TW201038636A

TW201038636A - Process for the production of multilayer-coated rubber particles, and multilayer-coated rubber particles

Info

Publication number: TW201038636A
Application number: TW099100576A
Authority: TW
Inventors: Andreas Berlineanu; Kirsten Luce; Margit Bukohl; Nicole Dudek; Siegfried Jittenmeier; Marisa Cruz; Rainer Fuchs; Frank Dieter Kuhn
Original assignee: Evonik Degussa Gmbh
Priority date: 2009-01-13
Filing date: 2010-01-11
Publication date: 2010-11-01
Also published as: DE102009000178A1; WO2010081632A1

Abstract

The invention describes a novel production process for coated particles composed of rubber granulate, the coating, the particles coated therewith and the uses of the coated particles. The coating is solvent-free.

Description

201038636 六、發明說明：【發明所屬之技術領域】本發明關於一種用以塗覆從舊輪胎製造之橡膠粒之方法、塗料組成物及塗覆方法和經塗覆之橡膠粒，及亦關於該橡膠粒作爲人造草皮中或其他地板覆蓋物之塡充物之用途’例如在運動器材建構中。亦有可能塗覆橡膠表面。 0 【先前技術】 EP 1 416 009 ( Miilsener Recycling-und Handelsgesellschaft mbH )說明一種以聚胺甲酸酯爲基之黏合劑覆蓋之鬆散且可流動橡膠粒。亦可將黏合劑隨意地著色。橡膠粒之直徑係從0·5毫米至2.5毫米，且塗層之平均層厚度係從5微米至20微米，而在某些位置上的層厚度可爲高至35微米。未揭示經塗覆之橡膠粒之機械或化學性質。在塗覆過程期間’未特別關注任何添加塗覆材料之特殊方法，例如單〇 —及/或多重塗覆。塗覆方法係如此據稱完全塗覆粒化之舊輪胎，但是未爲此目的說明特殊的技術測量。然而，實際上可假定當使用與從95至90%之橡膠相比爲例如從5至1 0 %之塗覆材料比例時，則不可能完全塗覆橡膠。反而許多因此塗覆之橡膠粒有不完全塗覆之表面。有部分未經塗覆之橡膠從塗覆材料區域凸出，或有噴漆 '未分布至相對深的裂縫或凹處中，或有不完全塗覆的橡膠粒邊緣。此尤其可在顯微鏡下詳細硏究以此方式塗覆之顆粒時觀察到。 -5- 201038636 DE 196 31 251 (Conti Tech Holdings)說明一種以阻燃之黏合劑覆蓋物塗覆之粒化橡膠產物。所使用之黏合劑包含橡膠，且所使用之阻燃劑包含無機阻燃劑，諸如氫氧化鎂或氫氧化鋁。具備有低可燃性塗層之粒化橡膠產物係經加工以得到低可燃性橡膠工件。 DE 24 55 679 (Bayer AG)說明以聚異氰酸酯爲基之黏合劑塗覆直徑從〇. 5至6毫米之橡膠粒，將該等經塗覆之橡膠粒進一步加工以得到彈性地板覆蓋物。 DE 2 5 24 8 7 7 ( Schramm )說明一種由經塗覆之粒子所組成的地板覆蓋物，例如用於動物棚地板，覆蓋物係當場硬化。未提供關於塗層之物理性質的進一步資訊。 DE 2 1 1 0 32 7 ( Allwelt)說明一種彈性運動地板之製造方法，該地板係由舊輪胎所衍生之顆粒及黏合劑所組成。將顆粒與黏合劑混合且硬化，以得到該地板。上述後四種專利公開案未說明任何可用作爲人造草皮之塡充物的粒狀且可流動產物，反而主要努力朝向所獲得的經塗覆粒子之交聯，以得到固體地板覆蓋物。 DE 1 96 3 8 3 1 2 ( Martin)說明一種由粒化橡膠材料及黏合劑所組成的無接縫絕緣材料，在此所使用之黏合劑包含環氧樹脂或（甲基）丙烯酸酯樹脂。 WO 2002/18706 (Fieldturf Inc.)說明一種可運送的模組化人造草皮元件，其係由草皮表面元件和基底元件及用於草皮表面元件之塡充物所組成。塡充物可由沒有任何更詳細指明之橡膠粒，或沙或沙與橡膠粒所組成的混合物 -6 - 201038636 所組成。未述及橡膠粒的任何塗覆。 WΟ 2002/060290 ( Groundscape Technologies LLC) 說明一種由硫化橡膠粒、覆蓋硫化橡膠粒之第一層有色塗層及保護有色塗層免於磨耗之第二塗層所組成的材料。第二塗層包含作爲黏合劑的聚丙烯酸酯、聚胺甲酸酯或苯乙烯/丁二烯橡膠。 US 2002/0 1 28 3 66 ( Coffey )說明一種用以製造由硫化 0 橡膠所組成的有色粒之方法，其包含下列步驟：將水性顏料分散液添加至尙未著色之硫化橡膠粒中，並將兩種成份混合，直到橡膠粒著色爲止，接著添加彈性體乳膠，並重複混合且容許乳膠固定。所使用之彈性體包含苯乙烯/丁二烯橡膠或聚丁二烯橡膠。 DE 103 45 964 (Weitzel)說明一種由橡膠粒所組成且具備有包含礦物質之覆蓋物之顆粒。該包含礦物質之覆蓋物的缺點在於包含礦物質之覆蓋物具有實質上低於黏合〇劑的彈性且因此可具有斷裂傾向的事實。當配備覆蓋物之人造草皮受到長期運動使用時，則包含礦物質之覆蓋物可另外導致人造草葉或人造草皮系統的磨損增加，因爲塡充物材料在人造草葉上凸起的無機及硬表面的磨擦增加。亦有可能使運動使用者可能遭受由人造草皮塡充物材料上高度磨耗之外部塗層所引起對皮膚的磨耗損害。 DE 10 2008 000 367.0說明一種可藉由使用特別好的塗覆材料系統製造經塗覆之橡膠粒之方法。據稱有可能塗覆一或多層。未說明在多層塗覆事件中會達到的特殊影響 201038636 先前技術之缺點所引述之先前技術具有缺點，其未提供由橡® m纟且成的經塗覆之顆粒的任何製造條件，在此塗覆材料特別有效的利用係經由經控制之多層塗覆而進行。此外，未揭示用以提供人造草皮塡充物材料所需之長期耐候性之證據的任何物理及/或化學數據。亦缺少關於經塗覆之橡膠粒之耐磨耗性的數據，此對配備有人造草皮塡充物材料之運動器材沒問題的運動使用爲重要的性質，因爲過度磨耗導致大量的粉塵產生，且過多比例的附聚粒導致不受控制及不可預知的球彈起。【發明內容】鑑於以上引述之先前技術都有其缺點’因此本發明之目的係提供一種用以製造自由流動的橡膠粒之另一製造方法。意欲使此方法簡單且輕易地能夠放大規模’並具有足以能夠以溶劑或不以溶劑操作的可變通性。而且’意欲使此方法花費不多且達成最大的著色強度’同時所使用之塗覆材料量減至最少。 DIN V 18035-7 (初步標準）著手對用於運動器材之人造草皮表面制定技術需求。該標準可應用於各種廣泛的運動類型，實例爲足球、曲棍球、美式足球及網球。當塡充材料暴露於濕氣及由包含重金屬之特殊水溶液 -8 - 201038636 造成之浸濾時’則塡充材料必須具有特定的抗性水平，因爲DIN V 1 8 03 5-7 (初步標準）規定可提供增濕人造草皮表面之措施’以改進運動特性及風險預防特性，且降低磨損。該標準的表6第1 9行指明彈性塡料可以實例說明由 EPDM硫化橡膠及/或回收橡膠所組成。意欲使粒徑範圍從〇 . 5至4毫米，且意欲使低於〇 . 5毫米之成分的比例少於 0 1 %。意欲使顆粒具有切角形狀。進一步意欲發展另一用於橡膠粒的簡單之塗覆方法，以滿足花費不多的製造要求。進一步意欲發展一種用於橡膠粒的簡單但有效之塗覆方法，以滿足花費不多的製造要求。意欲達成最大的著色強度，同時所使用之塗覆材料量減至最少。意欲使橡膠粒上的色彩分布品質達到最大。亦期望根據本發明之方法能夠降低重金屬（諸如Ζη )的浸濾程度。 ❹ 本發明之目的的達成本發明之目的係經由申請專利範圍第1或2項之方法而達成。其他有利的具體例由附屬項保護。本發明之目的係經由在 '流體化床裝置' 固體混合器或轉鼓混合器中用以塗覆粒化橡膠產物之多組份系統及經由製造塗料之方法而達成。該系統係由以環氧樹脂爲基之黏合劑組份及軒硬化劑所組成。可使用各種觸媒來促進交聯反應。 -9 - 201038636 塗層係在從6 0 °C至1 5 0 °C之溫度範圍內，較佳在從8 〇 t至120 °C之溫度範圍內硬化。添加塗覆材料至橡膠粒之方式係使得顆粒在混合器中以第一部分塗覆材料塗覆’接著進行硬化步驟或觀察等待時間’接者添加另一部分塗覆材料，進行硬化步驟或觀察等待時間等。在最後添加塗覆材料的步驟之後，進行另一硬化步驟或觀察等待時間，並接著釋出顆粒。介於個別步驟之間的等待時間係從5至5 〇分鐘，較佳從5至20分鐘，而最特別佳從5至15分鐘。在塗覆過程結束時的硬化步驟需要從5至6 〇分鐘，較佳從5至50分鐘，而最特別佳從5至40分鐘。第一部分塗覆材料爲約1/3之塗覆材料總量，第二部分塗覆材料同樣爲約1 /3之塗覆材料總量及第三部分塗覆材料同樣爲約丨/3之塗覆材料總量，但該等數據被視爲粗略指南。欲塗覆之粒子或塗覆材料調配物與粒子之混合物亦可以紅外線源加熱。以紅外線源加熱可在例如塗覆材料與欲塗覆之粒子混合之後的步驟中進行。而且’有可能使用根據本發明之方法及根據本發明之混合物不僅塗覆橡膠粒’亦可塗覆橡膠表面或橡膠覆蓋物〇顆粒的塗覆係在複數個層中進行。在每次塗覆個別的塗覆材料量之後’併入交聯步驟（以添加塗覆材料所使用之溫度維持特定的時間或以超過添加塗覆材料所使用之溫 -10- 201038636 度的增加溫度維持特定的時間）塗覆材料進料/ 試驗方法單次 (比較用）三次 (根據本發明）連續 (比較用）磨耗性實例 1 ·· 1.92 實例2 : 1.35 實例3 : 1.50 實例4 : 1.70 在UV後的磨耗性實例1 : 3.05 實例2 : 2.20 色彩測量實例 1 : 19.82 a : -4.79 b : 4.22 實例 2 : 24.31 a ： -7.60 b ： 7.74 △ E*ab=6.36 實例顯示根據本發明之塗覆方法的產物性質比先前技藝之方法更好。（實例顯示使用三部分塗覆材料來塗覆實現比使用連續添加塗覆材料或使用單次添加塗覆材料來塗覆更好的結果）。顯著的改進不僅見於UV處理前及後的磨耗性，並亦見於色彩。 Ο 色彩測量係使用以DIN 503 3爲基準之方法。根據本發明用於照射後的磨耗性之加速試驗包含以T 步驟： i-) 測定照射前之顆粒磨耗値， ϋ·) 照射顆粒， iii.)測定經照射顆粒之磨耗値。耐磨耗性測定包括下列步驟·· A)在切削磨碎機中磨碎首先，試圖以磨碎來達成至少一些顆粒粉碎。就此以 -11 - 201038636 本發明之目的而言’使用經常由配備有刀片的水平或垂直排列之轉子所組成的切削磨碎機’就本發明的第一個特別佳的具體例之目的而言，該刀片係與固定在磨碎機罩殼內的刀片逆向操作。此類型的磨碎機之示意圖出現於R0mpp Lexikon Chemie [Rompp5 s Chemical encylopaedia]，Editor: J. Falbe, M. Regitz, 10th Edition, Georg Thieme Verlage, Stuttgart, New York, 1 9 9 8, Band: 4，Stichwort: “Muhle” [Volume 4，Keyword: “Mill”], page 2770 中。關於更多細節，因此參考具有所述及之參考文獻的該發表案。就本發明的第二個特別佳的具體例之目的而言，磨碎機罩殼不包含任何固定的刀片，且因此更容易從罩殻移出經磨碎顆粒。切削磨碎機的操作原理較佳爲切削/撞擊。磨碎過程的強度可以磨碎機耗散的能量方式控制。就本發明之目的而言，較佳的是使用在此耗散之切削磨碎機能量係在從1 0 W至400 W之範圍內，特別在從50 W至 300 W之範圍內的切削磨碎機。切削磨碎機的旋轉速度較佳地在從100 /分鐘至30000/ 分鐘之範圍內’特別在從1000 /分鐘至25000 /分鐘之範圍內。切削磨碎機的週邊速度較佳地在從1〇 m/s至100 m/s 之範圍內，特別在從20 m/s至80 m/s之範圍內。磨碎機的尺寸原則上可自由選擇且適合於每一個別例子的需求。有利的是切削磨碎機的磨碎室在磨碎過程期間 -12- 201038636 的塡充水平係以切削磨碎機的最大容量爲基準計至少1 〇% 0 切削磨碎機及切削工具較佳地由比欲硏究之顆粒更硬的材料所製成。經證實使用由高品質鋼，特別爲1.4034 鋼所組成的磨碎室及切削刀片特別成功。就本發明之目的而言，將欲硏磨之產物較佳地放入切削磨碎機室內且接受經由高品質鋼所製成之撞擊器在預定 0 之暴露時間磨碎時間〃）內的剪切。此過程伴隨有顆粒或在顆粒上的層相互摩擦、破裂及切削。以剪切過程的高剪切水平及複雜本性達成顆粒，特別爲經塗覆之粒化塑料的耐磨耗性之快速測試。下列變化尤其影響此試驗的結果： •塗層的彈性， •塗層的抗剪切性， •塗層對粒子的黏著性，〇 •粒子尺寸， •粒子的尺寸分布， •粒子的彈性， •粒子的抗剪切性。結果亦受到磨碎時間之影響。就本發明之目的而言，較佳地選擇在從5秒至1 0分鐘之範圍內的磨碎時間，特別在從5秒至1 5 0秒之範圍內。切削磨碎機的磨碎力可連續或不連續起作用。經證實以其中磨碎力較佳地在磨碎過程期間不變更的程序特別成 -13- 201038636 功。若必要時，切削磨碎機的磨碎室可在磨碎期間受到溫度控制，特別經加熱或冷卻，以獲得關於顆粒在其他溫度下的磨耗性能之認識。亦可設想在磨碎過程期間以裝備改變的溫度控制。爲此目的，較佳的是將適合的溫度受控制之液體（例如，水）引入磨碎室的加熱/冷卻室中。在商業上可取得適合於本發明之目的的切削磨碎機。下列的磨碎機經證實最特別成功： >分析用磨碎機：M20萬用磨碎機，〇製造商：IK A - W erk e G mb Η & C ο · K G 〇操作原理：切削/撞擊〇最大旋轉速度（1/分鐘）：20000 〇撞擊器/刀片材料：1.4034鋼。磨碎室材料：1.4301鋼 Β )經剪切顆粒之篩分在磨碎過程之後，經磨碎產物的粒徑分布係以篩分析測定，且較佳的程序在此係以D IN 5 3 4 7 7 ( 1 9 9 2年1 1月 )爲基準。較佳的是使用圓形分析篩（其爲所使用之篩的縮寫術語），在此該等篩之篩架較佳地由金屬所組成。篩的標稱直徑較佳爲2 0 0毫米。篩蓋、所有的篩架及篩盤較佳地緊密接合於彼此之上或彼此之中。篩較佳地具有根據 DIN ISO 33 10 Part 1之金屬絲網。在許多例子中，以6個使用金屬絲網的篩之篩組（網目寬度：63微米、125微米、 -14- 201038636 250微米、500微米、1毫米、2毫米）足夠了。就本發明之目的而言，特別佳的是使用包含500微米篩及底座之篩組。不建議機械篩分輔助，諸如橡膠方塊，因爲有結果曲解且損害具有金屬絲網的篩之風險。平面篩分機的選擇較佳地使得用以分離欲篩分之材料成爲粒徑分組之適當方法在15分鐘之內完成。分離較佳 0 地經由使用較佳爲3 00±30/分鐘之旋轉頻率及15毫米振幅之篩組的水平環狀移動而達成。篩分過程較佳爲不連續，且特別佳地以複數次間隔進行，最特別佳地經3至10次間隔，特別經5次間隔。間隔在此較佳地具有相等長度且有利於從1分鐘至5分鐘，特別爲3分鐘長度。在每次間隔之後，較佳地將篩分過程中斷及接著重新開始。此有可能按篩分機內的程式進行。在商業上可取得適合於本發明之目的的篩分機。下列〇的篩分機經證實特別成功： > 舗分機：AS 400 Control 〇製造商：Retsch GmbH 〇篩分之材料的移動：水平環狀。旋轉速度數字顯示：50-300/分鐘 0從1至1 〇分鐘之間隔操作〇 WxHxD ： 540x260x507 毫米 C)秤出各種篩分之分組重量：粒徑分布係藉由秤出篩的重量而以已知的方式測定。 -15- 201038636 將篩分析法的結果與至少一個參考値比較，以分級所硏究之顆粒的磨耗値。在此較佳的是將經磨碎產物所測定之粒徑分布與至少一個其他顆粒的結果比較，以分級與其他顆粒比較的所硏究之顆粒的磨耗値。就本發明的另一較佳的具體例之目的而言，將經磨碎產物所測定之粒徑分布與未磨碎之起始材料之粒徑分布比較，以分級所硏究之顆粒的磨耗値。就本發明的第三個較佳的具體例之目的而言，將經磨碎產物所測定之粒徑分布與至少一個預定的閾値比較，以分級所硏究之顆粒的磨耗値。經證實特別適合於評定就本發明之目的的粒子之磨耗値的另一準則特別爲小於5〇〇微米之粒子比例。 D)隨意的：測試在磨碎室壁上的沉積物就本發明的一個特別佳的變型之目的而言，在磨碎過程之後檢查壁可能的沉積物，該等係由於顆粒暴露於切削磨碎機中的剪切而引起。通常有可能使用光學比較（例如，與適合的參考樣品、參考値、參考刻度比較）來評估或評定在表面上或多層顆粒之中間層中的物質層之強度及黏著性。根據本發明關於顆粒的照射，將顆粒排列在樣品容器中且使用照射燈照射，在照射過程期間定期混合顆粒，如此使顆粒的不同表面受到照射。在此上下文中的用語 ''定期〃係指以相等的間隔規律 -16- 201038636 循環的動作（在此例子中爲混合過程），在此優先選擇包含至少2次程序的重複系統，較佳爲至少5次程序，特別爲至少1 0次程序。動作（在此例子中爲混合過程）的重複率較佳爲每分鐘至少1次程序，優先爲每分鐘至少5次程序，^別爲每分鐘至少1 0次程序。就本發明特別佳的具體體之目的而言，在照射過程期間進行連續混合。 0 就本發明之目的而言，用語 ' 混合〃係指顆粒的徹底混合。此較佳地導致至少兩個顆粒的三維方向改變，較佳爲至少5個顆粒，特別爲至少10個顆粒。此外，使至少兩個顆粒，較佳爲至少5個顆粒，特別爲至少1 0個顆粒的位置較佳地彼此相對改變。就本發明的一個特別佳的具體例之目的而言，將顆粒混合，以此方式使顆粒的至少兩個不同的表面，較佳爲至少3個不同的表面相繼地受到照射，該等表面各受到至少〇兩次照射，較佳爲至少5次，特別爲至少1 0次。因爲在照射過程期間定期的顆粒混合，所以根據本發明之照射過程與其中顆粒不在照射過程期間混合且顆粒僅一個表面受到連續照射的已知之照射過程不同。根據本發明之方法導致在顆粒的整個表面上非常均勻的照射過程’。照射過程較佳地以使得顆粒表面最短的照射時間與顆粒表面最長的照射時間之間的差異爲至多1 00% ，較佳爲至多50%，特別爲至多20%之顆粒表面最長的照射時間的此一方式進行。 -17- 201038636 以照射模擬光線（特別爲日光）對顆粒之影響。光線因此較佳地包含天然日光成分；照射過程較佳地使用從1 奈米至1000奈米之範圍內的波長，較佳從200奈米至400 奈米之範圍內的波長（已知爲近UV輻射）’特別從295 奈米至315奈米之範圍內的波長（已知爲UVB輻射）。就本發明之目的而言’特別有利於使用根據本發明之裝置照射顆粒。該裝置包含： a.至少一個照射燈，及 b .至少一個用於欲照射顆粒之樣品容器，且樣品容器在此具有一個相聯的驅動器，使樣品容器可在照射過程期間移動且可將顆粒混合。照射燈相對於樣品容器的位置原則上可自由選擇，但是排列較佳地以照射燈在樣品容器內部。然而，亦可排列在樣品容器外部，雖然此爲較不佳的變型。此外，優先選擇以輻射直接作用於欲照射之顆粒上。若可能時，應該因此避免可以某種程度或完全吸收或偏離照射源光線之材料在照射燈與顆粒之間的直線上，除非使用特殊的材料（例如，濾片）達到所欲減少的非所欲輻射，例如IR輻射（熱輻射），同時達到最大的穿透性，特別對UVB輻射。照射燈較佳地具有以惰性氣體沖洗且較佳地排列在照射燈與樣品容器之間的護套。就本發明之目的而言，特別適合的惰性氣體特別包含氮氣亦及所有稀有氣體，諸如氦氣和氣氣。 -18" 201038636 就本發明的一個特別佳的具體例之目的而言’亦提供以至少一種氣體及/或至少一種液體沖洗在樣品室中的顆粒，以硏究氣體及/或液體在照射過程期間對顆粒性質之影響。空氣、水、水蒸氣、酸化水蒸氣及酸化雨水特別適合於該等目的。而且，較佳的是照射燈具備有濾片，其瀘除至少一些照射燈的輻射能譜之IR輻射（從780奈米至1毫米）。 0 就此目的而言，較佳的是照射燈具有驟冷室護套’其包含 IR驟冷液且較佳地排列在照射燈與樣品容器之間，特別佳地在惰性氣體沖洗系統與樣品容器之間。特別適合於本發明之目的的IR驟冷液包含在硏究條件下爲液體且吸收在從7 80奈米至1毫米之範圍內的光線至少至某種程度的任何液體。 IR濾片的使用實質上避免顆粒在照射過程期間加熱。未特別限制樣品容器的形狀。然而，經證實特別成功〇的樣品容器具有包含直立圓柱狀之區域，在此照射燈較佳地排列在圓柱中間的中央位置。就本發明的一個特別佳的具體例之目的而言，照射燈具有細長形狀，在此照射燈的方向較佳地對應於樣品容器的主軸，特別爲樣品容器的直立圓柱部分之主軸。樣品容器的內壁較佳地包含反射材料，使例如未撞擊或到達顆粒之光線在反射之後引導至顆粒。因此可顯著地增加照射過程的有效性。在此上下文中，特別適合的反射材料導致至少5 %，較佳爲至少2 5 %，特別佳爲至少5 0 % -19- 201038636 之入射輻射反射。鋼爲最特別適合於此目的的材料。較佳的是樣品容器的整個內表面之至少8 0 %以反射材料塗覆及/或由此材料所組成。就本發明的一個特別佳的具體例之目的而言，樣品容器另外包含具有高導熱性之材料，較佳爲25 °C下所測量大於1 W/ ( m · K )之導熱性，特別大於3 W/ ( m · K )。較佳的是樣品容器之至少8 0 %係由具有高導熱性之材料所組成。本發明之裝置較佳地亦包含至少一種溫度控制元件，較佳爲一種加熱或冷卻元件，特別爲一種冷卻元件，其容許在限定的預定溫度條件下或在限定的預定溫度範圍內照射塑膠粒。樣品容器較佳地亦包含至少一種在照射過程期間用以混合顆粒的混合元件。在此上下文中，在容器旋轉期間使沿著容器主軸的顆粒移動以某種程度偏離的擋板經證實特別成功。爲了增加顆粒的混合效果，使樣品容器的頂端及/或底端，特別佳爲頂端及底端成錐形或成斜面，以增加顆粒在照射過程期間的混合水平。樣品容器的內徑在此較佳地向成錐形或成斜面端的方向減少。樣品容器之大小不大重要。樣品容器之尺寸較佳地使得其可容納從1 0公克至5 00公斤顆粒。就本發明之目的而言，最特別佳的樣品容器之容量係在從1公斤至1 0公斤之範圍內。 -20- 201038636 在照射過程期間裝入樣品容器的顆粒量較佳地從 0.1 %至10%，較佳從0.5%至5%，其係以樣品容器的總容積爲基準計。就本發明之目的而言，較佳地將樣品容器旋轉，以達成顆粒混合。此旋轉較佳地在容器主軸周圍進行，且照射燈在此較佳地同樣沿著該主軸放置。旋轉速度較佳地在從1 rpm至500 rpm之範圍內。 Q 圖1爲特別適合於本發明之目的的照射裝置之結構圖。其包含照射燈（3 )及樣品容器（2 )，在此照射燈（3 )具有細長設計且以置中方式沿著樣品容器（2)的主軸排列。樣品容器（2)具有直立圓柱狀，在其頂端及底端（7 )成具.有某種程度的錐形或斜面，且樣品容器（2 )的內徑在此向成錐形或成斜面端（7 )的方向減少。樣品容器（2 )較佳地由導熱性鋼所製造，其反射至〇少5%之入射輻射。照射燈具有套式惰性氣體沖洗系統（4 )，其係排列在照射燈（3 )與樣品容器（2 )之間。而且，照射燈（3)具有套式驟冷室（5)，其包含IR 驟冷液且排列在惰性氣體沖洗系統（4 )與樣品容器（2 ) 之間。裝置包含溫度控制元件（1 )，較佳爲冷卻水浴’用於照射過程期間的樣品容器（2 )之溫度控制。在照射過程期間，較佳的是驅動器使樣品容器（2 ) -21 - 201038636 在樣品容器的主軸（3 )周圍連續旋轉，此軸爲照象 )沿著其放置的軸。在照射過程期間的溫度原則上可自由選擇，且配合欲模擬或再現的條件。就本發明之目的而言，佳地在從〇°C至95°c之範圍內。可使用照射時間及照射強度來控制顆粒的照射較佳的是照射時間係在從1小時至1 0 0 0小時之範特別在從2 4小時至5 0 0小時之範圍內。而且，較顆粒受到在UVB範圍內從1 W/m2至1 0000 W/m2 內，特別從1 00 W/m2至1 000 W/m2之範圍內的照照射。根據本發明之加速試驗，就其一個特別佳的變而言，在照射過程前及後另外硏究顆粒的色彩性質的色彩測量方法在此係以D IN 5 0 3 3爲基準。在照射過程前及後另外硏究顆粒的鋅溶析。鋅此較佳地係以初步標準 DIN V 1 8 03 5 -7, 6.1 1.3 ( grounds, P art 7 : S yntheti c tur f ar e as )爲基準之方。下列的程序經證實特別成功：201038636 VI. Description of the Invention: [Technical Field] The present invention relates to a method for coating rubber pellets manufactured from used tires, a coating composition and coating method, and coated rubber pellets, and also relates to The use of rubber granules as an entanglement in artificial turf or other floor coverings, for example in the construction of sports equipment. It is also possible to coat the rubber surface. 0 [Prior Art] EP 1 416 009 (Miilsener Recycling-und Handelsgesellschaft mbH) describes a loose and flowable rubber particle covered with a polyurethane-based adhesive. The adhesive can also be optionally colored. The diameter of the rubber particles ranges from 0.5 mm to 2.5 mm, and the average layer thickness of the coating ranges from 5 micrometers to 20 micrometers, and the layer thickness at some locations can be as high as 35 micrometers. The mechanical or chemical properties of the coated rubber particles are not disclosed. No particular attention has been paid to any particular method of adding a coating material during the coating process, such as a single coating - and/or multiple coating. The coating process is so alleged to completely coat the granulated old tires, but no special technical measurements have been stated for this purpose. However, it can be practically assumed that it is impossible to completely coat the rubber when a ratio of the coating material of, for example, from 5 to 10% is used in comparison with the rubber from 95 to 90%. Instead, many of the rubber particles thus coated have incompletely coated surfaces. Some of the uncoated rubber protrudes from the area of the coating material, or the paint is 'not distributed to relatively deep cracks or recesses, or there are edges of rubber particles that are not completely coated. This can be observed in particular when the particles coated in this way are examined in detail under a microscope. -5- 201038636 DE 196 31 251 (Conti Tech Holdings) describes a granulated rubber product coated with a flame retardant adhesive cover. The binder used contains rubber, and the flame retardant used contains an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide. A granulated rubber product having a low flammability coating is processed to obtain a low flammability rubber workpiece. DE 24 55 679 (Bayer AG) describes the application of polyisocyanate-based adhesives to rubber pellets having a diameter of from 0.5 to 6 mm, which are further processed to obtain an elastic floor covering. DE 2 5 24 8 7 7 (Schramm) describes a floor covering consisting of coated particles, for example for animal shed floors, which are hardened on the spot. Further information on the physical properties of the coating is not provided. DE 2 1 1 0 32 7 (Allwelt) describes a method of making an elastic sports floor which consists of particles and binders derived from used tires. The granules are mixed with a binder and hardened to obtain the floor. The latter four patent publications above do not describe any granular and flowable product that can be used as a filling for artificial turf, but instead strive primarily for cross-linking of the obtained coated particles to obtain a solid floor covering. DE 1 96 3 8 3 1 2 (Martin) describes a jointless insulating material composed of a granulated rubber material and a binder, and the binder used herein contains an epoxy resin or a (meth) acrylate resin. WO 2002/18706 (Fieldturf Inc.) describes a transportable modular artificial turf component consisting of a turf surface element and a base element and an entanglement for the turf surface element. The sputum may consist of a rubber granule without any more specific specification, or a mixture of sand or sand and rubber granules -6 - 201038636. Any coating of rubber particles is not mentioned. WΟ 2002/060290 (Groundscape Technologies LLC) describes a material consisting of vulcanized rubber particles, a first layer of colored coating covering the vulcanized rubber particles, and a second coating that protects the colored coating from