 重量份的Is〇PMDI 92^0(包括二苯基甲烷二異氰酸酯 (MDI)之調配物）互相混合。 .將1〇重量份的聚胺基甲酸酯反應混合物i與由9〇重量份 的礦物混合物（粒度2/5，Piesberger)組成之9〇重量份的混 合物及與10重量份的來自瀝青頂層之經破碎的以瀝青為主 的標準回收材料混合，將其裝入尺寸1〇〇xl〇〇xl〇〇mm的模 具中，以8.5 N/mm2壓緊以及硬化。 所得樣本在儲存超過24小時之後測得的壓縮強度為7 〇 N/mm2。此值顯示可由此類型材料製造頂層。 144931.doc -22-Preferably, the mixture comprising the ground pavement, the mineral material and the polymer reaction mixture, and the additional additives to the right are preferably compacted after application to the matrix material. The density of compaction depends on the desired application, for example, and it uses very little compression for the production of water-dispersible drainage asphalt, but it is used for the manufacture of high-load asphalt. The degree of compaction required depends also on the composition of the rock. The method of the invention is preferably used to repair roads. The ground surface is preferably obtained by surface grinding directly at the place of use to remove material from the road to be repaired. The material obtained by the grinding method is preferably crushed, ground and/or sieved to obtain a preferred particle size distribution. The recycled material is mixed with the binder and with additional mineral materials and is preferably placed in situ on the road as a load bearing layer or top layer. For this purpose, it is preferred to pre-treat a suitable substrate with a conventional adhesion promoter system, such as a spray adhesive based on a polyamine formic acid. This results in an even better improvement in adhesion between the layers and to compensate for any difference in thermal expansion coefficient caused by high loads (such as severe traffic loads) or between the substrate and the load bearing or top layer. The stress caused. These materials are hereby installed using conventional equipment in road construction. The mounting device used herein preferably has an anti-adhesive coating or is wetted by a preferably biologically based excipient. Then, the mounted top layer preferably has a coating of dispersed fine-grained mineral material (e.g., sand) to obtain an even better improvement in good wet skid resistance. 144931.doc -21 - 201030211 Compared to conventional methods in which fresh bitumen is obtained only in fixed bitumen plants, the method of the present invention can be time and energy enhanced by omitting trucking required in other situations. The area used for the track, road and traffic of the present invention is additionally characterized by extremely high durability (especially when subjected to a frost-dissolution cycle), and high elasticity and extremely high strength. Therefore, the top layer of the present invention is combined with asphalt! Advantageous properties of the top layer based on a polymer based reaction mixture such as polyurethane or epoxide. The invention is illustrated by the following examples: Polyurethane reaction mixture i: 100 parts by weight of the polyol component of the Elastan 655 1/101 system and 5 parts by weight of Is〇PMDI 92^0 (including diphenyl) Methane diisocyanate (MDI) formulations are mixed with each other. a mixture of 1 part by weight of the polyurethane reaction mixture i and 9 parts by weight of 9 parts by weight of a mineral mixture (particle size 2/5, Piesberger) and 10 parts by weight of the top layer from the asphalt The crushed asphalt-based standard recycled material is mixed and placed in a mold of size 1〇〇xl〇〇xl〇〇mm, compacted and hardened at 8.5 N/mm2. The resulting sample had a compressive strength of 7 〇 N/mm 2 measured after storage for more than 24 hours. This value shows that the top layer can be made from this type of material. 144931.doc -22-