CN1126454A - 形状精确的颗粒及其制法 - Google Patents
形状精确的颗粒及其制法 Download PDFInfo
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- CN1126454A CN1126454A CN94192606A CN94192606A CN1126454A CN 1126454 A CN1126454 A CN 1126454A CN 94192606 A CN94192606 A CN 94192606A CN 94192606 A CN94192606 A CN 94192606A CN 1126454 A CN1126454 A CN 1126454A
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- mould
- abrasive
- adhesive precursor
- shape
- particle
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/2438—Coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明方法包括以下步骤:a)提供一模具(16),它的表面上至少有一孔通入其至少一个模腔;b)提供一个将粘合剂前体引入模具中的装置(14);c)提供一个令粘合剂前体至少部分固化的装置(25);d)将粘合剂前体填入模具的模腔;e)连续移动模具使其中的粘合剂前体固化成粘合剂,其形状与模腔形状对应;f)使固化的粘合剂脱离模具;g)将粘合剂转变成形状精确的颗粒(26)。步骤f)和g)可以是同时的。所得颗粒可粘合在一起成为一个形状物体如轮子。若颗粒物质中还含有磨粒,则这种颗粒可粘接于涂覆磨料制品的背衬,或者可粘合进非纺织纤维基材制成非纺织磨料制品。
Description
发明的背景1.发明的领域
本发明涉及含有粘合剂的颗粒物质及其制造方法,当这种颗粒物质中还含有磨粒时,它可用于粘合磨料制品、涂覆磨料制品以及非纺织磨料制品。2.本技术的讨论
常规的涂覆磨料制品通常是一层磨粒粘着在背衬上。这层磨粒中一般只有一小部分在涂覆磨料制品的有效寿命中实际使用,而其大部分是浪费掉的。而且,作为涂覆磨料制品中成本更高的组件的背衬,在它还没有破损时也就弃去了。
人们曾经对背衬上改进磨粒分布作了不少努力,目的是使得有更高百分数的磨粒能被实际使用,从而延长涂磨覆料制品的有效寿命。涂覆磨料制品的寿命既经延长,则可较少地更换研磨带或研磨盘,从而节省时间,降低操作成本。在背衬上仅仅涂覆更厚的磨粒层并不能解决问题,因为在顶上面磨料下方的那些磨粒是不大可能在磨削过程中使用到的。
人们知道有几种方法可用来在涂覆磨料制品中分布磨粒,以延长其使用寿命。一种方法是将磨料团粒加入涂覆磨料制品中。磨料团粒系由一些磨粒用粘合剂接在一起的颗粒。由于团粒形状与大小都不均匀,所以难以控制与工作表面接触的磨粒数量。因此,很有必要有一种制备形状精确的磨料团粒的经济上可行的方法。
发明的提要
本发明提供形状精确的颗粒以及制备这种颗粒的方法。这种颗粒含有粘合剂。在一种需要采用的实施方案中,是将许多晶粒分散在该粘合剂中。
本发明的方法包括如下步骤:
(a)提供一个三维体的模具,它具有至少一个连续表面,所述表面上至少有一个孔,通过它可进入所述三维体的模腔中;
(b)提供一个能将含有热固性树脂的粘合剂前体通过该至少一个孔引入该至少一个模腔中的引入装置;
(c)提供一个具有固化区的装置,供至少部分地固化所述粘合剂前体之用;
(d)将所述粘合剂前体引入所述至少一个模腔的至少一部分空间中;
(e)令所述的至少一个模腔连续地通过所述固化区,使所述粘合剂前体至少部分固化,以提供一固化的可手持的粘合剂物质,其形状对应于粘合剂前体被引入模腔的那部分空间的形状;
(f)将所述粘合剂由所述至少一个模腔卸出;
(g)将所述粘合剂转变形成为形状精确的颗粒。
步骤(f)和步骤(g)可以是同时进行的。
在一个要采用的实施方案中,在步骤(d)中将许多磨粒掺入在粘合剂前体中。而在步骤(f)中,从模具的至少一个模腔中卸出的粘合剂颗粒中就含有磨粒了。也可以在粘合剂前体中掺入磨粒以外的物质。
固化区中可以用热源,也可用幅射源,也可两者都用。幅射源包括电子束、可见光和紫外光。在一般方法的一种变体中,可以通过热能或者幅射能与热量的结合来进行固化。
在一般的和优选的实施方案中,最好是令步骤(d)、(e)、(f)连续进行。在这些实施方案中,模具宜为一环形带子或一转筒,最好是绕其轴旋转的固柱形转筒。也可以使用具有两个末端的带子。这种有两个末端的带子从一退绕筒向一重绕筒运动。模具最好有许多个模腔。
在方法的步骤(e)中,粘合剂前体固化成为可手持的粘合剂。
粘合剂转变为颗粒的方式有几种。一个方式就是粘合剂由模具的模腔中卸出的即是一些单个的颗粒。这些颗粒中可含,也可不含添加物质。通常掺入的添加物质就是磨粒。这样获得的颗粒最好具有与模具基本相同的形状。因此颗粒形状即取决于模腔的形状。在这第一种方式中,步骤(f)和(g)是同时进行的,因为当成形的颗粒由模具的模腔中释放出来时就具有模腔的特定形状。
第二种方式中,从模具的主要表面卸出的粘合剂,其形状是一个片材,它含有与模腔尺寸与和形状基本相同的许多形状部分,但这些部分由一相对较薄的粘合剂材料层连接在一起。在这第二种方式中,接着就将该片材在这个薄的连接层处破碎掉,形成本发明的颗粒物质。这些颗粒可进行筛选或分级,得到所需的颗粒尺寸分布。只要这层粘合剂连接层仔细破碎或压碎,得到颗粒的形状即基本上与模腔的形状相同。
使用一种传送带将粘合剂前体输入到模具中也属本发明范围。可以将粘合剂前体涂覆在该传送带的一个主表面即前表面上,然后将此已涂覆了粘合剂前体的传送带与内含模腔的模具的连续表面相接触。当模具中的粘合剂前体已至少部分固化以后,与传送带表面粘接较强的粘合剂,先与模具脱离,然后再与传送带脱离。另一个办法是,将粘合剂前体涂覆在含模腔的模具连续表面上,并填满模腔,然后令传送带与其模腔中装有粘合剂前体的模具的连续表面相接触,务使模膛中所填的粘合剂前体与传送带表面接触。在粘合剂前体至少部分固化以后,粘合剂就粘着于传送带表面,而不与模具粘着。然后从传送带上卸除粘合剂。随后形成形状精确的颗粒。
这种形状精确的颗粒可以通过添加研磨用途的物质得到改进,或用其本身,或用作磨料制品的一个组分。本发明的颗粒可用于制造含有许多一定形状颗粒的磨料制品,这些颗粒含有至少一个磨粒和一种粘合剂,该粘合剂是由一种热固性树脂的粘合剂前体经幅射能或热能或这两种能量固化而生成的。这些颗粒可以进而粘合成一定形状的物体,例如磨轮;也可以粘着在一背衬上形成涂覆磨料制品;还可以粘着于一非纺织纤维基材形成非纺织的磨料制品。
在本发明中,可以通过改变颗粒的形状和组成来设计制出适合于各种特定用途的颗粒。用本发明方法制造颗粒,特别是形状精确的磨料颗粒,既简便迅速,又很经济,而且制成的磨料颗粒每个批次都能做到尺寸和形状相同,使磨料制品的重复性很好。
附图的简单说明
图1、2、3是表示进行本发明工艺好几种方法的侧视图。
图4和图5是采用本发明进行的磨料制品的显示其纵剖面的侧视图。
图6是图1所用模具一段的透视图。
图7是用本发明方法制成的具有一定形状的磨料颗粒的扫描电子显微镜照片。该颗粒为三棱锥形。