abrasion. The second coating comprises polyacrylate, polyurethane or styrene/butadiene rubber as a binder. US 2002/0 1 28 3 66 ( Coffey ) describes a method for producing colored particles consisting of vulcanized rubber comprising the steps of: adding an aqueous pigment dispersion to the uncolored vulcanized rubber particles and The two components are mixed until the rubber particles are colored, then the elastomer latex is added and the mixing is repeated and the latex is allowed to settle. The elastomer used contains styrene/butadiene rubber or polybutadiene rubber. DE 103 45 964 (Weitzel) describes a granule composed of rubber granules and having a covering comprising minerals. A disadvantage of the mineral-containing coating is that the mineral-containing cover has a fact that is substantially lower than the elasticity of the adhesive agent and thus can have a tendency to fracture. When the artificial turf with the cover is used for long-term exercise, the inclusion of minerals may additionally lead to increased wear of the artificial grass or artificial turf system, as the swell material is raised on the artificial grass and the inorganic and hard surfaces The friction increases. It is also possible that a sports user may suffer from abrasion damage to the skin caused by an external coating that is highly abrasive on the artificial turf filling material. DE 10 2008 000 367.0 describes a process for producing coated rubber granules by using a particularly good coating material system. It is said that it is possible to coat one or more layers. The special effects that can be achieved in a multi-layer coating event are not illustrated. The prior art cited in the shortcomings of the prior art 201038636 has the disadvantage that it does not provide any manufacturing conditions for the coated particles formed from the rubber and is coated there. A particularly effective use of the coating material is carried out via controlled multilayer coating. Moreover, no physical and/or chemical data is provided for providing evidence of the long-term weatherability required for artificial turf filling materials. There is also a lack of data on the abrasion resistance of the coated rubber particles, which is an important property for sports equipment equipped with artificial turf-filled materials, because excessive wear causes a large amount of dust to be generated, and Excessive proportions of agglomerated particles cause uncontrolled and unpredictable ball bounces. SUMMARY OF THE INVENTION The prior art cited above has its disadvantages. Thus, it is an object of the present invention to provide another method of making rubber particles for free flow. It is intended to make this method simple and easy to scale up' and have sufficient flexibility to operate with or without solvent. Moreover, 'the intention is to make this method inexpensive and achieve maximum color strength' while minimizing the amount of coating material used. DIN V 18035-7 (Preliminary Standard) sets out the technical requirements for the surface of artificial turf for sports equipment. The standard can be applied to a wide variety of sports types, examples of football, hockey, American football and tennis. When the filling material is exposed to moisture and leaching caused by a special aqueous solution containing heavy metals -8 - 201038636' then the filling material must have a specific level of resistance, as DIN V 1 8 03 5-7 (preliminary standard) Provision is made to provide measures to moisturize the surface of artificial turf to improve kinetic and risk prevention properties and to reduce wear. Line 9 of Table 6 of the standard indicates that the elastic coating can be exemplified by EPDM vulcanized rubber and/or recycled rubber. It is intended to have a particle size ranging from 〇 5 to 4 mm, and is intended to have a ratio of less than 1 5 mm to less than 0 1 %. It is intended that the particles have a chamfered shape. It is further intended to develop another simple coating method for rubber pellets to meet the costly manufacturing requirements. It is further intended to develop a simple but effective coating method for rubber pellets to meet the less expensive manufacturing requirements. It is intended to achieve maximum color strength while minimizing the amount of coating material used. It is intended to maximize the quality of the color distribution on the rubber particles. It is also desirable to reduce the degree of leaching of heavy metals such as Ζη in accordance with the method of the present invention.达到 The object of the present invention is achieved by the method of claim 1 or 2. Other advantageous specific examples are protected by an accessory. The object of the present invention is achieved by a multicomponent system for coating a granulated rubber product in a 'fluidized bed unit' solid mixer or drum mixer and by a method of making a coating. The system consists of an epoxy-based adhesive component and an enamel hardener. Various catalysts can be used to promote the crosslinking reaction. -9 - 201038636 The coating is hardened from a temperature range of 60 ° C to 150 ° C, preferably from 8 〇 t to 120 ° C. The method of adding the coating material to the rubber particles is such that the particles are coated with the first portion of the coating material in the mixer 'following the hardening step or observing the waiting time', adding another portion of the coating material, performing the hardening step or observing the waiting time Wait. After the last step of adding the coating material, another hardening step or observation waiting time is performed, and then the particles are released. The waiting time between individual steps is from 5 to 5 minutes, preferably from 5 to 20 minutes, and most preferably from 5 to 15 minutes. The hardening step at the end of the coating process needs to be from 5 to 6 minutes, preferably from 5 to 50 minutes, and most preferably from 5 to 40 minutes. The first portion of the coating material is about 1/3 of the total amount of coating material, the second portion of the coating material is also about 1/3 of the total amount of coating material, and the third portion of the coating material is also about 丨/3. The total amount of material covered, but such data is considered a rough guide. The particles to be coated or the mixture of coating material and particles may also be heated by an infrared source. Heating with an infrared source can be carried out, for example, in the step after the coating material is mixed with the particles to be coated. Further, it is possible to use a coating according to the present invention and a mixture according to the present invention to coat not only rubber particles but also a coating surface of a rubber surface or a rubber covering granule in a plurality of layers. Incorporation of the crosslinking step after each application of the amount of individual coating material (the temperature used to add the coating material is maintained for a specific period of time or exceeds the temperature used for the addition of the coating material - an increase of -10- 201038636 degrees Temperature maintained for a specific time) Coating material feed / test method Single (comparative) Three times (according to the invention) Continuous (comparative) Abrasion Example 1 ·· 1.92 Example 2: 1.35 Example 3: 1.50 Example 4: 1.70 Abrasion after UV Example 1: 3.05 Example 2: 2.20 Color Measurement Example 1: 19.82 a: -4.79 b: 4.22 Example 2: 24.31 a: -7.60 b: 7.74 Δ E*ab=6.36 Example shows according to the present invention The product properties of the coating process are better than those of the prior art. (Examples show that coating with a three-part coating material achieves better results than using continuous addition of coating material or coating with a single addition of coating material). Significant improvements are not only found in the wearability before and after UV treatment, but also in color.色彩 The color measurement system uses the method based on DIN 503 3. The accelerated test for abrasion after irradiation according to the present invention comprises the steps of T: i-) measuring the particle abrasion 照射 before irradiation, ϋ·) irradiating the particles, iii.) measuring the abrasion enthalpy of the irradiated particles. The abrasion resistance measurement included the following steps: A) Grinding in a cutting attritor First, an attempt was made to achieve at least some particle pulverization by grinding. For the purposes of the present invention, -11 - 201038636, the use of a cutting mill consisting of a rotor arranged horizontally or vertically with blades is used for the purpose of the first particularly preferred embodiment of the invention. The blade is operated in reverse operation with a blade that is fixed within the shredder housing. A schematic of this type of grinder appears in R0mpp Lexikon Chemie [Rompp5 s Chemical encylopaedia], Editor: J. Falbe, M. Regitz, 10th Edition, Georg Thieme Verlage, Stuttgart, New York, 1 9 9 8, Band: 4 , Stichwort: “Muhle” [Volume 4, Keyword: “Mill”], page 2770. For more details, reference is made to this publication with the references cited. For the purposes of the second particularly preferred embodiment of the present invention, the grinder casing does not contain any fixed blades and thus it is easier to remove the ground particles from the casing. The operating principle of the cutting and grinding machine is preferably cutting/impacting. The strength of the grinding process can be controlled by the energy dissipated by the grinder. For the purposes of the present invention, it is preferred to use a cutting mill energy source that is dissipated therein in a range from 10 W to 400 W, particularly in the range from 50 W to 300 W. Broken machine. The rotational speed of the cutting and grinding machine is preferably in the range of from 100 / min to 30,000 / min', particularly in the range from 1000 / min to 25,000 / min. The peripheral speed of the cutting attritor is preferably in the range from 1 〇 m/s to 100 m/s, particularly in the range from 20 m/s to 80 m/s. The size of the grinder is in principle freely selectable and suitable for the needs of each individual case. It is advantageous that the grinding chamber of the cutting and grinding machine is at least 1 〇% of the maximum capacity of the cutting and grinding machine during the grinding process -12-201038636. 0 The cutting and grinding machine and the cutting tool are better. The ground is made of a material that is harder than the particles to be studied. Grinding chambers and cutting inserts consisting of high quality steel, particularly 1.4034 steel, have proven to be particularly successful. For the purposes of the present invention, the product to be honed is preferably placed in a cutting and grinder chamber and subjected to a shearer made of high quality steel at a predetermined time of 0 exposure time 〃) cut. This process is accompanied by particles or layers on the particles that rub, break and cut. Particles are achieved with high shear levels and complex nature of the shearing process, particularly for the rapid testing of the abrasion resistance of coated granulated plastics. The following changes particularly affect the results of this test: • the elasticity of the coating, • the shear resistance of the coating, • the adhesion of the coating to the particles, • the particle size, • the size distribution of the particles, • the elasticity of the particles, • The shear resistance of the particles. The result is also affected by the grinding time. For the purposes of the present invention, the milling time in the range from 5 seconds to 10 minutes is preferably selected, particularly in the range from 5 seconds to 1500 seconds. The grinding force of the cutting mill can act continuously or discontinuously. It has been confirmed that the procedure in which the grinding force is preferably not changed during the grinding process is particularly effective as -13-201038636. If necessary, the grinding chamber of the cutting and grinding machine can be temperature controlled during grinding, in particular by heating or cooling, to obtain an understanding of the wear properties of the particles at other temperatures. Temperature control with equipment changes during the grinding process is also envisaged. For this purpose, it is preferred to introduce a suitable temperature controlled liquid (e.g., water) into the heating/cooling chamber of the grinding chamber. A cutting and grinding machine suitable for the purpose of the present invention is commercially available. The following grinders have proven to be the most particularly successful: > Analytical Grinder: M20 Million Grinder, 〇 Manufacturer: IK A - W erk e G mb amp & C ο · KG 〇 Principle of Operation: Cutting / Impact 〇 Maximum rotation speed (1/min): 20000 〇 impactor / blade material: 1.4034 steel. Grinding chamber material: 1.4301 steel Β) Screening by shearing particles After the grinding process, the particle size distribution of the ground product is determined by sieve analysis, and the preferred procedure is here D IN 5 3 4 7 7 (1 January 1992) is the benchmark. Preferably, circular analysis screens (which are abbreviations for the screens used) are used, where the screen frames of the screens are preferably comprised of metal. The nominal diameter of the screen is preferably 200 mm. The screen cover, all of the screen frames and screen trays are preferably tightly joined to one another or to each other. The screen preferably has a wire mesh according to DIN ISO 33 10 Part 1. In many cases, a sieve set of 6 screens using wire mesh (mesh width: 63 microns, 125 microns, -14-201038636 250 microns, 500 microns, 1 mm, 2 mm) is sufficient. For the purposes of the present invention, it is particularly preferred to use a screen comprising a 500 micron screen and a base. Mechanical screening aids, such as rubber squares, are not recommended as there is a risk of misinterpretation and damage to the screen with wire mesh. The selection of the planar screening machine preferably allows the separation of the material to be screened into a suitable method of particle size grouping within 15 minutes. The separation is preferably achieved by using a horizontal annular movement of a sieve set preferably having a rotational frequency of 300 ± 30 / minute and a amplitude of 15 mm. The sieving process is preferably discontinuous, and particularly preferably at a plurality of intervals, most