CN1181774A - 具有新型沉淀碳酸钙颜料的喷墨记录纸 - Google Patents
具有新型沉淀碳酸钙颜料的喷墨记录纸 Download PDFInfo
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- CN1181774A CN1181774A CN96193358A CN96193358A CN1181774A CN 1181774 A CN1181774 A CN 1181774A CN 96193358 A CN96193358 A CN 96193358A CN 96193358 A CN96193358 A CN 96193358A CN 1181774 A CN1181774 A CN 1181774A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 37
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- 239000000049 pigment Substances 0.000 title claims description 31
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
公开了一种具有热老化和/或磨细的沉淀碳酸钙(“PCC”)和粘合剂的改进了的热喷墨记录纸。该热老化和研磨方法可生产出具有增强PCC与喷墨油墨结合的能力而又不是结合得太强以至改变油墨颜色的表面形态和化学性质的PCC离散微粒。已生产出本发明的具有这种PCC和粘合剂的喷墨记录纸,由于降低了洇纸、散开和渗透或背面透印以及改进了光密度、干燥时间和耐水牢度,因而这种纸优于多功能的办公用纸。本发明的喷墨记录纸可在远低于原价的价格下与二氧化硅为基础的商品纸媲美。
Description
本发明涉及用于喷墨记录纸的新型热老化和磨细的沉淀碳酸钙颜料。更具体而言,本发明涉及一种喷墨记录纸,该记录纸具有上述颜料和至少一种水溶性粘合剂,以便提高打印质量。本发明还涉及将这些组分涂覆在纸上的方法以及生产这类新型颜料的方法。
热喷墨法是通过将带有朝向记录纸的锐孔的小室中的少量油墨加热,使水性稀油墨喷涂在纸面上的方法。加热后的少量油墨很快达到其沸点,所形成的蒸气泡将微细的油墨液滴推送到纸上,该液滴即在纸上产生形成字符或图像的点阵中的单点。这种方法要求一种固体和高沸点组分含量低的油墨,以便能很快沸腾而不留下会污染加热元件和堵塞锐孔的残渣。因此,喷墨打印油墨中的至多96%是水和低分子量二元醇的混合物。虽然这种油墨在加热时能很快沸腾,以保证快速打印而不易于堵塞,但是它导致所喷涂的油墨很容易流动且干燥缓慢。因此,只有当油墨的着色剂或染料能保持在纸的外表面或附近,而且不会从所喷涂的位置上散开或移动,才能得到满意的打印质量。
能迅速干燥以避免着色剂蹭脏也是很重要的。在未配备加热元件的打印机中,油墨中的水和二元醇组分必然要渗入纸体内,使纸面上的着色剂适当地干燥。如果着色相随着渗入纸内的液相带进纸中,或如果着色剂迁移穿过纸的表面,则所得到的打印件或图像的质量将会很差。同样,如果将打印过的表面弄湿或用辉光剂作记号、则未永久固定在纸上的干燥油墨着色剂就会渗开或流动。因此,为了获得最佳的性能,干了的油墨必须具有极好的耐水和耐辉光剂的牢度。
在大多数应用中,多功能办公用纸所提供的热喷墨打印质量不能满足要求或很差。这在采用伴随叠加喷涂油墨的彩色打印时特别如此。在一些打印头向右移时以一种顺序而打印头向左移时又以相反顺序喷涂各种着色剂的打印机中,打印质量差的情况更加重。多功能办公用纸常常会使着色剂渗入纸中,这导致打印出的图像的光密度降低,并在纸的反面增加背面透印。高度施胶的多功能办公用纸可避免液体渗透,导致较高的油墨光密度,但是也会使油墨过分洇纸和散开。