图8和图9是实施本发明工艺另一些方法的侧视图。
本发明的详细叙述
用于这里的“粘合剂前体”一词指的是任意一种物质,它是可保形的,或者可藉压力或加热或这两者的作用而可保形,同时又可藉幅射能或热能或两者的作用而成为不能保形。用于这里的“固化的可手持的粘合剂”指的是经聚合或固化的粘合剂前体,其聚合或固化程度使它不能显著地流动即产生显著的变形;这个词并不意味着粘合剂前体已充分聚合即固化,只是聚合固化到当模具继续运动时粘合剂能由模具脱卸出来而不致有显著变形。粘合剂离开模具之后,可再接受附加的能量,进行进一步的聚合或固化。在本发明中,“粘合剂”一词与“固化的可手持的粘合剂”是同义词。
本发明的一个方面是制造颗粒物质的方法;另一方面是涉及含有固化的可手持粘合剂的形状精确的颗粒;再一方面是涉及采用本发明形状精确颗粒的磨料制品、例如粘合磨料制品、涂覆磨料制品、非纺织磨料制品等。
图1表示了能够制造本发明颗粒的本发明方法的一套设备。在该设备10中,粘合剂前体藉重力由料斗14喂入到模具16上,该模具的形式是根环形带。带子绕着两个辊子18、20运动,其中至少有一个辊子是驱动辊。图6是该模具16一段的透视图。由图6可见,模具16是一个三维体,它有个连续表面21,其上有孔22与三维体中的模腔23连通。将粘合剂前体12填入模腔23的至少一部分空间内。然后装有粘合剂前体12的模具16通过一固化区24,在那里接受能量源25的作用,结果粘合剂前体12至少部分固化成可手持的粘合剂。具有精确形状的颗粒26脱离模具26,收集在容器28中。外界装置29,例如超声能量发生装置,可用来帮助粘合剂颗粒26由模具脱卸下来。将留在模具中的碎屑清除以后,可再将粘合剂前体装入模具中。
图2表示可实施本发明方法的另一种设备。该设备30中,有一个传送带32由退绕筒34喂进,该传送带32的材料可以是纸、布、聚合物薄膜、非纺织材幅、硬化纸板或它们的复合物,这些材料还可以经受过某种处理。传送带32的优选材料是聚合物薄膜,如聚酯薄膜。图2中的传送带对于幅射是透明的。粘合剂前体36藉重力由料斗38喂到传送带32的主表面上。装有粘合剂前体的传送带32的主表面通过一夹紧辊42压紧在模具40的表面上。与传送带接触的模具40的表面是曲面形的,但它在其它方面都与图6所示模具的那一段相同。夹紧辊42也起着将粘合剂前体36压入模具40的模腔的作用。然后粘合剂前体通过固化区43,接受转量源44的作用,至少部分地硬化,生成固化的可手持的粘合剂。然后,其表面上载有固化可手持粘合剂的传送带在另一夹紧辊46上绕过。在传送带32与固化可手持的粘合剂之间必需具有足够的粘着作用,使得粘合剂随后能由模具40的模腔脱卸出来。形成的粘合剂物质的颗粒48然后再从传送带32脱离下来收集在容器50中。外界装置51如超声发生装置可用来帮助颗粒48从传送带32上脱离。传送带32然后再在重绕筒52上回收,供再次使用。
粘合剂颗粒从传送带上的脱离,可以用另一种方法有效地进行。在此方法中,传送带的表面上可涂以一层水溶性的薄层,这个薄层接受来自料斗38的粘合剂前体36。当粘合剂前体36部分固化后,令带有已固化可手持粘合剂的传送带32通过一水源中,水将传送带32上的水溶性层溶解掉,从而使粘合剂颗粒与传送带32脱离。可用于此方法的水溶性层物质的例子有水溶性聚合物,如聚乙烯醇、聚乙烯吡咯烷酮、纤维素衍生物。
图3表示可实施本发明方法的又一种设备。在该设备70中,粘合剂前体70从料斗74刀涂在模具76上。这里的模具形式是一个园柱形转筒,其轴为78。该模具的连续表面是曲面,但在其它方面与图6所述模具的那一段相同。随着模具76绕其轴78旋转,粘合剂前体72就通过固化区79,接受能量源80的作用,至少部分固化,形成固化可手持的粘合剂。接着,由固化步骤生成的粘合剂82的颗粒从模具76卸脱收集在容器84中。卸脱方法最好用机械手段,如喷水法进行。在下次再加入新鲜粘合剂前体之前,宜将留在模具76中的碎屑清除掉,用刷子、用喷气法或任何其它的常规方法进行之。在图中未表示的附加装置,有助于粘合剂脱离模具76。
模具是一个三维体,它具有至少一个连续表面,该表面上至少有一个孔(最好是许多个孔)。每个孔与三维体中的一个模腔连通。本文中所谓的“连续”是指在空间中不受中断的延伸;孔和模腔是连续表面的特征,但它们并不将表面分割成许多单个的表面。模具的形式可以是材幅、带子例如环形带、片材、涂布辊、或装在涂布辊上的套管。模具宜用可连续操作的形式,例如环形带或绕轴转动的圆柱形涂布辊。圆柱形涂布辊通常为笔直的圆柱体形状,直径约25~45cm,用刚性材料制成。采用有两个末端的带子的设备,也可以适用于连续操作。好的模具材料为聚合物如聚酯(如聚丙烯)或金属如镍。模具材料也可用陶瓷材料。
金属模具的制法可用镂刻、光刻、滚铣、蚀刻、滚花、由加工成所需构型的若干金属零件进行装配、冲压等机械方法,也可用电成形方法。制造金属模具或母模的较佳方法是金刚石车削。这些方法在Encyclopaedia of Polymer Science and Technology Vol.8 JohnWiley&Sons,Inc.(1968),p651~665以及美国专利3,689,346第7栏第30至55页中都有叙述。模具中也可覆上一层防粘涂层,以便于粘合剂从模腔中分离,并尽量减少模具的磨损。这类防粘涂层例如有硬质涂层如金属碳化物、金属氮化物、金属硼化物、金刚石或类金刚石的碳。对模具加热也属本发明范围,此时模具宜用金属。模子加热便于操作、使固化加快,也使成形颗粒更易从模具卸脱出来。
在有些情况下,可以由原来的母模复制出聚合物模具,当模具呈带子或材幅形状时,尤为适宜。聚合物模具比金属模具的一个好处是其成本较低。聚合物模具的另一好处是能够允许幅射由幅射源透过模具进入粘合剂前体中。制造聚合物模具可以是将熔融的热塑性树脂如聚乙烯涂布在母模上,然后急冷生成母模的热塑性复型。此聚合物复型即可用作模具。此外,模具表面可有一层防粘涂层,如用硅氧烷基的或含氟化合物基的材料,以改善粘合剂由模具的卸脱。将防粘剂物质掺入到构成模具的聚合物中也属本发明范围。通用的防粘剂有硅氧烷基和含氟化合物基的材料。由卸脱性能良好的聚合物制造模具也属本发明范围。这种聚合物在发表于1992年9月17日的WO92—15626中有叙述。这一资料中叙述了一种含氟的接枝共聚物,它是由具有末端烯双键的单体衍生物的聚合单元构成,该聚合单元的一部分上面接枝了一氟代脂肪族基团。该接枝的氟代脂肪族基团衍生于一个由一氟代酯肪族基团与一可聚合双键构成的含氟烯烃。
该含氟烯烃的氟代脂肪族基团,一般通过一连接基团键合在该可聚合双键上。这种含氟烯烃可用下式表示:
(Rf)aQ(CR=CH2)b式中b代表氢、三氟甲基或含1至4个碳原子的直链或支链烷基;a为1至10的整数;b为1至6的整数;Q代表一个对自由基聚合作用不产生显著干扰的a+b价的连接基团;R1代表一个含有至少7个氟原子的完全氟化的端基。
制造母模的方法可与制造金属模具的方法相同。制造模具的其它方法在1993年1月14日提交的受让人的待批申请Serial No.08/004,929中有叙述。
若模具由热塑性材料制成,其制法的条件应使固化区中产生的热量不致对模具有不良的影响。