preferably 3 to 10 intervals, in particular 5 intervals. The spacing here preferably has an equal length and is advantageously from 1 minute to 5 minutes, in particular 3 minutes. After each interval, the sieving process is preferably interrupted and then restarted. This may be done by the program in the screening machine. Screening machines suitable for the purposes of the present invention are commercially available. The following sieving machines have proven to be particularly successful: > Paving Machine: AS 400 Control 〇 Manufacturer: Retsch GmbH 移动 Screening of material movement: horizontal ring. Rotating speed digital display: 50-300/min 0 from 1 to 1 minute interval operation 〇WxHxD: 540x260x507 mm C) Weighing the weight of each sieve group: The particle size distribution is based on the weight of the sieve Know the way to determine. -15- 201038636 Compare the results of the sieve analysis with at least one reference enthalpy to classify the wear enthalpy of the granules studied. Preferably, the particle size distribution determined by the milled product is compared to the results of at least one other particle to classify the abrasion enthalpy of the granule of the smear compared to the other granules. For the purpose of another preferred embodiment of the present invention, the particle size distribution measured by the ground product is compared with the particle size distribution of the unmilled starting material to classify the abrasion of the particles value. For the purposes of the third preferred embodiment of the present invention, the particle size distribution determined by the ground product is compared to at least one predetermined threshold 以 to classify the wear enthalpy of the granules in question. Another criterion that has proven to be particularly suitable for assessing the wear of particles for the purposes of the present invention is in particular a proportion of particles of less than 5 microns. D) Random: testing deposits on the walls of the grinding chamber. For the purpose of a particularly preferred variant of the invention, the possible deposits of the walls are examined after the grinding process, as the particles are exposed to the cutting mill Caused by shearing in the crusher. It is often possible to evaluate or assess the strength and adhesion of a layer of material on a surface or in an intermediate layer of a plurality of layers of particles using an optical comparison (e.g., compared to a suitable reference sample, reference enthalpy, reference scale). According to the invention, with respect to the irradiation of the particles, the particles are arranged in a sample container and irradiated with an irradiation lamp, and the particles are periodically mixed during the irradiation process, thereby irradiating different surfaces of the particles. The term ''periodic in this context' refers to the action of the cycle of equal intervals - 1638653636 (in this case, the mixing process), where a repeating system comprising at least 2 programs is preferred, preferably At least 5 procedures, especially at least 10 programs. The repetition rate of the action (in this case, the mixing process) is preferably at least 1 program per minute, preferably at least 5 times per minute, and ^ at least 10 times per minute. For the purpose of the particularly preferred embodiment of the invention, continuous mixing is carried out during the irradiation process. 0 For the purposes of the present invention, the term 'mixed oxime' refers to the thorough mixing of the granules. This preferably results in a change in the three dimensional direction of at least two particles, preferably at least 5 particles, especially at least 10 particles. Furthermore, the positions of at least two particles, preferably at least 5 particles, particularly at least 10 particles, are preferably changed relative to each other. For the purpose of a particularly preferred embodiment of the invention, the particles are mixed in such a way that at least two different surfaces of the particles, preferably at least three different surfaces, are successively illuminated, each of said surfaces It is subjected to at least two irradiations, preferably at least 5 times, in particular at least 10 times. Because of the regular particle mixing during the irradiation process, the irradiation process according to the present invention is different from the known irradiation process in which the particles are not mixed during the irradiation process and only one surface of the particles is continuously irradiated. The method according to the invention results in a very uniform illumination process on the entire surface of the particles'. The irradiation process is preferably such that the difference between the shortest irradiation time of the particle surface and the longest irradiation time of the particle surface is at most 100%, preferably at most 50%, particularly at most 20% of the surface of the particle having the longest illumination time This way is done. -17- 201038636 The effect of illuminating simulated light (especially daylight) on particles. The light thus preferably comprises natural daylight constituents; the illumination process preferably uses wavelengths in the range from 1 nm to 1000 nm, preferably in the range from 200 nm to 400 nm (known as near UV) Radiation) 'Special wavelengths in the range from 295 nm to 315 nm (known as UVB radiation). It is particularly advantageous for the purposes of the present invention to illuminate particles using the apparatus according to the present invention. The apparatus comprises: a. at least one illumination lamp, and b. at least one sample container for the particles to be illuminated, and the sample container has an associated actuator therein such that the sample container can be moved during the irradiation process and the particles can be moved mixing. The position of the illumination lamp relative to the sample container is in principle freely selectable, but the arrangement is preferably such that the illumination lamp is inside the sample container. However, it can also be arranged outside the sample container, although this is a less preferred variant. In addition, it is preferred to directly act on the particles to be irradiated with radiation. If possible, it should therefore be avoided that the material that can absorb or deviate from the source light to some extent or completely will illuminate the line between the lamp and the particle, unless a special material (for example, a filter) is used to achieve the desired reduction. To radiate, for example IR radiation (thermal radiation), while achieving maximum penetration, especially for UVB radiation. The illumination lamp preferably has a sheath that is flushed with an inert gas and preferably arranged between the illumination lamp and the sample container. Particularly suitable inert gases for the purposes of the present invention include, inter alia, nitrogen as well as all noble gases such as helium and gas. -18 " 201038636 for the purpose of a particularly preferred embodiment of the invention 'also provides for rinsing particles in the sample chamber with at least one gas and / or at least one liquid to investigate the gas and / or liquid during the irradiation process The effect on the nature of the particles during the period. Air, water, steam, acidified water vapor and acidified rainwater are particularly suitable for these purposes. Moreover, it is preferred that the illumination lamp be provided with a filter that removes at least some of the IR radiation (from 780 nm to 1 mm) of the radiant energy spectrum of the illumination lamp. 0 For this purpose, it is preferred that the illumination lamp has a quench chamber jacket which comprises an IR quench liquid and is preferably arranged between the illumination lamp and the sample container, particularly preferably in an inert gas flushing system and a sample container between. IR quench liquids which are particularly suitable for the purposes of the present invention comprise any liquid which is liquid under the conditions of the study and which absorbs light in the range from 780 nm to 1 mm, at least to some extent. The use of an IR filter substantially prevents the particles from heating during the irradiation process. The shape of the sample container is not particularly limited. However, sample containers which have proven to be particularly successful have a region containing upright cylindrical shapes, where the illumination lamps are preferably arranged centrally in the middle of the cylinder. For the purpose of a particularly preferred embodiment of the invention, the illumination lamp has an elongated shape, wherein the direction of the illumination lamp preferably corresponds to the major axis of the sample container, particularly the major axis of the upright cylindrical portion of the sample container. The inner wall of the sample container preferably contains a reflective material such that, for example, light that has not impinged or reaches the particle is directed to the particle after reflection. Therefore, the effectiveness of the irradiation process can be significantly increased. In this context, a particularly suitable reflective material results in an incident radiation reflection of at least 5%, preferably at least 25%, particularly preferably at least 50% -19-201038636. Steel is the material most suitable for this purpose. Preferably, at least 80% of the entire inner surface of the sample container is coated with a reflective material and/or consists of the material. For the purpose of a particularly preferred embodiment of the invention, the sample container additionally comprises a material having a high thermal conductivity, preferably having a thermal conductivity greater than 1 W/(m · K ) measured at 25 ° C, particularly greater than 3 W / ( m · K ). Preferably, at least 80% of the sample container is comprised of a material having high thermal conductivity. The apparatus of the present invention preferably also comprises at least one temperature control element, preferably a heating or cooling element, in particular a cooling element which permits irradiation of the plastic pellets under defined predetermined temperature conditions or within a defined predetermined temperature range. . The sample container preferably also contains at least one mixing element for mixing the particles during the irradiation process. In this context, a baffle that moves the particles along the main axis of the container to some extent during rotation of the container has proven to be particularly successful. In order to increase the mixing effect of the particles, the top and/or bottom ends of the sample container, particularly preferably the top and bottom ends, are tapered or beveled to increase the level of mixing of the particles during the irradiation process. The inner diameter of the sample container is here preferably reduced in the direction of a tapered or beveled end. The size of the sample container is not important. The sample container is preferably sized to accommodate from 10 grams to 500 kilograms of particles. For the purposes of the present invention, the most particularly preferred sample containers have capacities ranging from 1 kg to 10 kg. -20- 201038636 The amount of particles charged into the sample container during the irradiation process is preferably from 0.1% to 10%, preferably from 0.5% to 5%, based on the total volume of the sample container. For the purposes of the present invention, the sample container is preferably rotated to achieve particle mixing. This rotation is preferably carried out around the main shaft of the container, and the illumination lamp is here preferably placed along the main axis as well. The rotational speed is preferably in the range of from 1 rpm to 500 rpm. Q Fig. 1 is a structural view of an irradiation apparatus which is particularly suitable for the purpose of the present invention. It comprises an illumination lamp (3) and a sample container (2), wherein the illumination lamp (3) has an elongated design and is arranged in a centered manner along the major axis of the sample container (2). The sample container (2) has an upright cylindrical shape and is formed at its top end and bottom end (7) with a certain degree of taper or bevel, and the inner diameter of the sample container (2) is tapered or beveled thereto. The direction of the end (7) is reduced. The sample container (2) is preferably made of thermally conductive steel that reflects to less than 5% of the incident radiation. The illumination lamp has a jacketed inert gas flushing system (4) arranged between the illumination lamp (3) and the sample container (2). Moreover, the illumination lamp (3) has a sleeve quenching chamber (5) comprising an IR quench liquid and arranged between the inert gas flushing system (4) and the sample container (2). The apparatus comprises a temperature control element (1), preferably a cooling water bath' for temperature control of the sample container (2) during the irradiation process. During the irradiation process, it is preferred that the actuator rotates the sample container (2) -21 - 201038636 continuously around the main axis (3) of the sample container, which is the image along which the axis is placed. The temperature during the irradiation process can in principle be freely chosen and adapted to the conditions to be simulated or reproduced. For the purposes of the present invention, it is preferably in the range from 〇 ° C to 95 ° C. Irradiation time and irradiation intensity can be used to control the irradiation of the particles. Preferably, the irradiation time is in the range of from 1 hour to 100 hours, particularly from 24 hours to 500 hours. Moreover, the comparative particles are exposed to radiation in the range of from 1 W/m 2 to 1 0000 W/m 2 in the UVB range, particularly from 1 00 W/m 2 to 1 000 W/m 2 . In accordance with the accelerated test of the present invention, in a particularly preferred variant, the color measurement method for additionally examining the color properties of the particles before and after the irradiation process is based on D IN 5 0 3 3 . Zinc dissolution of the particles was additionally investigated before and after the irradiation process. Zinc is preferably based on the preliminary standard DIN V 1 8 03 5 -7, 6.1 1.3 (grounds, P art 7 : Syntheti c tur f ar e as ). The following procedures have proven to be particularly successful:

爲了測定重金屬濃度，將1 00公克顆粒在具有口儀器的燒瓶中使用具有固定的co2氣體供給（約升co2/分鐘）的1公升去離子水溶析（顆粒：水 )24小時。將溶析液經由玻璃濾器濾出（經酸洗，微米至1微米）（第一溶析液）。接著使相同的樣爲期24小時的第二次溶析（第二次溶析：從24小I f燈（3 可特別溫度較強度。圍內，佳的是之範圍射強度型目的。較佳溶析在 Sports 法測量 co2入 50毫 =1 ： 1 〇從0.3 品接受時至48 -22- 201038636 小時，"酸性48小時溶析液〃），並將溶析液濾出。在溶析過程期間偶爾搖動燒瓶（有可能在搖動台上），以釋出任何黏附之氣泡。評估較佳地係以酸性4 8小時溶析液中測定的重金屬濃度爲基準。根據本發明之加速試驗，就其一個特別佳的變型目的而言’在照射過程前亦硏究顆粒的保水能力。而且，特別 0 佳的是在照射過程後測定顆粒的保水能力。在此上下文中經證實以下列的程序用以測定保水能力特別成功：引入樣品材料以形成在塑膠圓柱（內徑=27毫米，高度=16〇毫米）中約40毫米高的鬆散地層，在圓柱的下端具有篩網（約0.4毫米網目寬度）。將圓柱安裝在天平上且插入水容器中，使得液體完全覆蓋鬆散的顆粒地層（約 1 0毫米上清液層）。爲了以去礦質水弄濕樣品，將樣品與〇水在最初插入過程之後混合。實驗結果確定以色彩三次塗覆橡膠粒達成更好的色彩，此係與以相同的色彩量單次塗覆顆粒比較時。塗料成分黏合劑組份可由一或多種環氧樹脂所組成。在此可使用傳統的材料：雙酚A樹脂、雙酚F樹脂、雙酚AF樹脂、環脂族環氧樹脂及以氫化雙酚A爲基之環氧樹脂。有用於固體樹脂溶解於反應性稀釋劑中，實例爲脂族單縮水甘 -23- 201038636 油醚、甲苯酚基縮水甘油醚、對-第三丁酚縮水甘油醚、丁二醇二縮水甘油醚、己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚等，及低黏度液體環氧樹脂。此黏合劑組份可爲上述物質所組成的混合物，但亦可包含顏料、塡料（諸如經細磨碎之二氧化矽（粉末狀石英，諸如來自 Quarzwerke GmbH 之 Sikron SF 800，較佳地經矽烷化之石英砂，實例爲Silbond FW 600 EST，以達成與聚合物基質更好的偶合，例如藉由使用由 Evonik Degussa GmbH 所生產且以 DYNASYLAN® GLYMO 所銷售之縮水甘油氧基甲基丙基三甲氧基矽烷））、添加劑、抗氧化劑、UV吸收劑、溶劑、流動控制劑、觸媒。然而，較佳的是使用已知爲來自 Hexion之Epikote® Resin 760的環脂族環氧樹脂。酐硬化劑可包含以各種化學品爲基之經順丁烯二酸酐改質之聚合物及/或甲基六氫苯二甲酸酐（Epikure® Curing Agent 868 > Hexion)、甲基四氫苯二甲酸酐（ Epikure® Curing Agent 866 ' Hexion )。經順丁烯二酸酐改質之聚合物爲聚亞烯烴（卩〇1丫&11^11丫161^)，較佳以1，3-丁二嫌、異戊二嫌、2,3-二甲基-1，3-丁二烯及氯丁二烯爲基者。可使用前述單體之均-或共聚物，但優先選擇爲均聚物，尤其爲那些1,3-丁二烯均聚物。聚亞烯烴可具有1，4鍵聯或1，2鍵聯。然而，同樣有可能使用由1,2鍵聯與1，4鍵聯所組成的混合物’在此以 -24- 201038636To determine the concentration of heavy metals, 100 gram of granules were dissolved in a flask equipped with a mouth apparatus using 1 liter of deionized water (particle: water) with a fixed supply of co2 gas (about liter co2/min) for 24 hours. The eluate was filtered off through a glass filter (acid washed, micron to 1 micron) (first eluent). Then the same sample was used for the second time of 24 hours of dissolution (second dissolution: from 24 small I f lamps (3 can be particularly temperature-strength. Within the circumference, the best is the range of intensity-type purposes. Good dissolution in the Sports method measured co2 into 50 mA = 1 : 1 〇 from 0.3 product acceptance to 48 -22- 201038636 hours, " acidic 48 hours of solution 〃), and the solution was filtered out. Occasionally shake the flask during the precipitation process (possibly on a rocking table) to release any adhering air bubbles. The evaluation is preferably based on the concentration of heavy metals determined in the acidic 48-hour eluent. Accelerated test according to the invention For the purpose of a particularly good variant, the water retention capacity of the particles is also investigated before the irradiation process. Moreover, it is particularly preferable to determine the water retention capacity of the particles after the irradiation process. In this context, the following The procedure was particularly successful in determining the water retention capacity: The sample material was introduced to form a loose formation approximately 40 mm high in a plastic cylinder (inner diameter = 27 mm, height = 16 mm) with a screen at the lower end of the cylinder (approximately 0.4 m) Mesh width). Install the cylinder on the balance and insert it into the water container so that the liquid completely covers the loose particle formation (about 10 mm supernatant layer). In order to wet the sample with demineralized water, the sample is separated from the hydrophobic water. Mixing after the initial insertion process. The experimental results determined that the rubber particles were coated three times in color to achieve a better color, as compared to a single coating of the same amount of color. The coating composition binder component may be one or more epoxy Resin composition. Traditional materials can be used here: bisphenol A resin, bisphenol F resin, bisphenol AF resin, cycloaliphatic epoxy resin and epoxy resin based on hydrogenated bisphenol A. Dissolved in a reactive diluent, examples being aliphatic monocondensed glycan-23- 201038636 oil ether, cresyl glycidyl ether, p-third butanol glycidyl ether, butanediol diglycidyl ether, hexanediol Diglycidyl ether, trimethylolpropane triglycidyl ether, etc., and low viscosity liquid epoxy resin. The binder component may be a mixture of the above substances, but may also contain pigments, dips ( For example, finely ground ruthenium dioxide (powdered quartz, such as Sikron SF 800 from Quarzwerke GmbH, preferably decidated quartz sand, exemplified by Silbond FW 600 EST, for better coupling with polymer matrix) , for example, by using glycidoxymethylpropyltrimethoxydecane produced by Evonik Degussa GmbH and sold by DYNASYLAN® GLYMO), additives, antioxidants, UV absorbers, solvents, flow control agents, touch However, it is preferred to use a cycloaliphatic epoxy resin known as Epikote® Resin 760 from Hexion. The anhydride hardener may comprise a maleic anhydride-modified polymer based on various chemicals and/or methyl hexahydrophthalic anhydride (Epikure® Curing Agent 868 > Hexion), methyltetrahydrobenzene Dimethyl Anhydride ( Epikure® Curing Agent 866 ' Hexion ). The polymer modified by maleic anhydride is a polyalkylene (卩〇1丫&11^11丫161^), preferably 1,3-butane, isoprene, 2,3- Dimethyl-1,3-butadiene and chloroprene are the base. The homo- or copolymers of the foregoing monomers may be used, but are preferably selected as homopolymers, especially those 1,3-butadiene homopolymers. The polyalkylene oxide may have a 1,4 linkage or a 1,2 linkage. However, it is also possible to use a mixture consisting of 1, 2 linkages and 1, 4 linkages. Here, -24- 201038636