一种改进热喷墨打印质量的方法是将一种材料涂覆在纸的表面上,使油墨着色剂与该表面结合,而让水/二元醇液相进入纸体内,以加速干燥。然而,油墨着色剂常常是一种不饱和的或芳族的有机化合物,如果该表面材料与着色剂相互作用太强,则油墨的颜色会变化。因此,必须得到一种可以防止油墨着色剂渗入纸内,但不会因相互作用太强而影向着色剂致使颜色变化的表面材料。
Oshima等人的美国专利4,478,910公开了一种涂以高比表面积的胶体二氧化硅颜料和聚乙烯醇粘合剂的纸基材料,该胶体二氧化硅的的比表面积大于200m2/g。
Migamoto的美国专利4,576,867和Kojima等人的美国专利4,830,911讲述了将阳离子型的季铵聚合物涂覆在纸料上可以改进所得纸的耐水牢度。Malhotra的美国专利5,223,338也公开了在施胶机上涂覆这种季铵聚合物。然而,高质量的商品热喷墨记录纸是用机外涂覆设备生产的,即该记录纸不是在造纸机的施胶机上处理,而必须将其取出并在采用单独涂覆操作的附加步骤中涂覆。
沉淀碳酸钙(“PCC”)已公开作为喷墨纸中的有效颜料或填料,但是,它通常被包括在列有许多化合物的表中,其中也包括磨细的天然碳酸钙,这是一种在物理和化学性质上与PCC大不相同的化合物形态;例如,磨细的天然碳酸钙颗粒是远大于PCC的颗粒,且通常是阴离子型的,而PCC天然地是阳离子型的。
Kondo等人的美国专利5,320,897叙述了用现成的颜料和水溶性粘合剂涂覆的喷墨记录纸。所公开的这种有效的颜料具有的表观比重为0.10-0.50g/cm3,生产的纸具有水接触角为45°-100°。
Tsukisaka等人的美国专利5,007,964公开了一种掺入螯合剂的普通沉淀法,以便得到BET比表面积为25-55m2/g、可用于记录纸的多孔链状PCC颗粒的附聚物。BET比表面积大于55m2/g的颗粒,因其具有较高的密度、不是多孔的,且表现出较低的吸油和吸水能力,已公开认为是不适用的。另外,还公开了可以使用呈糊剂的PCC,或使用通过将干燥了的糊剂磨细而得的粉末,该专利公开认为这不会影响颗粒的附聚。
Kunesh等人的美国专利5,215,734公开了一种加速热老化PCC的方法,该方法可生产比表面积约为3至约15m2/g、平均离散粒度约为0.2至约0.9微米的结晶。这种PCC可用以改进纸的光学性质。
从上述情况看出,在现有技术中并无如何改进喷墨记录纸打印质量的建议。本发明提供了解决上述问题的办法。
本发明涉及具有新型热老化和/或磨细的沉淀碳酸钙颜料和粘合剂的增强了性能的喷墨记录纸。该热老化的PCC是通过将氢氧化钙浆体碳酸化以形成沉淀碳酸钙浆体,将该浆体过筛除去杂质,将有机膦酸盐类化合物例如双(亚甲基膦酸)乙醇胺添加到浆体中,并将PCC浆体在有机膦酸盐的存在下热老化以产生可用于喷墨记录纸的改进了的颜料而制得的。
本发明的喷墨记录纸是通过采用包括热老化和/或磨细的PCC和粘合剂的涂料涂覆在纸基材料的至少一面上以形成喷墨记录纸而生产的。这种热老化和/或磨细的沉淀碳酸钙是通过将碳酸钙浆体碳酸化,将PCC在有机膦酸盐类化合物的存在下热老化和/或将该PCC磨细以制得具有增强PCC与喷墨打印机油墨着色剂结合能力的表面形态和化学性质的PCC离散微粒而生产的。
已制得了一种喷墨记录纸,该记录纸在大幅度降低价格的情况下可提供接近或优于最佳喷墨专用纸的彩色喷墨打印质量。PCC的粒度、表面积、表面化学性质和聚集度的选择及其与适当配方的粘合剂的组合可对各种热喷墨打印特性逐个地加以调整和优化。