模具的至少一个连续表面上具有至少一个模腔,最好有许多个模腔。固化的可手持粘合剂前体将具有与模腔形状对应的形状。模腔可为任意几何形状,例如棱锥体、棱柱体、圆柱体、圆锥体、或具有相对多角形面的薄物体等形状,也可以是上述各种几何体截断部分的形状。模具中的模腔可以形状不同、或尺寸不同、或形状和尺寸都不同,这些都属本发明范围。在模具是带子形式的情况下,模腔可以完全贯穿在其中。模腔之间也可以邻接,也可以有格壁。模腔的侧面宜做成一定斜势,以便粘合剂从模具中容易脱卸出来。
适于用作本发明的粘合剂前体是一种能够藉辐射能或热能固化的热固性树脂。粘合剂前体可通过缩合固化机理或加成机理而聚合。较好的粘合剂前体是藉加成机理聚合的。粘合剂前体可通过自由基机理或阳离子机理或这两种机理而聚合。粘合剂前体中可以没有填料,也可能含有常规的填料。
粘合剂前体最好是藉辐射能或热能的作用固化。辐射能源包括电子束、紫外光、可见光和激光。如用紫外或可见光,混合物中宜掺入光引发剂。一旦受到紫外或可见光的照射,光引发剂即产生一种自由基源或阳离子源,它们就引发粘合剂前体的聚合。当用电子射线能量时,光引发剂是可用可不用的。
可藉幅射能固化的粘合剂前体包括丙烯酸化聚氨酯、丙烯酸化环氧、烯键不饱和化合物、具有侧链不饱和羰基的氨基塑料衍生物、具有至少一个侧链丙烯酸酯基的异氰酸酯衍生物、乙烯基醚、环氧树脂以及它们的混合物。丙烯酸酯包括丙烯酸酯类和异丁烯酸酯(甲基丙烯酸酯)类。
丙烯酸化聚氨酯是羟基末端的异氰酸酯扩展的聚酯或聚醚。丙烯酸化聚氨酯商品的例子有“UVITHANE 782”,Morton ThiokolChemical生产,还有“CMD6600”、“CMD8400”、“CMD8805”,Radcure Specialities生产。
丙烯酸化环氧是环氧树脂的二丙烯酸酯,例如是双酚A环氧树脂的二丙烯酸酯。其商品例如有“CMD 3500”、“CMD3600”、“CMD3700”,Radcure Specialities生产。
烯键不饱和化合物包括含有碳、氢、氧原子;有时还或可含有氮和卤素原子的单体或聚合化合物。氧或氮原子或这两种原子通常在醚、酯、聚氨酸、酰胺和脲基团中都有。烯键不饱和化合物最好具有的分子量小于约4,000,且最好是由含脂族一羟基或脂族聚羟基的化合物与不饱和羧酸如丙烯酸、异丁烯酸、衣康酸、巴豆酸、异巴豆酸、马来酸等进行反应生成的酯类。丙烯酸酯的代表性例子有:异丁烯酸甲酯、异丁烯酸乙酯、乙二醇二丙烯酸酯、乙二醇异丁烯酸酯、己二醇二丙烯酸酯、三甘醇二丙烯酸酯、三甲醇丙烷三丙烯酸酯、甘油三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇异丙烯酸酯、季戊四醇四丙烯酸酯。其它烯键不饱和化合物还包括一烯丙基、聚烯丙基、聚甲基烯丙基的酯类以及羧酸的酰胺如邻苯二甲酸二烯丙酯、己二酸二烯丙酯、N、N-二烯丙基已二酰二胺。还有其它的烯键不饱和化合物,它们是苯乙烯、二乙烯基苯和乙烯基甲苯。其它含氮的烯基不饱和化合物包括三(2-丙烯酰—乙氧基)异氰脲酸酯、1,3,5-三(2—异丁烯酰乙氧基)—S—三嗪、丙烯酰胺、异丁烯酰胺、N-异丁烯酰胺、N、N-二异丁烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基哌啶酮。
氨基塑料可以是单体的或低聚物的。氨基塑料树脂每个分子具有至少一个侧链的α、β—不饱和羰基。这些α、β—不饱和羧基可以是丙烯酸酯、异丁烯酸酯或丙烯酰胺的基团。这些树脂的例子有N-羟甲基—丙烯酰胺、N,N′—氧二亚甲基二丙烯酰胺、邻和对丙烯酰氨甲基化酚、丙烯酰氨甲基化可溶酚醛树脂、以及它们的组合。这些材料在美国专利4,903,440和提交于2/24/91的美国专利申请连续号07/659,752中都进一步有所描述,这两种资料均参考结合于本发明中。
具有至少一个侧链丙烯酸酯基团的异氰脉酸酯衍生物和具有至少一个侧链丙烯酸酯基团的异氰酸酯衍生物,在美国专利4,652,274中有进一步的叙述。较好的异氰脲酸酯物质是三(羟乙基)异氰脲酸酯。
适用于本发明的乙烯基醚有乙烯基醚官能化的聚氨酯低聚体、有Allied Signal的商标为“VE4010”、“VE4015”、“VE2010”、“VE2020”、“VE4020”的产品。
环氧具有一个环氧乙烷环,藉开环作用而聚合。环氧树脂包括单体环氧树脂和聚合环氧树脂。这些树脂在其主链和取代基团的本性方面,可有很大不同。例如,其主链可以是通常与环氧树脂相关的任何类型,其取代基团可以是不含有与环氧乙烷环会在室温起反应的活性氢原子的任何基团。环氧树脂取代基团的代表性例子有卤素、酯基、醚基、磺酸根、硅氧烷基、硝基、磷酸根。宜用于本发明的环氧树脂包括2,2—二[4—(2,3—环氧丙氧基)苯基]丙烷(双酚A的二环氧甘油醚)以及Shell Chemical Co.的商标为“Epon 828”、“Epon1004”、“Epon 1001F”的商品,Dow Chemical co的商标为“DER-331”、“DER-332”、“DER-334”的商品。其它适用的环氧树脂还有酚醛清漆的缩水白油醚(如Dow Chemical Co.的"DEN-431”和“DEN-428”)。本发明的环氧树脂可通过与适当光引发剂加成作用的阳离子机理而聚合。这些树脂在Smith的美国专利4,318,766和Tumey等人的美国专利4,751,138中有进一步的叙述。
当受到紫外光照射会产生自由基源的光引发剂例如有(但不限于):有机过氧化物、偶氮化合物、醌、二苯酮、亚硝基化合物、酰基卤、腙(hydrozones)、巯基化合物、吡
化合物、三丙烯酰基咪唑、联咪唑、氯化烷基三嗪、苯偶姻醚、苯偶酰酮缩醇、噻吨酮、乙酰苯衍生物以及它们的混合物。受到紫外幅射作用时会产生自由基源的光引发剂的例子,在美国专利4,735,632中有叙述。
阳离子光引发剂会产生一种酸源,引发环氧树脂或聚氨酯的聚合。阳离子光引发剂可包括含有一种鎓阳离子和金属或准金属的含卤素的配阳离子的盐。其它的阳离子光引发剂包括一种含有金属有机配阳离子和金属或准金属的含卤素配阴离子的盐。这些光引发剂在美国专利4,751,138(由第6栏第65行至第9栏第45行)中有叙述。另一个例子是叙述于美国4,985,340(第4栏第65行至第14行第50行)和欧洲专利申请306,161中的一种有机金属盐和一种鎓盐。还有其它的阳离子光引发剂,它们是一种有机金属配离子盐,其中的金属选自IVB,VB,VIB,VIIB、VIIIB族元素。这种光引发剂在欧洲专利申请109,581中有叙述。
在一个特别有用的实施方案中,颗粒中除有粘合剂前体外,还含有磨粒。固化了的粘合剂前体即粘合剂起着将磨粒粘合在一起形成形状精确的磨料颗粒的作用。磨粒通常的平均粒径为0.1~1500微米,1~500微米较为适宜,1~150微米最佳。磨粒的莫氏硬度至少应约为8,最好大于9。这类磨粒例如有电熔氧化铝,陶瓷氧化铝,白色电熔氧化铝、热处理氧化铝,二氧化硅、碳化硅,绿色碳化硅、铝氧锆氧、金刚石、氧化铈、立方氮化硼、石榴石、硅藻石或它们的混合物。陶瓷氧化铝用溶胶凝胶法制造,如美国专利4,314,827、4,744,802、4,623,364、4,770,671、4,881、951、5,011,508、5,123,591所述。陶瓷磨粒含有α氧化铝,或可含有一种金属氧化物改性剂,如氧化镁、氧化锆、氧化锌、氧化镍、氧化铪、氧化钇、二氧化硅、氧化铁、氧化钛、氧化镧、氧化铈、氧化钕以及它们的混合物。陶瓷氧化铝中也或可含有一种成核剂、如α氧化铝、氧化铁、氧化铁前体、氧化钛、氧化锆或它们的混合物。陶瓷氧化铝可具有一定形状,如美国专利5,201,916和5,090,968所述的陶瓷磨粒也可能具有一表面涂层。