的雙種烯分烯質油〇：% 14 包或丁〇經 ;s a S 單達 EP 1，4鍵聯所呈現之排列可爲順式或反式排列。最特別佳是使用具有約75%之1，4-順式雙鍵、約24%之1,4-反式鍵及約1%之1，2雙鍵的聚丁二燦（p〇iy6i，Degussa)。亦有可能使用由前述單體二烯中至少一者及一或多乙烯基化合物及/或烯烴所組成的聚亞烯烴。適合的乙基化合物之實例爲苯乙烯或經取代之苯乙烯、乙烯醚及別以丙烯酸或甲基丙烯酸之酯。適合的烯烴之實例爲乙 ❹ 、丙烯'丁烯或異丁烯。天然油亦可以順丁烯二酸酐改，實例爲椰子油、棕櫚油、蓖麻油、橄欖油、花生油、菜籽油、大豆油 '葵花油、罌粟油、亞麻仁油、木油等經順丁烯二酸酐改質之聚合物可包含從1至20重量之順丁烯二酸酐。較佳的順丁烯二酸酐含量係從7至重量％。以實例說明所使用之經順丁烯二酸酐改質之聚合物含 POLYVEST® OC 8 00 S ' POLYVEST® EP OC 1 000 S 〇 POLYVEST® EP OC 1 200 S。以實例說明所使用之經順烯二酸酐改質之聚合物包含產品POLYVEST® OC 800 S P OLY VESΤ® ΟC 8 00 S 爲取自 Evonik Degussa GmbH 之順丁烯二酸酐改質之PolySl 110且可從Evonik Degus GmbH以此名稱獲取。 POLYVEST® OC 800 S、POLYVEST® EP OC 1000 及POL YVES T® EP OC 1200 S含有無規分布之琥珀酸酐元。此使得最初爲非極性之聚丁二烯更具極性且使其易成各種化學反應。POLYVEST® OC 8 00 S、POLY VEST® -25- 201038636 OC 1 000 S 及 POLYVEST® EP OC 1 200 S 具有好的電絕緣性質及低溫性質。POLYVEST® OC 800 S、POLYVEST® EP OC 1 000 S 及 POLYVEST® EP OC 1 200 S 可溶於脂族化合物、芳族化合物及醚中，且與長鏈油醇酸樹脂、松香、樹脂酯及樹脂酸鋅可相容。其可用作爲2C系統中的交聯組份，作爲用於橡膠混合物，而特別用於EP DM混合物及水溶性氧化乾燥之黏合劑的聚合性白堊活化劑。可將硬化劑組份及/或黏合劑組份隨意地調配成不含溶劑或含溶劑且呈透明塗層或經塡充之系統形式。因此，可隨意添加至硬化劑組份中的另外組份爲有機或無機顏料、濕潤劑、分散劑、潤滑劑、有機及/或無機塡料、抗氧化劑、UV吸收劑、UV安定劑、IR吸收劑、流動助劑、釋出劑或流動控制劑。所使用之溶劑可包含在塗料工業中習知的溶劑，實例爲有機羧酸及脂族醇所組成的酯，例如乙酸乙酯、乙酸丙酯、乙酸丁酯或乙酸甲氧基丙酯。同樣有可能使用脂族及芳族烴、酮及醚。可使用觸媒加速交聯反應。這些觸媒可在塗覆過程之前添加，作爲由黏合劑組份及硬化劑組份所組成的混合物之第三組份。一些觸媒可在各個硬化劑組份或黏合劑組份之製造過程結束之前添加。與黏合劑組份或硬化劑組份摻合亦有可能。三級胺可用作觸媒，實例爲三乙胺、環己基二甲胺、苯甲基二甲胺、N-甲基咪唑、有機鈦酸鹽、銷酸鹽及羧酸鋅和羧酸鉍。 -26- 201038636The two kinds of olefinic olefinic oil 〇: % 14 packets or butyl hydrazine; s a S alone EP 1,4 linkages can be arranged in cis or trans. Most particularly preferably, polypyrylene (p〇iy6i) having about 7% of a 1,4-cis double bond, about 24% of a 1,4-trans bond, and about 1% of a 1,2 double bond is used. Degussa). It is also possible to use a polyalkylene composed of at least one of the aforementioned monomeric dienes and one or more of a vinyl compound and/or an olefin. Examples of suitable ethyl compounds are styrene or substituted styrenes, vinyl ethers and esters of acrylic or methacrylic acid. Examples of suitable olefins are ethyl hydrazine, propylene 'butene or isobutylene. Natural oils can also be modified with maleic anhydride. Examples are coconut oil, palm oil, castor oil, olive oil, peanut oil, rapeseed oil, soybean oil, sunflower oil, poppy oil, linseed oil, wood oil, etc. The enedionic acid modified polymer may comprise from 1 to 20 parts by weight of maleic anhydride. The preferred maleic anhydride content is from 7 to wt%. An example of a maleic anhydride-modified polymer used includes POLYVEST® OC 8 00 S ' POLYVEST® EP OC 1 000 S 〇 POLYVEST® EP OC 1 200 S. By way of example, the urethenedeic anhydride-modified polymer used contains the product POLYVEST® OC 800 SP OLY VESΤ® ΟC 8 00 S is a polySl 110 modified from maleic anhydride of Evonik Degussa GmbH and is available from Evonik Degus GmbH is available under this name. POLYVEST® OC 800 S, POLYVEST® EP OC 1000 and POL YVES T® EP OC 1200 S contain randomly distributed succinic anhydride elements. This makes the initially non-polar polybutadiene more polar and makes it susceptible to various chemical reactions. POLYVEST® OC 8 00 S, POLY VEST® -25- 201038636 OC 1 000 S and POLYVEST® EP OC 1 200 S have good electrical insulation properties and low temperature properties. POLYVEST® OC 800 S, POLYVEST® EP OC 1 000 S and POLYVEST® EP OC 1 200 S are soluble in aliphatic compounds, aromatic compounds and ethers, and with long-chain oil alkyds, rosins, resin esters and resins Zinc acid is compatible. It can be used as a cross-linking component in the 2C system as a polymeric chalk activator for rubber mixtures, particularly for EP DM blends and water-soluble oxidative drying binders. The hardener component and/or the binder component can be optionally formulated into a solvent-free or solvent-containing system in the form of a clear coat or a filled system. Therefore, the other components which can be optionally added to the hardener component are organic or inorganic pigments, wetting agents, dispersants, lubricants, organic and/or inorganic terpenes, antioxidants, UV absorbers, UV stabilizers, IR Absorbent, flow aid, release agent or flow control agent. The solvent to be used may contain a solvent conventionally known in the coatings industry, and examples are esters of an organic carboxylic acid and an aliphatic alcohol such as ethyl acetate, propyl acetate, butyl acetate or methoxypropyl acetate. It is also possible to use aliphatic and aromatic hydrocarbons, ketones and ethers. The catalyst can be used to accelerate the crosslinking reaction. These catalysts may be added prior to the coating process as a third component of the mixture consisting of the binder component and the hardener component. Some catalysts may be added before the end of the manufacturing process for each of the hardener components or adhesive components. It is also possible to blend with the binder component or the hardener component. A tertiary amine can be used as a catalyst, examples being triethylamine, cyclohexyldimethylamine, benzyldimethylamine, N-methylimidazole, organotitanate, pinate, and zinc carboxylate and bismuth carboxylate. . -26- 201038636