本发明的阳离子型PCC可在不用昂贵的阳离子型树脂的情况下与油墨着色剂结合,并能在造纸厂就地生产,因此,它们不像二氧化硅那样需要干燥、运输,然后再加水处理才能使用。本发明的制剂设计成能在例如单价低的大型造纸机上安装的计量施胶机上施用。因此,本发明的PCC组合物可作为造纸操作的一部分加以施用,而不是在正常的造纸操作完成之后在增加加工费用和最终产品成本的单独的附加工序中施用。由于计量施胶机通常是双面施胶,而不是像所见到的昂贵的市售优质纸那样单面施胶,因此在这种施胶机上施胶后的纸的两面均可用于打印。虽然聚乙烯醇是本发明优选的粘合剂,但是用热老化和/或磨细的PCC和价格较低的粘合剂处理喷墨记录纸也可以显著改进打印质量。最后,本发明的制剂提供的纸还适用于复印,使其具有多种用途。
PCC通常是通过将含有二氧化碳的气体鼓入氢氧化钙的水悬浮液中生产的。其他无机材料特别是含有铝的无机材料例如明矾可以与PCC其沉淀,或可以沉淀在PCC沉淀的表面上。然而,已意外地发现,当将这种PCC热老化和/或磨细,用适宜的粘合剂处理,然后以组合物的形式用以处理热喷墨记录纸时,可制得优质的喷墨记录纸,该记录纸提供的打印质量可与涂有二氧化硅的市售高价热喷墨纸媲美,但价格却大幅度降低。
热老化和研磨的方法可生产出具有增强PCC与喷墨油墨着色剂结合的能力而又不是结合得太强以至改变油墨颜色的表面形态和表面化学性质的PCC离散微粒。已生产出本发明的具有这种PCC和粘合剂的喷墨记录纸,由于这种纸降低了洇纸、散开和渗透或背面透印以及改进了光密度、干燥时间和耐水牢度,因而优于多功能的办公用纸。
本发明的PCC是通过将含有二氧化碳的气体通入氢氧化钙的悬浮液中的常规沉淀法生产的。然后,在使用前先将该碳酸钙沉淀热老化和/或磨细。具有这种PCC的喷墨记录纸的打印质量通过颗粒的聚集状况以及颜料和粘合剂的表面化学性质控制。颜料表面的化学性质通过该颜料的特定合成路线和合成后的处理控制。
特别适用于本发明的PCC是采用包括将二氧化碳在约7°至约18℃的温度下通入氢氧化钙含水浆体中的方法制备的。该浆体按反应料浆中与氢氧化钙相当的碳酸钙量计,含有约为0.02-1%(重量)的阴离子型有机多膦酸盐聚电解质(典型的是Briquest 221-50A,双-(亚甲基膦酸)乙醇胺,Albright & Wilson Americas,Inc.,Richmond,VA)和0-10%(重量)的硫酸铝十八水合物(Al2SO4·16H2O)。连续通入二氧化碳直到碳酸钙基本上完全沉淀为止。通常,这是在碳酸化了的浆体的pH约为10-11、电导率达到最小值时出现的。
除添加硫酸铝十八水合物之外,有关这方面的方法基本上是美国专利4,367,207的方法,该专利讲述的内容引入本文作为参考。在美国专利4,892,590中公开了添加硫酸铝十八水合物,该专利讲述的内容也引入本文作为参考。
一旦制得所需粒度和比表面积的PCC,即将该PCC热老化或磨细以得到优质、廉价的喷墨记录纸所要求的PCC特性。
研磨可使颜料聚集体破碎成许多单个的颗粒,使原来接合的PCC表面暴露出来,这些暴露出的表面在化学上与聚集体的表面不同。通常,对具有偏三角面体的、针状的、棱柱形或菱形形态的PCC进行研磨。一般对菱形的或棱柱形的PCC进行热老化,该方法不仅将聚集体分离,而且还包括在颗粒表面上进一步沉淀。可以认为,新沉淀的材料在化学性质上可能与原来的表面材料不同;例如热老化或磨细的PCC的表面可能具有较高的钙-镁比。
常规的热老化法,也称为奥斯特瓦尔德熟化法是一种加工方法,借助该方法可使原来处于较高内能态并具有较高相溶解度的结晶例如碳酸钙通过溶解和再沉积在处于较低内能态的结晶上而进行相变。该方法导致最终的结晶产品具有更好的晶格结构完整性、更窄的粒度分布、更大的颗粒离散度以及更低的表面能等特征。