磨粒也可能具有表面涂层,它能改善磨料颗粒中磨粒与粘合剂之间的粘接力和/或改变磨粒的研磨特性。这些表面涂层在美国专利5,011,508,1,960,444,3,041,156,5,009,675,4,997,461、5,213,591,5,042,991中均有叙述。磨粒也可在其表面上有偶合剂,如硅烷偶合剂。粘合剂前体中可有一种磨粒、两种或多种不同的磨粒、或至少一种磨粒与至少一种稀释剂物质。稀释剂例如有碳酸钙、玻璃小泡、玻璃珠、灰石、大理石、石膏、粘土、SiO2、KBF4、Na2SiF6、冰晶石、有机物质小泡、有机物质珠等。
与用于本发明粘合剂前体一起使用的,还可进一步用一些添加剂物质、例如填料(包括助磨剂)、纤维、润滑剂、润湿剂、表面活性剂、颜料、染料、偶合剂、增塑剂、抗静电剂与悬浮剂等。适用于本发明的填料有木质纸浆、蛭石和其混合物,金属碳酸盐如碳酸钙(如白垩、方解石、泥灰岩、石灰华、大理石、石灰石)、碳酸钙镁、碳酸钠、碳酸镁,二氧化硅如无定形二氧化硅、石英、玻璃珠、玻璃小泡、玻璃纤维,硅酸盐如滑石粘土(蒙滑石)、长石、云母、硅酸钙、偏硅酸钙,金属硫酸盐如硫酸钙、硫酸钡、硫酸钠、硫酸铝钠、硫酸铝,石膏,蛭石,木粉,铝的二水合物,金属氧化物如氧化钙(石灰)、氧化铝、氧化钛,以及金属亚硫酸盐如亚硫酸钙。
助磨剂定义为一种颗粒状物质,它加入到磨料制品中对于研磨的化学和物理过程产生显著影响,从而改善其性能。具体来说,人们认为助磨剂会(1)减少磨粒与被研磨工件之间的磨损,(2)防止磨粒被“盖帽”,即防止研磨下来的金属颗粒焊在磨粒的顶部,(3)降低磨粒与工件之间的界面温度,或(4)减小研磨力。加入助磨剂通常可延长涂覆磨料制品的有效寿命。助磨剂包括一大类不同的材料,可以是无机或有机的。助磨剂的例子有石蜡、有机卤化物、卤化盐、金属及其合金等。有机卤化物在研磨过程中通常会分解放出卤酸或气态卤化物。这些物质的例子包括卤化石蜡如四氯萘、五氯萘、聚氯乙烯。卤化盐的例子包括氯化钠、钾冰晶石、钠冰晶石、铵冰晶石、四氟硼酸钾、四氟硼酸钠、氟化硅、氯化钾、氯化镁等。金属例如为锡、铅、铋、钴、锑、镉、铁、钛等。其它助磨剂有硫、有机硫化合物、石墨、金属硫化物。使用上述不同助磨剂的组合也属本发明的范围,有时这会产生协同效应。上述的那些助磨剂例子只是作为代表而已,并不意味着已经包括了全部可用的助磨剂。
适用于本发明的偶合剂例如有:有机硅烷、铝酸锆(zircoaluminates)和钛酸盐。抗静电剂例如有石墨、炭黑、导电性聚合物、湿润剂、氧化钒等。这些添加物质均可调节其用量以提供所需的性能。粘合剂前体中还可以含有水或一种有机溶剂。
如果本发明的颗粒中含有磨粒,这种颗粒最好在研磨过程中能破碎。粘合剂、磨粒和添加的用量选择会影响颗粒的破碎性能。
为了形成粘合物与其它物质如磨粒的混合物,这些组分可用任何一种常规方法如高剪切混合、空气搅拌或鼓转等方法混合之。混合时可用真空以减少空气的截留。
可以采用任何常规方法的引入装置将粘合剂前体引入到模具的模腔中。这些方法如重力加料、泵送、模涂或真空落模涂。粘合剂前体也可以通过一传送带引入模具模腔中。在混合阶段中或者涂覆阶段之前,为了降低其粘度对粘合剂前体可施用超声波。
虽然粘合剂前体只需要填入模腔的部分空间,但最好是填满模腔至模具的表面,使得生成的颗粒物质中只有很少的空隙或缺陷。这些缺陷会使颗粒形状与所需的精确形状有偏离。而且,当形状精确的粘合剂颗粒由模具卸脱时,颗粒的边缘会脱开,造成缺陷,致使与形状的精确性不符。所有工艺步骤均应仔细进行以尽量减少缺陷。有时生成的颗粒中有空隙或缺陷却是需要的,因为它们在颗粒中产生孔隙,使其具有较大的侵蚀性。而且,粘合剂前体不应显著伸出在模具的连续表面之外,也不应显著伸出模腔孔之外。
有时需要对粘合剂前体在其引入模具之前进行加热,通常加热至约40°~90℃。当粘合剂前体受热,其粘度就降低,它在模腔中可良好流动。
将粘合剂前体加入到模腔之后的步骤,包括趁其在模腔中对之施加幅射能或热能,使之至少部分地固化。当粘合剂从模具模腔卸出之后可以再进行后固化处理,但也可不用后固化处理。固化的程度应足以使生成的固化粘合剂颗粒在从模具脱去时仍保持其形状。
使用于固化区的幅射能源,例如有电子射线、紫外光、可见光、激光。电子束幅射又称为电离幅射,其使用剂量可为0.1~20兆拉德,1~10兆拉德更佳。紫外幅射系指一种非粒子辐射,其波长约为200~40纳米,250~400纳米更佳。其使用剂量约为50~1000MJ/cm2,100~400MJ/cm2更佳。适合于产生这种剂量的灯源能提供约100~600瓦/时,300~600瓦/吋更佳。可见辐射系指一种非粒子幅射,其波长约为400~800纳米,400~550纳米更佳。足使粘合剂前体充分固化的辐射能量取决于许多因素,例如模腔中粘合剂前体的深度,粘合剂前体的物质种类、以及加载物质的种类(如果有的话)。热固化的条件,温度约为50°~200℃,时间为零点几分钟至千分之几分钟。实际所需的热量与粘合剂前体的化学本性有很大关系。
使固化的可手持的粘合剂(简称为粘合剂)从模具取出的方法可有许多种。一种方法是,粘合剂直接从模具卸脱进入一收集容器如料斗中。在此方法中,若模具材料为聚合物,可以藉超声能量、真空、空气刀方法或这几种方法结合使用,使粘合剂脱离模腔,也可用其它通用的机械方式。如模具材料为金属,可用水喷射法或空气喷射法。如果模具中的模腔是贯穿整个模具的,例如模具是一根有许多孔贯穿其中的带子,则不论模具的结构材料是什么,使粘合剂脱离模具的方法可用超声能量、机械力,水喷射、空气喷射或者这些方法结合使用。
在另一类方法中,粘合剂是间接从模具卸脱进入收集容器的。其一个实施办法是将粘合剂从模具转换到一光滑辊子上。条件是粘合剂与光滑辊子的粘接力比粘合剂与模具的粘结力大。然后,可用刮削、真空、水喷射、空气喷射或其它机械方式将粘合剂再从光滑辊子上除去。在又一种具体实施办法中,可将粘合剂从模具转移到一传送带的主表面上。粘合剂与该传送带的主表面之间的粘结力大于它与模具的粘结力。传送带的主表面上可以先覆一层可溶于水或一种有机溶剂的物质。只要将该可溶层物质溶解掉,即可很容易地使粘合剂脱离传送带。此外,也可用机械方式如刮削、真空、超声来除去粘合剂。超声能量可以直接加在传送带的一个主表面上,也可加在其一个主表面的侧边上。在另一实施办法中,传送带的主表面上可有一层底剂。适用于传送带的底剂物质例如有乙烯丙烯酸共聚物、聚偏二氯乙烯、交联己二醇二丙烯酸酯、氮丙啶物质等。粘合剂会优先粘着于打了底剂的传送带。然后再用机械方式如刮削、真空或超声使粘合剂从其脱离。
当粘合剂从模具藉直接方式或间接方式脱离后,然后转化为颗粒。其一种转化方式是,粘合剂即以颗粒的形式脱离模具。一个给定的颗粒即基本上具有模腔该部分空间的形状,颗粒是在该部分至少部分固化的。这种方式的好处是生成的颗粒已有适合的粒级即适合的粒度分布,供以后之用,如在磨料制品中使用。而在常规的磨料颗粒即团粒的制品中,则磨料颗粒需另经破碎和筛选,才能获得恰当的粘度分布。
在另一种转化方式中,粘合剂以一个片材的形式从模具脱离,该片材是许多精确成形的粘合剂颗粒以一薄层粘合剂材料相互连接。这种粘合剂片材然后破碎掉其相连接部分,形成本发明的颗粒。