黏合劑組份B B組份 B1 B2 B3 B4 B5 B6 B7 Epikote Resin 760 73.2 36.4 44.2 40.4 30.3 45.4 22.7 Tegomer E-Si 2330 2.6 一 • 1.4 1.4 1 乙酸甲氧基丙酯（溶劑） • 9 7 10 12 _ 16.9 Tego Dispers 650 - - . 0.4 0.4 0.4 Blanc fixe micro 13.2 32 9.8 27.6 32.9 30.3 41 Kronos 2190 10 15 30 15 15 15 12 Heliogen Green L 8730 2 3 6 3 0.5 0.5 0.5 Hostaperm Yellow H3G 0.6 1 2 3 - 6 4.5 Hostaperm Yellow H5G _ _ _ 6.5 _ - Monolith Green 600 734 • • - _ • _ Heucodur Yellow 150 Brufasol Yellow 2300 • • - _ _ _ - Wingstay L 1 1 1 1 1 1 1 100 100 100 100 100 100 100Adhesive component BB component B1 B2 B3 B4 B5 B6 B7 Epikote Resin 760 73.2 36.4 44.2 40.4 30.3 45.4 22.7 Tegomer E-Si 2330 2.6 I• 1.4 1.4 1 Methoxypropyl acetate (solvent) • 9 7 10 12 _ 16.9 Tego Dispers 650 - - . 0.4 0.4 0.4 Blanc fixe micro 13.2 32 9.8 27.6 32.9 30.3 41 Kronos 2190 10 15 30 15 15 15 12 Heliogen Green L 8730 2 3 6 3 0.5 0.5 0.5 Hostaperm Yellow H3G 0.6 1 2 3 - 6 4.5 Hostaperm Yellow H5G _ _ _ 6.5 _ - Monolith Green 600 734 • • - _ • _ Heucodur Yellow 150 Brufasol Yellow 2300 • • - _ _ _ - Wingstay L 1 1 1 1 1 1 1 100 100 100 100 100 100 100

硬化劑組份A A組份 A1 A1 A2 A3 A4 A5 A5 Epikure Curing Agent 868 10 10 10 30 15 30 30 Polyvest OC 800 S 60 60 90 70 . _ Polyvest EP OC 1000 S - - _ 85 - _ Polyvest EP OC 1200 S - . _ _ - 70 70 Blanc fixe micro 11 11 . _ _ 一 - Kronos 2190 15 15 - - _ • Heliogen Green L 8730 3 3 _ _ _ - _ Hostaperm Yellow H3G 1 1 _ _ - _ • 100 100 100 100 100 100 100 -27- 201038636 混合比黏合劑(B)= 硬化劑(A) B1:A1 B2:A1 B3:A2 B4:A3 B5:A4 B6:A5 一 — · B7:A5 混合比 1:4 1:2 1:2 1:1 1:1 1:1 2:1 ______ 觸媒觸媒(B): 硬化劑(A) Bl.Al B2.A1 B3.A2 B4:A3 B5:A4 B6:A5 B7：A5 100雷量％之 Epikure 3.2 1.5 2.2 1.3 1.2 1.4 2.2 | - 欲塗覆之粒子包含橡膠粒，其較佳地藉由回收舊輪胎而獲得。橡膠粒之大小係從0.1毫米至1 0毫米，較佳從 0.5毫米至7.5毫米，而特別佳從〇.4毫米至4毫米。因爲製造過程不得到任何規則形狀的橡膠粒，所以要瞭解上述値僅作爲準則値而已。塗層厚度係從1微米至100微米，較佳從2微米至50 微米’而最特別佳從5微米至2 5微米。因爲製造過程不得到任何規則形狀的橡膠粒，所以要瞭解上述値僅作爲準則値而已。特別地，局部厚度顯著較大的塗層可經由塡充橡膠粒中的凹穴而製造。可將組份以預混合形式塗覆或以多組份混合系統的方式塗覆’例如以2C混合及噴霧系統。塗覆過程所必要之由A組份、B組份及觸媒組份所組成的塗覆材料係以複數個步驟塗覆。在塗覆每一個別層之後，可穿插交聯步驟（時間’加熱）。在最後一層塗覆材料添加結束時，則著手 -28- 201038636 交聯步驟（時間，加熱）。【實施方式】本發明之運作將由下列者所組成的混合物B : •環脂族環氧樹脂，使用從1 〇重量％至8 0重量％之環脂族環氧樹脂，〇較佳從15重量％至70重量。/。之環脂族環氧樹脂，而最特別佳從20之50重量％之環脂族環氧樹脂， .從〇. 1重量％至5.9重量°/〇之聚矽氧油量’ •從〇. 1重量％至2.9重量％之濕潤及分散劑量， •抗氧化劑（若適當時）， •硫酸鋇，使用從1重量％至6 0重量％之硫酸鋇，較佳從2 0 重量％至50重量％之硫酸鋇，而最特別佳從30重 Ο 量％至4 5重量％之硫酸鋇， •有可能使用上述量之粉末狀石英及經矽烷改質之粉末狀石英代替硫酸鋇， •二氧化鈦， •若適當時更多顏料，及 .隨意的溶劑，約1 〇重量％-20重量％ (在此以其他組份湊成1 00重量％之總量）與由下列者所組成的混合物A : •脂族酐， -29- 201038636 使用從1重量％至5 0重量。/。之脂族酐’較佳從5重量％至40重量％之脂族酐，而最特別佳從5重量％至3 0重量％之脂族酐，及 .經順丁烯二酸酐改質之聚丁二烯，使用從9 9重量％至5 0重量％之經順丁烯二酸酐改質之聚丁二烯，較佳從9 0重量％至6 5重量％之經順丁烯二酸酐改質之聚丁二烯’而最特別佳從70 至8 5重量％之經順丁烯二酸酐改質之聚丁二烯，以從1 0重量份混合物Β : 1重量份混合物Α至1重量份混合物B : 1 〇重量份混合物A之比混合，並摻合觸媒及將材料硬化。將塗料在從6 0 °C至1 5 0 °C之溫度範圍內，較佳在從8 0 °C至1 2 0 °C之溫度範圍內硬化。將塗料與橡膠粒於轉鼓混合器中混合。觸媒量係以B與A之總和爲基準計從〇.5重量％至5重量％。而且，有可能設定其他的混合比及省略塗料組份之預混合且同時添加該等至橡膠粒的最初進料·中。較佳的混合比陳述於表中。顆粒的塗覆係在複數個層中進行。在每次塗覆個別的塗覆材料量之後，倂入交聯步驟（以添加塗覆材料所使用 t ?盘度維持特定的時間或以超過添加塗覆材料所使用之溫度的增加溫度維持特定的時間）。Hardener component AA component A1 A1 A2 A3 A4 A5 A5 Epikure Curing Agent 868 10 10 10 30 15 30 30 Polyvest OC 800 S 60 60 90 70 . _ Polyvest EP OC 1000 S - - _ 85 - _ Polyvest EP OC 1200 S - . _ _ - 70 70 Blanc fixe micro 11 11 . _ _ I - Kronos 2190 15 15 - - _ • Heliogen Green L 8730 3 3 _ _ _ - _ Hostaperm Yellow H3G 1 1 _ _ - _ • 100 100 100 100 100 100 100 -27- 201038636 Mixing ratio binder (B) = hardener (A) B1: A1 B2: A1 B3: A2 B4: A3 B5: A4 B6: A5 one - · B7: A5 Mix ratio 1:4 1:2 1:2 1:1 1:1 1:1 2:1 ______ Catalyst (B): Hardener (A) Bl.Al B2.A1 B3.A2 B4:A3 B5:A4 B6:A5 B7: A5 100 ray % of Epikure 3.2 1.5 2.2 1.3 1.2 1.4 2.2 | - The particles to be coated comprise rubber granules, which are preferably obtained by recycling old tires. The rubber granules range in size from 0.1 mm to 10 mm, preferably from 0.5 mm to 7.5 mm, and particularly preferably from 〇.4 mm to 4 mm. Since the manufacturing process does not get any regular shape of rubber particles, it is only a matter of course to understand the above. The coating thickness ranges from 1 micron to 100 microns, preferably from 2 microns to 50 microns and most preferably from 5 microns to 25 microns. Since the manufacturing process does not get any regular shape of rubber particles, it is only a matter of course to understand the above. In particular, coatings having a significantly greater local thickness can be made by filling the pockets in the rubber particles. The components can be applied in a pre-mixed form or in a multi-component mixing system, e.g., in a 2C mixing and spray system. The coating material consisting of component A, component B and catalyst components necessary for the coating process is applied in a plurality of steps. After each individual layer is applied, a cross-linking step (time 'heating) can be interspersed. At the end of the last layer of coating material addition, proceed to the -28-201038636 crosslinking step (time, heating). [Embodiment] The operation of the present invention will consist of a mixture of B: • a cycloaliphatic epoxy resin, using from 1% by weight to 80% by weight of a cycloaliphatic epoxy resin, preferably from 15 weights. % to 70 weight. /. The cycloaliphatic epoxy resin, and most preferably from 50% by weight of the cycloaliphatic epoxy resin, from 〇. 1% by weight to 5.9 weight ° / 〇 of the amount of polyoxylized oil 'from 〇. Wetting and dispersing amount of 1% by weight to 2.9% by weight, • Antioxidant (if appropriate), • Barium sulfate, using from 1% by weight to 60% by weight of barium sulfate, preferably from 20% by weight to 50% by weight % barium sulfate, and most particularly from 30% by weight to 45 % by weight of barium sulfate, • It is possible to use the above amount of powdered quartz and decane-modified powdered quartz instead of barium sulfate, • Titanium dioxide, • If appropriate, more pigment, and optional solvent, about 1% by weight to 20% by weight (in this case, the other components are made up of 100% by weight) and a mixture of the following: • Aliphatic anhydride, -29- 201038636 Use from 1% by weight to 50% by weight. /. The aliphatic anhydride 'preferably from 5% by weight to 40% by weight of the aliphatic anhydride, and most preferably from 5% by weight to 30% by weight of the aliphatic anhydride, and the polycondensation by maleic anhydride Butadiene, using from 98% by weight to 50% by weight of polybutadiene modified with maleic anhydride, preferably from 90% by weight to 5% by weight of maleic anhydride The polybutadiene of the quality is most particularly preferably from 70 to 85 % by weight of polybutadiene modified with maleic anhydride, from 10 parts by weight of the mixture Β : 1 part by weight of the mixture Α to 1 weight The mixture of parts B: 1 parts by weight of the mixture A is mixed, and the catalyst is blended and the material is hardened. The coating is hardened in a temperature range from 60 ° C to 150 ° C, preferably from 80 ° C to 120 ° C. Mix the coating with the rubber pellets in a tumble mixer. The amount of the catalyst is from 5% by weight to 5% by weight based on the total of B and A. Moreover, it is possible to set other mixing ratios and omit the pre-mixing of the coating components while adding the same to the initial feed of the rubber pellets. The preferred mixing ratio is set forth in the table. The coating of the particles is carried out in a plurality of layers. After each application of the individual amount of coating material, the crosslinking step is carried out (the t-disk used to add the coating material is maintained for a specific time or maintained at an increased temperature exceeding the temperature used to add the coating material) time).