在有一种方法中,模具是一转筒成带子,它绕轴旋转,结果,过程可连续进行。当模具静止不动,如现有技术的方法那样,则过程是间歇进行的。本发明的这种连续方法通常比现有技术的间歇方法更高效、更经济。
本发明还提供含有本发明方法所制造磨料颗粒的磨料制品。这些制品可是粘合磨料制品、涂覆磨料制品或非纺织磨料制品。对粘合磨料制品,是将此形状精确的磨料颗粒用一粘合介质粘合在一起成为一定形状的物体,如砂轮,砂轮切割片。粘合磨料制品的通常制法是模压法。对涂覆磨料制品,此形状精确的磨料颗粒是用粘合介质粘接到一背衬上。对非纺织磨料制品,则是将此形状精确的颗粒用粘合介质粘合到非纺织纤维状基材中去。
适合于制造涂覆磨料制品的背衬包括聚合物薄膜、有底层的聚合物薄膜、布、纸、硬化纸板、聚合物泡沫材料、非纺织织物(上述这些材料还可以是经过某种处理的)、以及它们的结合。如图4和图5所述,涂覆磨料制品100中有两个将磨料颗粒粘结于背衬的涂层。涂层102通常称为初始接合涂层,它是施涂在背衬104上面,将磨料颗粒106粘结于背衬104上。涂层108通常称为胶结涂层。它是施涂在磨料颗粒106上面,起着对磨料颗粒106增强的作用。也可以还有第三层涂层110施涂在胶结涂层108上面,它通常称为上胶结涂层。如前所述,磨料颗粒106中含有许多磨粒112和粘合剂114。将磨料颗粒施加在背衬上可以用常规的一些方法如滴式涂覆或静电涂覆。随涂覆方法而异,制品上的磨料颗粒可以是定向取向的(图4),也可是混乱取向的(图5)。
将磨料颗粒粘接于基材或相互粘合在一起所用的材料是一种固化的树脂粘接剂,其中也或可含有一些添加剂。适用于本发明的树脂粘结剂例如有酚醛树脂、氨基塑料树脂、聚氨酯树脂、环氧树脂、脲甲醛树脂、异氨脲酸酯树脂、丙烯酸化聚氨酯树脂、丙烯基树脂、丙烯酸化环氧树脂以及它们的混合物。或可采用的添加剂有填料(包括助磨剂)、纤维、润滑剂、润湿剂、表面活性剂、颜料、染料、偶合剂、增塑剂和悬浮剂等。填料包括滑石、碳酸钙、偏硅酸钙、二氧化硅以及它们的混合物。其用量须经选择以提供所需的性能。
非纺织磨料制品包括一个开放多孔的非纺织纤维基材,其中粘合着许多磨料颗粒。这种类型的非纺织磨料制品在美国专利2,958,593中有叙述。
本发明磨料制品可进一步含有磨料团粒或单独用的磨粒或两者都含有。通常的磨料团粒在美国专利4,311,489、4,652,275、4,799、939中有进一步叙述。单独用的磨粒也可选用其具有一定精确形状的,单独用的磨粒可用电熔氧化铝,陶瓷氧化铝,热处理氧化铝,碳化硅、铝氧锆氧、金刚石、氧化铈、立方氮化硼,石榴石以及它们的混合物。但本发明的磨料制品中,其磨料中至少有10%,较好有至少50%,最好有至少70%为本发明形状精确的磨料颗粒。在涂覆磨料制品中,单独用的磨粒可置于形状精确的磨料颗粒上面,但也可以位于其下方,或者位于两层形状精确的磨料颗粒之间。
这种形状精确磨料颗粒的尺寸不宜超过2500微米,宜为0.1~1500微米,0.1~500微米更佳。如前指出,该精确的形状对应于模具表面的一部分即在模具表面形成的模腔。这种精确形状是归因于粘合剂前体在模具模腔中部分固化的结果。若粘合剂前体在模腔中未充分固化,它就会流动、结果形状将不对应于模腔的形状,这样,颗粒的形状就不精确,不规则了。精确的形状可以是任意的几何形状,如圆锥体、三角柱体、圆柱体、角锥体、球以及具有两个间距恒定或不同的多角形面的物体即多面片状体。角锥体的底面宜有三条或四条边。磨料颗粒可以含有多种形状不同的磨料颗粒。图7是磨料颗粒放大300倍的扫描电镜照片,其形状为三角形底面角锥体。
在形状精确的磨料颗粒中,磨粒和粘合剂所占的重量百分数视多种因素而不同,这些因素例如为磨料颗粒的用途、其中磨粒的粒度及其分布。一般来说,磨粒的重量百分数约5~95%,粘合剂为95~5%;但磨粒重量百分数较佳为20~75%,粘合剂较佳为80~25%。
作为本发明的另一个内容,形状精确的颗粒中并不含有磨粒。它可用作为稀释剂颗粒用于涂覆磨料制品。例如,一种涂覆磨料制品可含有一背衬,其上面粘掊着磨粒和不含磨粒的本发明形状精确的颗粒。另一类涂覆磨料制品,是在其背衬的前表面上涂覆第一层固化树脂粘结剂(初始接合涂层),而磨粒和本发明的形状精确的颗粒藉该初始接合涂层固定于背衬上。在磨粒与形状精确的颗粒上面再有第二层固化树脂粘结剂(胶结涂层)。
形状精确的磨料颗粒可以混乱地涂覆于即置放在背衬上面,也可以按一定取向置于背衬上面。若形状精确的颗粒为角锥体、圆锥体和棱柱体(如三棱柱体)形,这些颗粒置于背衬上的取向可以是底面朝着背衬,而其顶点的指向背离背衬(图4),也可以是其顶点朝着背衬,而其底面则离背衬较远(图5中的四个颗粒)。对于角锥体如圆锥体而言,所指的顶点是该公共的顶点。
涂覆磨料制品的制法可用如下的步骤。取一条具有前表面和背表面的背衬。用第一层树脂粘结剂的可固化粘合介质涂覆在背衬的前表面上;然后将形状精确的磨料颗粒,有时还有单独的磨粒,涂覆即施加进入到这第一层可固化粘合介质中。涂覆形状精确的磨料以及或可有的磨粒,可以用滴涂法或静电涂法。这第一层粘合介质随后固化成一层树脂粘结剂。在形状精确的磨料颗粒上面或者还可以施涂第二层树脂粘结剂的可固化粘合介质,然后它也固化形成树脂粘结剂。第二层可固化粘合介质的施涂,可以在第一层可固化粘合介质的固化之前或之后进行。
在形状精确颗粒的外表面包覆一层涂层也属本发明的范围。这种涂层可以连续,也可以不连续。适用的涂层例如为金属、金属氧化物、碳化物、氮化物、硼化物、碳、金刚石、类金刚石碳等物质的涂层。在颗粒表面也可为有机涂层。该有机涂层中还可含有填料、偶合剂、抗静电剂、助磨剂等。
涂层种类的选择和用量取决于颗粒所需的性能。例如,有些涂层会使颗粒呈回复反射性。而有些涂层会改善颗粒与其它材料或基材的粘着作用。
下面的一些非限制性实施例将进一步说明本发明。若非另外指出,这些实施例中的所有份数、百分数、比例等均指以重量为基的。
在所有这些实施例中采用下列的缩写符号和商标名称。TATHEIC 三(羟乙基)异氰脲酸酯的三丙烯酸酯PH1 α,α-二甲氧基-苄基·苯基酮,商标为
“IRGACURE 651”的Ciba Geigy
Company的产品PH2 2—苄基—2—N、N—二甲胺基—1—(4—
吗啉代苯基)-1-丁酮,商标为
“IRGACURE369”的Ciba Geigy
Company的产品WA01 白色氧化铝,40微米级别的分布WA02 白色氧化铝,级别P-100TMPTA 三羟甲基丙烷三丙烯酸酯MSCA 3—甲基丙烯氧丙基—三甲基硅烷偶合剂,
商标为“A-174”的Union Carbide Corp的
产品ASF 平均表面积为50m2/g的无定形二氧化硅
颗粒,商标为“OX-50”的DeGussa Corp.
的产品PH3 新戊二醇丙氧基化物二丙烯酸酯,商标为
“Photomer 4127”的Henkel corp.产品HMPP 2—羟基异丙基·苯基酮,商标为“Darocur
1173”的Ciba Geigy Co.的商品IOA 丙烯酸异辛酯,CPS Chemicals的商品UDO 脂族聚氨酯二丙烯酸酯低聚物,用三聚丙
二醇二丙烯酸酯冲稀15%,商标为
“Ebecryl 4883”的Radcure Specialities,
Inc.的产品ACU 含有25%己二醇二丙烯酸酯的丙烯酸酯
聚氨酯,商标为“15-1525”的Cargill,Inc.