生產混合物A 混合物A係在氮氣下生產且貯存。就此而言： •將 15 重量份 Epikure Curing Agent 868 (脂族酉f， -30- 201038636Production Mixture A Mixture A was produced under nitrogen and stored. In this regard: • 15 parts by weight Epikure Curing Agent 868 (aliphatic 酉f, -30- 201038636

Hexion )以攪拌與 • 85 重量份 Polyvest EP 〇C 1000 S (來自 Evonik 之特殊的經順丁烯二酸酐改質之聚丁二烯）混合，直到所得調配物均勻爲止。根據本發明之調配物具有極佳的性質，實例爲在以光線照射和風蝕前及後的低磨耗性，及在以光線照射和風蝕前及後的好彈性，且具有對風蝕影響之抗性。而且，根據 0 本發明之調配物在以光線照射和風蝕後具有極佳的色彩牢固性，且亦對暴露於不同溫度及對暴露高溫（例如，以50 °C爲期4週）具有極佳的安定性。而且，當根據本發明之調配物塗覆之顆粒暴露於雨天時，彼等很容易乾燥。在另一具體例中，根據本發明之自由流動粒子可例如當場具備有黏著或聚合或交聯層，其容許粒子鑄塑於任何所欲形狀之基質內且予以硬化。所使用之聚合物基質可包含聚胺甲酸酯樹脂或環氧樹脂。任何所欲之色彩效果可透〇過不同的基質著色及橡膠粒而達成。根據本發明之混合物不僅可用以塗覆橡膠粒，亦可用以塗覆由橡膠所組成的三維物件或塗覆具有由橡膠所組成的表面之物件，實例爲玩具、橡膠墊或輪胎外壁。塡料可添加經細硏磨之無機塡料，實例爲硫酸鋇、碳酸鈣、粉末狀石英或三氫氧化鋁。 -31 - 201038636 塗覆實驗實例1 塗覆實驗係在混合器（製造商L6dige，M5R9 )中以每分鐘1 5 0轉之旋轉速度進行。將1 .5公斤"細"橡膠粒 (可獲自Genan Gruppen GmbH)裝入混合室中且在混合室中以使用加熱護套的熱流體方式加熱至90 °C。一旦橡膠粒達到意欲溫度時，將塗料組成物（藉由將組份A、組份 B與觸媒混合而獲得）以一份添加。接著將塗料在該溫度下經約3 0分鐘硬化。實例2 塗覆實驗係在混合器（製造商L5dige，M5R9)中以每分鐘150轉之旋轉速度進行。將1.5公斤"細〃橡膠粒 (可獲自 Genan Gruppen GmbH)裝入混合室中且在混合室中以使用加熱護套的熱流體方式加熱至90 °C。一旦橡膠粒達到意欲溫度時，將塗料組成物（藉由將組份A、組份 B與觸媒混合而獲得）分三份添加，在每次添加之間以 1 20 °C混合10分鐘。在添加第三份之後，將塗料在該溫度下經約1 5分鐘硬化。實例3 塗覆實驗係在Drais TD250混合器中以23轉/分鐘之旋轉速度進行。將90公斤 > 細"橡膠粒（可獲自Genan Gruppen GmbH )裝入混合室中且在混合室中以熱流體方 -32- 201038636 式加熱至90 °C。一旦橡膠粒達到意欲溫度時’將塗料組成物（藉由將組份A、組份B與觸媒混合而獲得）分三份添加，在每次添加之間以9 0 °C混合2 0分鐘。在添加第三份之後，將塗料在105 °C下經約1〇分鐘硬化。實例4 塗覆實驗係在具有25 0公升標稱容量的Drais TD250 0 真空槳式乾燥器中以23轉/分鐘之旋轉速度進行。將85 公斤 '"細"橡膠粒（可獲自 Genan Gruppen GmbH)裝入混合室中且在混合室中以熱流體方式加熱至8 5 °C。一旦橡膠粒達到意欲溫度時，在1 8分鐘期間內連續添加塗料組成物（藉由將組份A、組份B與觸媒混合而獲得），並接著將混合物加熱至12 0 °C且在該溫度下經20分鐘硬化。實例5 :生產包含溶劑之調配物〇在根據實例1-4之實驗中所使用之塗覆材料調配物係Hexion) was mixed with 85 parts by weight of Polyvest EP® C 1000 S (special maleic anhydride modified polybutadiene from Evonik) until the resulting formulation was homogeneous. The formulations according to the invention have excellent properties, examples of low attrition before and after exposure to light and wind erosion, and good elasticity before and after exposure to light and wind erosion, and resistance to wind erosion . Moreover, the formulation according to the invention has excellent color fastness after exposure to light and wind erosion, and is also excellent for exposure to different temperatures and exposure to high temperatures (for example, 4 weeks at 50 °C). Stability. Moreover, when the granules coated with the formulations according to the present invention are exposed to rain, they are easily dried. In another embodiment, the free-flowing particles according to the present invention may, for example, be provided with an adhesive or polymeric or crosslinked layer on the spot that allows the particles to be cast into a matrix of any desired shape and hardened. The polymer matrix used may comprise a polyurethane resin or an epoxy resin. Any desired color effect can be achieved by different matrix coloring and rubber particles. The mixture according to the present invention can be used not only to coat rubber particles, but also to coat a three-dimensional object composed of rubber or to coat an object having a surface composed of rubber, such as a toy, a rubber mat or a tire outer wall. Dilute The finely pulverized inorganic tanning material may be added, examples being barium sulfate, calcium carbonate, powdered quartz or aluminum trihydroxide. -31 - 201038636 Coating experiment Example 1 The coating experiment was carried out in a mixer (manufacturer L6dige, M5R9) at a rotational speed of 150 revolutions per minute. 1.5 kg of "fine" rubber pellets (available from Genan Gruppen GmbH) were charged into the mixing chamber and heated to 90 °C in the mixing chamber as a hot fluid using a heated jacket. Once the rubber particles have reached the desired temperature, the coating composition (obtained by mixing component A, component B with the catalyst) is added in one portion. The coating is then hardened at this temperature for about 30 minutes. Example 2 The coating experiment was carried out in a mixer (manufacturer L5dige, M5R9) at a rotational speed of 150 revolutions per minute. 1.5 kg of fine rubber pellets (available from Genan Gruppen GmbH) were charged into the mixing chamber and heated to 90 °C in the mixing chamber using a heated fluid using a heated jacket. Once the rubber particles reached the desired temperature, the coating composition (obtained by mixing component A, component B with the catalyst) was added in three portions, and mixed at 10 ° C for 10 minutes between each addition. After the addition of the third portion, the coating was hardened at this temperature for about 15 minutes. Example 3 The coating experiment was carried out in a Drais TD250 mixer at a rotation speed of 23 rpm. A 90 kg > fine "rubber pellet (available from Genan Gruppen GmbH) was charged into the mixing chamber and heated to 90 °C in the mixing chamber as hot fluid -32-201038636. Once the rubber particles reach the desired temperature, 'the coating composition (obtained by mixing component A, component B with the catalyst) is added in three portions, and mixed at 90 ° C for 20 minutes between each addition. . After the addition of the third portion, the coating was hardened at 105 ° C for about 1 minute. Example 4 The coating experiment was carried out at a rotational speed of 23 revolutions per minute in a Drais TD250 0 vacuum paddle dryer having a nominal capacity of 25 0 liters. 85 kg of '"fine" rubber pellets (available from Genan Gruppen GmbH) were charged into the mixing chamber and heated to 85 °C in a mixing chamber. Once the rubber particles reach the desired temperature, the coating composition is continuously added over a period of 18 minutes (obtained by mixing component A, component B with the catalyst), and then the mixture is heated to 120 ° C and It hardens at this temperature for 20 minutes. Example 5: Production of a formulation comprising a solvent 〇 A coating material formulation used in the experiments according to Examples 1-4

如以下方式生產：生產混合物A •混合物A係在氮氣下生產且貯存。就此而言：將 15 重量份 Epikure Curing Agent 868 (脂族酐， Hexion )以攪拌與 • 85 重量份 Polyvest EP OC 1000 S (來自 Evonik 之特殊的經順丁烯二酸酐改質之聚丁二烯）混合， -33- 201038636 直到所得調配物均勻爲止。Produced as follows: Production Mixture A • Mixture A was produced under nitrogen and stored. In this regard: 15 parts by weight of Epikure Curing Agent 868 (aliphatic anhydride, Hexion) with stirring and • 85 parts by weight of Polyvest EP OC 1000 S (special polybutadiene modified by maleic anhydride from Evonik) ) Mix, -33- 201038636 until the resulting formulation is homogeneous.

生產混合物B 混合物B係如以下方式生產： • 73.2重量％之Epikote Resin 760 (環脂族環氧樹脂，H ex i ο η ) ， • 13.2重量％之 Blanc fixe micro (硫酸鋇塡料， Sachtleben )， • 10 重量％之 Kronos 2190 ( Ti02 顏料，Kronos)， • 2 重量％之 Heliogen Green L 8730 (顏料，BASF) • 0.6 重量 °/。之 Hostaperm Yellow H3G(顏料， C1 ariant ) ’ • 1 重量％之 Wingstay L (抗氧化劑 ’ Eliokem) ’ 將上述分散且在球磨機中磨碎’直到達成適當的粒度（ Grindo値$5微米）爲止。Production Mixture B Mixture B is produced as follows: • 73.2% by weight of Epikote Resin 760 (cycloaliphatic epoxy resin, H ex i ο η ), • 13.2% by weight of Blanc fixe micro (sulphate, Sachtleben) , • 10% by weight of Kronos 2190 (Ti02 pigment, Kronos), • 2% by weight of Heliogen Green L 8730 (pigment, BASF) • 0.6 weight °/. Hostaperm Yellow H3G (pigment, C1 ariant)' • 1% by weight of Wingstay L (antioxidant 'Eliokem'' Disperse the above and grind in a ball mill until a suitable particle size (Grindo® $5 microns) is achieved.

Grindo値係根據DIN EN ISO 1 524而測定。Grindo® is determined according to DIN EN ISO 1 524.

生產混合物A 混合物A係在氮氣下生產且貯存。就此而言： .將 15 重量份 Epikure Curing Agent 8 6 8 (脂族酉干’Production Mixture A Mixture A was produced under nitrogen and stored. In this regard: . 15 parts by weight Epikure Curing Agent 8 6 8 (aliphatic dried ’

Hexion)以攪拌與 • 85 重量份 Polyvest ΕΡ ΟC 1 0 0 0 S (來自 Evonik 之特殊的經順丁烯二酸酐改質之聚丁二烯）混合’ -34- 201038636 直到所得調配物均勻爲止。實例1 組份A :根據A3之成分組份B :成分B 7 觸媒·· 1.2公克Epikote A : B之定量比例=1 : 1Hexion) was mixed with <85 parts by weight Polyvest® 1C 1 0 0 0 S (special maleic anhydride modified polybutadiene from Evonik) to -34- 201038636 until the resulting formulation was homogeneous. Example 1 Component A: Component according to A3 Component B: Component B 7 Catalyst · 1.2 g Epikote A: Quantitative ratio of B = 1 : 1

G 實例2 :不含溶劑之調配物將由下列者所組成的混合物B : •環脂族環氧樹脂，使用從1 0重量％至8 0重量％之環脂族環氧樹脂，較佳從4 0重量％至8 0重量％之環脂族環氧樹脂，而最特別佳爲45重量％之環脂族環氧樹脂’ • 從0.1重量％至5.9重量％之聚矽氧油量’ 〇 •從0.1重量％至2.9重量％之濕潤及分散劑量， •抗氧化劑， •硫酸鋇，使用從1重量％至5 0重量％之硫酸鋇’較佳從2 〇重量％至4 5重量％之硫酸鋇，而最特別佳從3 0重量％至4 0重量％之硫酸鋇， •二氧化欽， •更多顏料，及 .(在此以其他組份湊成1 〇〇重量％之總量） -35- 201038636 與由下列者所組成的混合物A : •脂族酐，使用從1重量％至50重量％之脂族酐，較佳從5重量％至4 0重量％之脂族酐，而最特別佳從7重量。/〇至30重量％之脂族酐，及 •經順丁烯二酸酐改質之聚丁二烯，使用從99重量％至50重量％之經順丁烯二酸酐改質之聚丁二烯，較佳從90重量％至65重量％之經順丁烯二酸酐改質之聚丁二烯，而最特別佳爲70 重量％之經順丁烯二酸酐改質之聚丁二烯，以從1 〇重量份混合物B : 1重量份混合物A至1重量份混合物B: 10重量份混合物A之比混合，並摻合觸媒且將產物在從80°C至120°C下於轉鼓混合器中與橡膠粒混合。亦有可能設定其他的混合比及省略塗料組份之預混合且同時添加該等至橡膠粒的最初進料中。較佳的混合比陳述於表中〇G Example 2: a solvent-free formulation will be a mixture of the following: B: • a cycloaliphatic epoxy resin, using from 10% by weight to 80% by weight of a cycloaliphatic epoxy resin, preferably from 4 0% by weight to 80% by weight of a cycloaliphatic epoxy resin, and most preferably 45% by weight of a cycloaliphatic epoxy resin' • From 0.1% by weight to 5.9% by weight of the amount of polyoxyxene oil 〇• From 0.1% by weight to 2.9% by weight of the wetting and dispersing amount, • Antioxidant, • Barium sulphate, using from 1% by weight to 50% by weight of barium sulphate, preferably from 2% by weight to 45% by weight of sulphuric acid钡, and most particularly from 30% to 40% by weight of barium sulfate, • Dioxin, • More pigments, and (in this case, the other components are made up to 1% by weight) -35- 201038636 with a mixture of the following: A: • an aliphatic anhydride, using from 1% by weight to 50% by weight of an aliphatic anhydride, preferably from 5% by weight to 40% by weight of an aliphatic anhydride, and Most particularly good from 7 weights. /〇 to 30% by weight of aliphatic anhydride, and • polybutadiene modified with maleic anhydride, using from 99% by weight to 50% by weight of polybutadiene modified with maleic anhydride Preferably, from 90% to 65% by weight of polybutadiene modified with maleic anhydride, and most preferably 70% by weight of polybutadiene modified with maleic anhydride, Mixing from 1 part by weight of the mixture B: 1 part by weight of the mixture A to 1 part by weight of the mixture B: 10 parts by weight of the mixture A, and blending the catalyst and rotating the product from 80 ° C to 120 ° C The mixer is mixed with rubber particles. It is also possible to set other mixing ratios and omit the premixing of the coating components while adding the same to the initial charge of the rubber pellets. The preferred mixing ratio is stated in the table〇

生產混合物B 混合物B可如以下方式生產： • 45.4重量％之Epikote Resin 760 (環脂族環氧樹脂，H ex i ο η ) ， • 1.4 重量％之 Tegomer E-Si 2330 (聚砂氧油，Production Mixture B Mixture B can be produced as follows: • 45.4% by weight of Epikote Resin 760 (cycloaliphatic epoxy resin, H ex i ο η ), • 1.4% by weight of Tegomer E-Si 2330 (polysilicate oil,

Evonik) ， • 0.4重量％之Tego Dispers 650 (濕潤及分散劑， -36- 201038636Evonik) , • 0.4% by weight of Tego Dispers 650 (wetting and dispersing agent, -36- 201038636

Evonik)， • 30.3重量％之 Blanc fixe micro (硫酸鋇塡料’Evonik), • 30.3% by weight of Blanc fixe micro

Sachtleben ) ’ .15 重量 °/。之 Kronos 2190 ( Ti02 顏料，Kronos)，Sachtleben ) ’ .15 weight °/. Kronos 2190 (Ti02 pigment, Kronos),

• 〇·5 重量％之 Heliogen Green L 8730 (顏料 ’ BASF )， • 6 重量％之 Hostaperm Yellow H3G (顏料 ’ Clariant O )，及 • 1 重量％之 Wingstay L (抗氧化劑，Eliokem)，將上述分散且在球磨機中硏碎，直到顆粒具有適當的細度爲止。• 〇·5 wt% of Heliogen Green L 8730 (pigment 'BASF), • 6 wt% of Hostaperm Yellow H3G (pigment 'Clariant O), and • 1 wt% of Wingstay L (antioxidant, Eliokem), disperse the above And mashed in a ball mill until the particles have the proper fineness.

生產混合物A 混合物A係在氮氣下生產且貯存。就此而言： .將 30 重量份 Epikure Curing Agent 868 (脂族酐， O Hexion)以攪拌與 • 70 重量份 Polyvest EP OC 1200 S (來自 Evonik 之特殊的經順丁烯二酸酐改質之聚丁二烯）混合，直到所得調配物均勻爲止。塗料亦可以塗覆技術習知的任何方法塗覆，實例爲噴霧、浸漬、以塗刷塗覆、刮刀片塗覆、滾筒塗覆或類似方法。可使用溶劑使塗料黏度適合於塗覆方法。根據本發明之塗覆材料系統以極佳的方式與欲塗覆之橡膠粒黏合’而且個別經完全或至某種程度硬化之塗覆材 -37- 201038636 料層彼此亦充份黏合。在先前硬化之塗層上的此滿意的塗層黏合容許再塗覆先前已塗覆且用過的粒子或已塗覆過的粒子。此方法可用於更新或改變在先前用過的橡膠粒上的塗覆材料。【圖式簡單說明】圖1顯示用於顆粒照射之裝置的一個較佳具體例。【主要元件符號說明】 1 :溫度控制元件 2 :樣品容器 3 ‘·照射燈 4 :惰性氣體沖洗系統 5 :驟冷室 7 :以某種程度成錐形或斜面之端 -38-Production Mixture A Mixture A was produced under nitrogen and stored. In this regard: . 30 parts by weight of Epikure Curing Agent 868 (aliphatic anhydride, O Hexion) with stirring and • 70 parts by weight of Polyvest EP OC 1200 S (specially modified by maleic anhydride from Evonik) The diene) is mixed until the resulting formulation is homogeneous. The coating may also be applied by any method known in the art, examples of which are spray, dipping, brush coating, doctor blade coating, roller coating or the like. A solvent can be used to adapt the viscosity of the coating to the coating method. The coating material system according to the invention is bonded to the rubber particles to be coated in an excellent manner and the individual coatings which are completely or to some extent hardened are also sufficiently bonded to one another. This satisfactory coating adhesion on the previously hardened coating allows recoating of previously coated and used particles or coated particles. This method can be used to update or change the coating material on previously used rubber particles. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a preferred embodiment of a device for particle irradiation. [Main component symbol description] 1 : Temperature control element 2 : Sample container 3 ‘· Illumination lamp 4 : Inert gas flushing system 5 : Quenching chamber 7 : To some extent tapered or beveled end -38-

Claims

201038636 VII. Patent application group: 1. A method for coating rubber particles, characterized in that a mixture A composed of an aliphatic anhydride and a polybutadiene modified with maleic anhydride is in a mixing device. Mixing with a mixture of a cycloaliphatic epoxy resin and a conventional adjuvant, a catalyst and, if appropriate, a solvent, and then adding the coating mixture to the coating device by mixing at a first moment In the rubber granules, and before the second and any more additions, the mixture is hardened and the final coating is cured in the final step. 2. The method of claim 1, wherein the coating mixture is added in from 2 to 7 sub-steps. 3. The method of claim 1, wherein the coating is added in from 2 to 5 sub-steps. 4. The method of claim 1, wherein the coating is added in from 2 to 3 sub-steps. 5. The method according to any one of claims 1 to 4, wherein the hardening step is in G It is carried out from 60 ° C to 150 ° C. The method according to any one of claims 1 to 4, wherein the hardening step is carried out at from 80 ° C to 120 ° C. 7. The method according to any one of claims 1 to 4, wherein the method is carried out in a fluidized bed reactor. 8. The method according to any one of claims 1 to 4, wherein the method is carried out in a solid mixer or a tumble mixer. 9. A coated rubber pellet, which can be obtained by the method of claims 1 to 8. -39 - 201038636 1 0 · The use of coated rubber pellets in claim 9 of the patent application is for the construction of sports equipment. 1 1. The use of a coated rubber pellet of claim 9 in the patent application, which is used as a filling for artificial turf. 1 2· An artificial turf characterized by being coated with rubber particles coated in the ninth application of the patent application. The use of coated rubber pellets of claim 9 is applied as an environmentally conscious ingredient. 1 4. The use of a coated rubber particle of claim 8 in the patent application as a filler for the manufacture of a cover by introducing the coated rubber particles into a polymer matrix and The polymer matrix hardens. 1 5 . A coated rubber obtainable by the method of claims 1 to 8. 1 6 - An article consisting of coated rubber which can be obtained by the method of claims § VIII to 8. 17. A method of coating previously coated rubber granules or rubber parts' characterized in that the previously coated rubber granules or rubber parts are coated in the method of claim 1 of the patent application. -40