的产品APC 3—(三甲氧基甲硅烷基)—异丁烯酸丙酯
的水解形式
所用的磨料颗粒是用下述制备磨料颗粒的一般程序中的某一种制造的。用本发明方法制造的磨料颗粒再按下述的制造涂覆磨料制品的一般程序掺入涂覆磨料制品中。磨料制品最后按下述测试程序中的一种测试之。制备磨料颗粒的一般程序I
将平均粒度为40微米的含有TATHEIC(50份)、TMPTA(50份)、PHI(2份)、MSCA(0.5份)和WA01(200份)的混合物涂覆到一个磨具的表面上,该磨具内含许多模腔的图型,模腔的特点是呈倒置角锥体形状。该磨具用镍制造,基本上为一片材。使用足够多的混合物充满模具的模腔。角锥体形状的模腔在图型上的安排使得角锥体的底面互相对接。角锥体底面的边长约为530微米,高度也约530微米。这种图型在美国专利5,152,917的图1中显示。其次,通过一辊子将一层聚脂薄膜(聚对苯二甲酸乙酯,130微米厚)压紧在模具上,这样,该混合物就润湿着聚酯薄膜的前表面。该聚酯薄膜的前表面上有一层厚约20微米的乙烯丙烯酸共聚物(ethylene acrylicacid)打底层。然后,让紫外光透过聚酯薄膜,进入到混合物中引发粘合剂前体的聚合。紫外光的光源包括两台Aetek中压泵灯、操作条件为300瓦/吋。然后,将聚酯薄膜与模具分离。形成的磨料颗粒此时是粘着在聚酯薄膜上,用某种机械方式将颗粒从聚酯薄膜上分离下来。然后将这些磨料颗粒通过一850微米的筛子,将其中互相粘着的颗粒分离,成为单个的磨粒。制备磨料颗粒的一般程序II
一般程序II与一般程序I相似,其不同的地方如下所述。
粘合剂前体的制备是将含29.5份的TMPTA:TATHEIC:PH2为50∶50∶1的混合物与0.5份APC、69份WA01和1份ASF的组合物进行混合。将一个混好的粘合剂前体珠形料倾倒在模具上,该模具与制备磨料颗粒的一般程序I中所用的相同。将一传送带放置到置有粘合剂模具的上面,其打底层的面朝下,用一塑料刮刀作用在传送带的背面,令粘合剂前体挤入模具的模腔中。将此传送带/粘合剂前体/模具结构用胶布固定在一金属板上,聚酯薄膜要朝上,然后以约3.1米/分的速度移动,接受幅照。幅射能源是一个600瓦的“V”形灯泡(Fusing System提供),该灯泡设备在高调节档上。使用氮气流喷吹。制造对比实施例涂覆磨料制品的一般程序
按美国专利5,152,917所述制造了涂覆磨料制品。将含有磨料与粘合剂前体的混合物涂覆在模具上。模具具有倒置角锥体形状的模腔。这些倒置角锥体形状模腔的位置安排,是使它们的底面相互对接。角锥底面的边长约为530微米,高也约530微米。其设置图型可见美国专利5,152,917的图1。先将混合物填满模腔。其次,将一聚酯薄膜(80微米厚)通过一辊子压紧在模具表面上,从而使混合物润湿聚酯薄膜表面。聚脂薄膜的前表面上覆有一乙烯丙烯酸共聚物打底层。令紫外光透过聚酯薄膜,照射到混合物上,引发粘合剂的聚合。混合物就转变的磨料复合体。紫外光的光源包括两个Aetek中压泵灯,操作条件为300瓦/吋。然后,将聚酯薄膜/磨料复合体从模具上分离,形成磨料制品。这个方法是个连续过程,运行速度为2.4米/分。最后将获得的磨料制品用双面粘带层压在硬化纸板(约0.8毫米厚)上。制造本发明的涂覆制品(盘)的一般程序
将本发明磨料颗粒用于制造背衬为硬化纸板盘的涂覆磨料制品。硬化纸板盘另行制造,其直径为17.8cm,中心孔直径为2.2cm。初始接合涂层的物质是填以酚醛树脂的常规碳酸钙(48%树脂,52%CaCO3)。磨料颗粒是用静电法涂入初始接合涂层的。粘接涂层的物质与初始接合涂层相同。这样制成的研磨盘在测试前先进行了弯曲。每个盘的初始接合涂层湿重约4克,粘接涂层湿重约7克。制造本发明涂覆制品(带)的一般程序
将本发明磨料颗粒用于制造其背衬无接头的环形涂覆磨料带,如1992年7月24日提出的美国专利申请系列号07/919,541中所述。其初始接合涂层物质是填以酚醛树脂的常规碳酸钙(48%树脂,52%CaCO3)。磨料颗粒是用滴涂法施加到背衬上的,涂覆重量为每10×15cm的样品涂有80个颗粒。粘接涂层物质与初始接合涂层相同。在测试前,对研磨带进行了弯曲。测试程序I
先将涂覆磨料的研磨盘装在一铝制的有斜面的支抬垫上,然后用它来研磨1018软钢工件的1.25cm×18cm表面。研磨盘的5500rpm的转速旋转,叠置在支撑填料边上的研磨盘部分以约4.5kg的负载与工件接触。研磨一个工件用一个研磨盘,一次研磨时间为一分钟,共研磨5分钟。记录下每一分钟研磨后除去的金属量。测试程序II
测试程序II与测试程序I相似,但有下述的不同。研磨负荷为300克;当工件开始烧坏即颜色变黑或蓝时才停止试验;一次研磨的时间为30秒。对测试程序II,初始磨削量系指第一次30秒研磨后除去的金属量,最后磨削量系指最后一次研磨30秒过程中除去的金属量。总磨削量则是全部测试各次磨削量的总和。试测程序III
制成的涂覆磨料制品是一种7.6cm×335cm的环形带,在一恒定负载表面磨床上测试。将一预先称重的尺寸为2.5cm×5cm×18cm的4150软钢工件装在一夹持器中。工件垂直安装,其2.5cm×18cm的表面对着一个36cm直径的橡皮接触轮(肖氏硬度85),接触轮的边缘表面是一叠一锯齿形的,被测试的环形研磨带即套在该轮子上。工件以每分钟25个来回作垂直往返运动,运动距离长18cm。在工件作垂直往返运动以及接触轮上的研磨带以线速2050米/分转动的同时,通过一弹簧加载柱塞以约6.8kg的负载将工件压紧在研磨带上。经一分钟研磨时间后,将工件从夹持器取出重新称重。算出研磨前后重量之差作为磨削除去的材料重量。再将一个预先称重的新工件和夹持器装在设备上。测试了大约两根研磨带。实施例1
实施例1的颗粒是在图8所示的设备上制备的。设备120包括一个带形的磨具122,它由第一个退绕筒喂进。磨具122用对幅射透明的聚合物材料制成,该聚合物具有一个聚乙烯主链,其上面接有氟代脂肪族基团。这种聚合物在1990年9月17日公布的WO92—15626中有进一步叙述。此聚合物键合在聚酯上。聚合物模具上模腔的特点是模腔为正方形底面的角锥体,这些角锥体的位置安排,使它们的底面互相对接。角锥体的高约500微米,其底面每边的长度约900微米。含模腔的表面与图6所示模具的一段相同。当模具离开退绕筒124时,传送带122则离开退线筒128。传送带126的材料是覆有聚乙烯醇的纸,是Schoeller Teehnical Papers的商品,料号89—84—4。粘合剂前体130用一涂布器132施加到模具122的模腔中。粘合剂前体含ACU(65份)、PH3(35份)、HMPP(1份)。模具装有粘合剂前体的部分134在一夹紧辊136处与传送带126接触,压紧贴在卷筒138上面。卷筒138绕轴140旋转。接着在固化区142的幅射源141发出的幅射能量穿透模具122,进入粘合剂前体中。幅射能量源是用一个中压汞蒸气紫外灯,其操作条件为300瓦/吋(120瓦/厘米)。粘合剂前体受到幅射能的照射即转变为固化可手持的粘合剂。内装固化粘合剂的模具和传送带通过卷筒的驱动,继续在固化区142中运动。在夹紧辊143的附近,传送带126与装有粘合剂的模具脱离。传送带126重新绕在一重绕筒144上。
这个过程是连续的,带速为3.1米/分。固化后,将上面粘接着颗粒的涂覆聚乙烯醇的纸传送带从设备上取下。在颗粒的外露表面上用阴极电弧法包覆一层铝。此铝层厚600埃。然后将聚乙烯醇层由纸背衬上脱除,即是溶入100℃的水中,伴以搅拌3分钟。颗粒则藉直空过滤收集之。这种覆有铝层的颗粒具有镜面回复反射性能,这是低指数材料需要的,可以提供良好回复反射体较大的倾危和功能。实施例2
实施例2的颗粒是在图9所示设备上制造的。设备160包括一个环形带形式的模具162,它绕着一系列辊子164运动,辊子中至少有一个是动力传动的。模具162所用的材料与实施例1相同,其模腔为三角形底面的角锥体,底面的位置也互相对接。角锥体高约75微米,其底面边长约125微米。粘合剂前体166藉一刀式涂布器168施加到模具162的模腔中。
粘合剂前体由UDO(67份)、IOA(28份)、MSCA(4份)、HMPP(1份)组成。粘合剂前体166然后通过固化区170,接受幅射能源172的照射。幅射能源用一个中压泵蒸气紫外灯,其操作条件为300瓦/吋(120瓦/厘米)。该过程连续,带速为0.6米/分。受到能源172的照射后,粘合剂前体166即转变为固化可手持的粘合剂。粘合剂颗粒178粘附在表面光滑的卷筒174上。离开固化区170后,颗粒178藉一刮削装置176从表面光滑的卷筒174上脱离,真空收集之(图中未示)。然后颗粒178按下述方法在滚动条件下用银蒸气涂覆之。这些精确成形的颗粒(8.0g)在一真空室中一面滚动,一面用来自溅射靶的银蒸气溅射包覆。圆片形的银靶(5cm直径,0.4cm厚)装在一个US,Inc.的200型US溅射枪上。溅射枪的操作条件是所用的功率0.10千瓦的直流平面磁控管模式,产生的阴极电位为476~502伏,溅射历时105分钟。溅射用的氩气压力约为6毫乇,背景压力为8×10-6乇。溅涂后的形状精确颗粒是银色的,粉末的体电阻率为0.3欧姆厘米。这种包覆颗粒具有很强的镜面反射涂层,使它适用于作标记和反射性外衣的用途。实施例3~9
实施例3的颗粒是按制备磨料颗粒的一般程序I制造的,不同的是用PH2代替PH1。实施例3—9的形状精确的颗粒利用超声能量从传送带上脱离。具体说来,在形状为单刃的超声传能器的前刃对面,传送带的背面受其产生的张力所牵引。该传能器以振幅约130微米、频率为19,100赫振动。该传能器的材料为6—4钛,通过2∶1Booster 802压电转换器的耦合受一900瓦184V Brauson能源所驱动。
下表列出实施例3—9每一例所用传送带的结构。实施例4—9的颗粒是按制备磨料颗粒的一般程序II制造的。
表I实施例 传送带基材1 基材厚度(μm) 传送带上的底剂2 底剂厚度(μm)3 PET 130 EAA 134 PET 110 PVA 135 PET 130 EAA/PVA3 20/1336 PET 100 PVDC -7 PET 265 HDDA -8 PET 76 氮丙啶+ -
硫化聚酯9 PET 76 氮丙啶
1:PET代表聚对苯二甲酸乙二醇酯
2:EAA代表乙烯丙烯酸共聚物;PVA代表聚乙烯醇;
PVDC代表聚偏二氯乙烯;HDDA代表二丙烯酸己二醇酯
3:该底剂为一EAA底层(20μm)和一PVA面层(13μm)。
表2列出了颗粒从传送带脱离情况的评定结果。试验了两种不同的脱离步骤:(1)令薄膜(即传送带)在超声传能器上方经过,(2)将薄膜先在115 ℃加热10分钟,再在超声传能器上方经过。
表2实施例 未经加热样品 经加热样品3 脱离容易 脱离困难,EAA熔化从而将颗粒固定在薄膜上4 —— PVA连同颗粒从薄膜脱离5 —— 脱离容易6 脱离容易 ——7 —— ——8 —— 薄膜破裂9 —— 脱离容易实施例10—13
实施例10—13表明使用水溶性底剂层使颗粒从传送带脱离的方法。实施例10
实施例10的颗粒是按制备磨料颗粒的一般程序II制造的,所不同的是模具材料是透明聚硅酮而非镍,但其形状结构相同。由设定在“高档”的600瓦“V”灯泡(Fusion Systems)发出的幅射透过该透明模具,使粘合剂前体固化,速度为3.1米/分。传送带是得自Schoeller Tsshnical Papers,Inc.的防粘纸板,其上面有一层13微米厚的聚乙烯醇涂层。粘合剂前体固化以后,将传送带/粘合剂/模具的夹层结构剥离开来。将粘附着固化颗粒的传送带置入自来水中。颗粒即由背衬上脱离下来,用机械方法收集之。实施例11
实施例11的颗粒是按制备磨料颗粒一般程序II制造的。将实施例10所述的准备有防粘聚乙烯醇层的纸板通过一对加热夹紧辊叠压到一层未施底剂层的100微米厚的聚对苯二甲酸酯薄膜上,使得聚乙烯醇涂层由防粘纸板转移到该薄膜上面。这层有聚乙烯醇底层的薄膜即用作传送带。待粘合剂前体固化后,将夹层结构剥离开来。粘附着固化颗粒的传送带置入自来水中。颗粒即由背衬上脱离下来,用机械方式收集之。实施例12
重复实施例11,唯一不同的是所用的聚对苯二甲酸乙二醇酯薄膜130微米,并具有一层聚偏二氯乙烯底剂层。实施例13
重复实施例12,唯一不同的是聚对苯二甲酸乙二醇薄膜用了13μm厚的乙烯丙烯酸共聚物打底。实施例14与对比实施例A和B
实施例14用的磨料颗粒按制备磨料颗粒一般程序I制造。实施例14的涂覆磨料制品按制造本发明涂覆磨料制品(盘)的一般程序制造。
对比实施例A用一个常规的研磨薄膜(40微米厚,3M 268LImperial Microfinishing Film,Minnesota Mining and Manufactur-ing Co.的商品),将它叠压在一硬化纸板背衬(0.8毫米厚)上面。
对比实施例B用的是一个常规的三维涂覆磨料制品(P400Multocut XF布涂覆磨料制品,Minnesota Mining and Manufactur-ing Co.的商品)。这种产品含有按美国专利4,652,275所述方法制造的磨料团粒。这种涂覆磨料制品再叠压在一层硬化纸板背衬(0.8毫米厚)上。
实施例14的磨料的磨料制品按测试程序I进行了测试,其结果列于表3。实施例3与对比实施例A和B的制品按测试程序II进行了测试,结果列于表4。
表3
时间(分) 除去金属量(克)
1 7
2 6
3 6
4 5
5 5
表4实施例 初始磨削量 最后磨削量 总磨削量
(克) (克) (克)14 1.7 1.0 27.2对比A 1.7 0.3 2.9对比B 1.5 0.3 8.4实施例15与对比实施例C和D
实施例15磨料制品的制法与实施例14磨料制品相似,不同的是有如下差异。所用磨粒为WA02。此外,角锥体底面边长和高度均约710微米。
对比实施例C的磨料制品是一个P100 Regal树脂结合的硬化纸板研磨盘,Minnesota Mining and Manufacturing Co.的商品。这种产品是常规的陶瓷氧化铝磨粒(“Cubitron”,也由该同一厂家生产)结合于硬化纸板背衬上的。
对比实施例D的磨料制品是按制造对比实施例涂覆磨料制品的一般程序制造的。制造实施例D所用磨料颗粒的混合物,是将TATHEIC(50份)、TMPTA(50份)、PH1(2份)、WA02(200份)混合制成的。
实施例15与对比实施例C和D的磨料制品均按测试程序II进行了测试。当工件烧损时结束测试。结果列于表5。
表5
实施例 初始磨削量 最后磨削量 总磨削量
(克) (克) (克)
15 6.2 1.8 83
对比C 10.6 3.4 95
对比D 5.9 1.6 37实施例15的涂覆磨料制品,其研磨性能比对比实施例D的性能好,与对比实施例C差不多一样好。实施例16与对比实施例E和F
实施例16的磨料制品与实施例14相似,不同的是有下述差异。光引发剂用PH2,角锥体底面的边长和角锥体高度均约为710微米。而且,按制造本发明涂覆磨料制品(带)的一般程序制造了环形涂覆研磨带。
对比实施例E的磨料制品是P400 Regal Multicut树脂结合研磨带,3M 359F,为Minnesota Mining and Manufacturing Co.的商品。这种产品中用的是常规的陶瓷氧化铝颗粒的团粒(“Cubitron”)。
实施例16和对比实施例E的磨料制品均按测试程序III进行了测试。结果见表6。
表6
实施例16 对比实施例E
时间 磨削量 总磨削量 磨削量 总磨削量
(分) (克) (克) (克) (克)
1 1.82 1.82 3.06 3.06
2 3.46 5.28 5.66 8.72
3 4.47 9.75 6.66 15.38
4 4.39 14.14 7.16 22.54
5 4.97 19.11 7.19 29.73
6 5.45 24.56 7.75 37.48
7 6.48 31.03 8.55 46.03
8 6.43 37.46 8.36 54.39
9 6.33 43.78 8.05 62.44
10 6.98 50.76 6.74 69.18
11 7.53 58.29 6.05 75.23
12 8.38 66.67 4.13 79.36
13 8.65 75.32 2.67 82.03
14 8.22 83.54 2.15 84.18
15 7.39 90.94 1.88 86.06
16 8.51 99.45 1.76 87.82
17 8.88 108.32 0.94 88.76
18 8.74 117.05 0.65 89.41
19 8.88 125.94 1.09 90.50
20 8.07 134.01 0.93 91.43
对于本技术中的熟练人员来说,在不偏离本发明的范围和精神条件下可用的各种修改是显而易见的;而且应该理解,本发明并不受这里说明性实施例的限制。
Claims (23)
1.一种制造形状精确的颗粒的方法,包括如上步骤:
(a)提供一个三维体的模具,它至少有一个连续表面,所述表面至少具有一个在所述连续表面上形成的孔,通过该所述至少一个孔能进入所述三维体的一个模腔中;
(b)提供能将粘合剂前体通过所述至少一个孔引入所述至少一个模腔的引入装置,该粘合剂前体是一种热固性树脂;
(c)在固化区内提供一个使所述粘合剂前体至少部分固化的装置;
(d)将所述粘合剂前体引入至少一个模腔的至少一部分空间;
(e)令所述至少一个模腔连续通过所述固化区,使所述粘合剂前体至少部分固化成为一固化的、可手持的粘合剂,它的形状对应于粘合剂前体被引入模腔的那部分空间;
(f)使所述粘合剂从所述至少一个模腔脱离;
(g)将所述粘合剂形成为形状精确的颗粒。
2.按权利要求1所述的方法,其中所述的粘合剂前体还含有磨粒。
3.按权利要求1所述的方法,其中所述的热固性树脂选自酚醛树脂、氨基塑料树脂、聚氨酯树脂、环氧树脂、丙烯酸酯树脂、丙烯酸化异氰脲酸酯树脂、脲甲醛树脂、异氰脲酸酯树脂、丙烯酸化聚氨酯树脂、丙烯酸化环氧树脂以及它们的混合物。
4.按权利要求1所述的方法,其中所述的热固性树脂选自丙烯酸化聚酯树脂、具有侧位的α、β不饱和基团的氨基塑料树脂、环氧树脂、丙烯酸酯树脂、丙烯酸化异氰脲酸酯树脂、丙烯酸化环氧树脂以及它们的混合物。
5.按权利要求1所述的方法,其中所述粘合剂前体还含有至少一种下述的添加剂:填料、助磨剂、纤维、润滑剂、润湿剂、表面活性剂、水、溶剂、颜料、染料、偶合剂、抗静电剂、增塑剂、悬浮剂以及它们的组合。
6.按权利要求1所述的方法,其中所述模具是一个绕轴旋转的圆柱体。
7.按权利要求1所述的方法,其中所述的至少一个模腔具有选自下述的特定形状:角锥体、截角锥体、圆锥体、截圆锥体、棱柱体。
8.按权利要求1所述的方法,其中幅射能量是透过所述模具的。
9.按权利要求8所述的方法,其中幅射能量选自电子射线、紫外光和可见光。
10.按权利要求1所述的方法,其中步骤(f)和步骤(g)是同时进行的。
11.按权利要求1所述的方法,其中所述的粘合剂前体基本上不出所述模具的所述模腔的所述孔之外。
12.按权利要求1所述的方法,其中步骤(a)、(b)、(c)、(d)、(e)、(f)、(g)各步骤都连续进行。
13.按权利要求1所述的方法,其中所述的模具是一个可挠曲的热塑性基材。
14.按权利要求13所述的方法,其中所述的可挠曲基材是一根环形带。
15.按权利要求13所述的方法,其中所述的或挠曲基材是一根具有两个末端的带子。
16.按权利要求1所述的方法,其中所述的固化装置是一个能量源,它是个热能源、幅射能源、或热能源和幅射能源两者。
17.按权利要求1方法制造的形状精确的颗粒。
18.一个包括许多形状精确的颗粒的磨料制品,这种颗粒中含有(a)许多磨粒和(b)可加成聚合的粘合剂前体生成的粘合剂,所述颗粒藉一粘合介质粘合在一起形成一形状体,或粘接到一多孔的无纺织纤维基材中。
19.按权利要求18所述的磨料制品,其中所述的形状精确的颗粒具有的形状选自角锥体、圆锥体、棱柱体、球体和椭球体。
20.按权利要求18所述的磨料制品,其中所述的粘合剂前体选自丙烯酸化聚氨酯树脂、丙烯酸化环氧树脂、烯键不饱和树脂、具有侧位不饱和羰基的氨基塑料树脂、具有至少一个侧位丙烯酸酯基的异氰脲酸酯树脂、具有至少一个侧位丙烯酸酯基的异氰酸酯树脂。
21.一种涂覆磨料制品,它包括:
(a)一个背衬;
(b)至少一层许多形状精确的按权利要求18所述的磨料颗粒,这些颗粒含有磨粒和由可加成聚合的粘合剂前体生成的粘合剂;
(c)将所述形状精确的磨料颗粒粘接于所述背衬上的粘合介质。
22.按权利要求21所述的涂覆磨料制品,其中所述形状精确的颗粒的形状选自角锥体、圆锥体、棱柱体、球体和椭球体。
23.一种形状精确的磨料颗粒,它包括:
(a)许多磨粒;
(b)由可加成聚合的粘合剂前体生成粘合剂;
该种磨料颗粒的尺寸不大于2500微米。
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US08/085,638 US5549962A (en) | 1993-06-30 | 1993-06-30 | Precisely shaped particles and method of making the same |
US08/085,638 | 1993-06-30 |
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EP (2) | EP0706440B1 (zh) |
JP (1) | JP3579053B2 (zh) |
KR (1) | KR100339099B1 (zh) |
CN (1) | CN1081971C (zh) |
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AU (1) | AU672316B2 (zh) |
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CN107685296B (zh) * | 2013-03-29 | 2020-03-06 | 圣戈班磨料磨具有限公司 | 具有特定形状的磨粒、形成这种粒子的方法及其用途 |
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Also Published As
Publication number | Publication date |
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EP0835724A3 (en) | 2000-09-27 |
WO1995001241A1 (en) | 1995-01-12 |
KR100339099B1 (ko) | 2002-10-11 |
ES2145138T3 (es) | 2000-07-01 |
JP3579053B2 (ja) | 2004-10-20 |
CN1081971C (zh) | 2002-04-03 |
CA2166398A1 (en) | 1995-01-12 |
US5628952A (en) | 1997-05-13 |
AU6953194A (en) | 1995-01-24 |
US5500273A (en) | 1996-03-19 |
BR9406987A (pt) | 1996-03-12 |
TW334462B (en) | 1998-06-21 |
DE69424167T2 (de) | 2000-12-21 |
EP0706440B1 (en) | 2000-04-26 |
AU672316B2 (en) | 1996-09-26 |
EP0835724A2 (en) | 1998-04-15 |
EP0706440A1 (en) | 1996-04-17 |
RU2123927C1 (ru) | 1998-12-27 |
JPH08512074A (ja) | 1996-12-17 |
DE69424167D1 (de) | 2000-05-31 |
US5690705A (en) | 1997-11-25 |
US5714259A (en) | 1998-02-03 |
ATE192059T1 (de) | 2000-05-15 |
US5549962A (en) | 1996-08-27 |
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