在本发明中,当浆体的电导率通常在pH约10-11下达到最低值时,二氧化碳与氢氧化钙的反应结束,就可以开始进行PCC的热老化。然后,将PCC过筛以除去杂质并添加至多占PCC重量约1%的有机膦酸盐,以控制热老化的限度或程度。其他对碳酸钙是表面活性的化学剂也可以像有机膦酸盐一样起控制热老化限度或程度的作用。这些化学剂包括,但不限于以下化合物,多磷酸钠、硅酸钠、聚丙烯酸钠、各种羧酸例如单、二、三和多羧酸及其盐、各种多糖类以及各种具有重复的羧酸官能度的胶。然后,将该浆体加热到至少约75℃,优选约80℃或更高以便热老化PCC颗粒。热老化步骤进行的时间视温度而定多达约10小时或更长。在约80-85℃的温度下,进行加热约2-5小时。由于有未反应的氢氧化钙存在,该浆体的pH升高到约10.5。然后,按每小时一次的间隔通过测定PCC的表面积来监测老化反应。回收作为本方法最终产品的热老化过的PCC具有菱形的或棱柱形的形态,比表面积约为60至约100m2/g,优选约为65至约95m2/g,最优选约为80-90m2/g。
用于本发明的有机膦酸盐是通常用作防垢剂、多价螯合剂、解絮凝剂和洗涤促进剂的不同分子量的有机多膦酸盐。这些有机瞵酸盐包括,但不限于氮川三(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、羟基乙烷-1,1-二膦酸、乙醇胺、双(亚甲基膦酸)乙醇胺、N,N-二亚甲基膦酸以及六亚甲基二胺四(亚甲基膦酸)。优选的有机膦酸盐是双-(亚甲基膦酸)乙醇胺。
碳酸钙的研磨可以在例如常规球磨机、喷射研磨机、微型研磨机或介质研磨机中以湿磨法或干磨法进行。优选通过将PCC的含水浆体引入装有尺寸约为0.7-0.9mm的玻璃介质的介质研磨机中进行研磨。该介质研磨机装有机械搅拌器,PCC桨体中的固体含量优选为该PCC和水总重的约10-30%(重量)。通常,对偏三角面体形态的PCC进行介质研磨时,可生产出比表面积约为10至约40m2/g,优选约为15至约30m2/g、柱状晶体较少的PCC。
用于喷墨记录纸涂料组合物的粘合剂的实例是本领域中迄今常用的粘合剂,它们包括聚乙烯醇(“PVOH”)及其衍生物;氧化淀粉、醚化淀粉、酯化淀粉、糊精和类似的淀粉类物质;羧甲基纤维素、羟乙基纤维素和类似的纤维素衍生物;酪蛋白、明胶、大豆蛋白质;马来酐树脂;常用的苯乙烯丁二烯共聚物、甲基丙烯酸甲酯-丁二烯共聚物以及类似的共轭二烯系聚合物或共聚物的网格结构物(lattices);丙烯酸酯和甲基丙烯酸酯的聚合物或共聚物以及类似的丙烯酸聚合物的网格结构物和胶乳。当需要时,该涂料组合物还可以在其中包含一定量的常用于本领域中的常规颜料分散剂、增粘剂、流动性改良剂、消泡剂、泡沫抑制剂、脱模剂、着色剂等。
已制备和测试了具有本发明的PCC制剂的喷墨记录纸。以下是制备步骤和所用测试方法的概述。一旦生产出PCC,整个测试方法可以归类为四个方面;颜料的制备、与粘合剂的配制、纸的涂覆和加工以及测试。兹将这些步骤的各个具体细节说明如下。颜料的制备:
待测试的颜料通常呈浆体或滤饼形式。通过真空过滤将浆体形式的样品浓缩至所需的固体含量。在某些情况下,例如采用比表面积约为10-35m2/g的介质研磨机研磨过的PCC时,为了重复试验条件,这种浆体的固体含量不再作改变。一旦确定了目标制剂的固体含量,如果需要,可用水稀释该颜料并充分混合。该颜料的特征以粒度分布(Sedigraph 5100)、比表面积(Flowsorb)、粘度(Brookfield)以及采用扫描电子显微镜(“SEM”)测得的形态来表示。
采用以氮气作为吸收气、应用BET理论的Micromeritics Flowsorb II2300测得该产品的表面积。用Micromeritics Sedigraph Model 5100,采用沉积技术,以约0.1%羧基化的聚电解质(Daxad 30)作为分散剂,对约为3%的产品的水分散体的粒度作了测定。制剂的配制:
典型的粘合剂是阳离子型的淀粉(Filmcote-54,National Starch)、聚乙烯醇即PVOH(Airvol 107,Air Products Inc.)和胶乳(Dow试验性的施胶机胶乳)。当采用淀粉作为粘合剂时,将干淀粉分散在水中达到约10-25%的固体含量,然后在实验室的自动蒸煮器中约于195℃下蒸煮50-190分钟。将所得的粘稠淀粉浆体与已经适当地配制以便达到目标制剂固体含量的颜料混合,然后在装有Cowles型开式叶轮片的Premier磨机中充分混合。将该制剂混合约5分钟直至获得完全均匀的浆体,所得的制剂以Brookfield粘度(10、20、50和100rpm)和固体含量表征。
聚乙烯醇的制备与用于淀粉的制备方法类似。将PVOH在实验室的蒸煮器中约于200℃下水合50-190分钟达到10%的固体含量。对胶乳粘合剂(50%固体含量)而言,在测试之前不必制备。这些粘合剂与颜料的配制如同与淀粉的配制一样。
用于测试的制剂固体含量为约20-28%,而典型的涂料制剂具有约20%的固体含量。纸的涂覆
通常,将未施胶的纸张定量为81.3-83.0g/m2的纸基材料用于测试。将该纸切割成12×17”的纸片并固定在CSD Drawdown Apparatus上,该装置由装在其上部具有弹簧夹的金属基底上的玻璃板(12×17”)构成。采用CSD压延棒涂覆涂料制剂,将根据目标涂层重量精选的压延棒放在纸的上部,用30mL的注射器将充分混合的10-15mL制剂样品以均匀线条添加到压延棒下方的纸上,并以轻微的压力和恒定、稳定的速率在约为2秒钟内从顶部到底部牵引压延棒涂覆该纸。
涂层的重量取决于不锈钢压延棒,该压延棒特别地开了槽以便将预定量的涂料传送到纸的表面上。凹槽较少的压延棒传送的涂料重量较重,因为凹槽之间的间隔较宽。反过来,具有更多间隔更紧凑凹槽的压延棒给出的涂料重量较轻。典型的涂层重量约为2-10g/m2。
一旦已涂覆了制剂,立即用手持式热喷枪将该纸干燥约30-60秒,然后在室温下经过约2-24小时彻底干燥。将干燥过的纸切割成8 1/2×11”的纸片供作测试之用。纸的测试
Hewlett Packard Corporation(“HP”)已制定了喷墨打印质量的最低规格。因此,大多数测试均采用HP的方法来测定以下打印性能。
光密度是图像的反射密度的一种量度。将特定的测试图案打印在纸上,采用反射式密度计(Macbeth RD918)测定纯黑色、复合黑色、青色、品红色和黄色的光密度。将所得的光密度与HP的最低规格作比较。
油墨的散开和洇纸都会降低喷墨打印的质量。油墨的散开被定义为打印过的区域增大或加宽。洇纸是会导致图象模糊的油墨芯吸现象。这可通过对用作光密度测定的相同打印图案的特定部分进行分析来测量。该特定部分用于评价油墨打印区、散开和油墨的周界、洇纸。对所得的数字化图形定量并与优质商品喷墨纸作比较。HP的测试方法对油墨的散开和洇纸并不采用上述方法,因为HP方法的测试是主观估计而不是定量的。
油墨的干燥时间是油墨吸收到一张纸中的速率的量度。打印特定的测试图案,图像被吸干后,测定转印的黑色油墨所产生的光密度。使所得结果符合HP的指数衰变模型,计算油墨的干燥时间。将最终的干燥时间与HP规定的最低标准作比较。
耐水牢度是着水时着色剂从打印区域转移到未打印区域的量的量度。将测定耐水牢度的测试图案打印在纸上,将250微升水施加在打印部位上,并让其流过打印区域和毗邻的未打印区域。测定转移到未打印区域上的黑色油墨的光密度。将所得的光密度与HP的标准作比较。
耐辉光剂牢度是在着色剂与两种辉光剂接触时从打印区域转移到来打印区域的着色剂的量度。将特定的测试图案打印在纸上,用碱性辉光剂和酸性辉光剂横过测试区域划垂直线。测定转移到未打印区域上的黑色油墨的光密度。并与HP的最低标准作比较。
用CIELAB体系进行颜色的评价,该方法是采用Elrephro Datacolor2000比色计测定L*、a*和b*的值,以便给青色、绿黄色、蓝色、品红色和红色打印区域的颜色外观评分。将结果与HP的彩色品质图作比较。
调色剂的粘着性是非喷墨静电复印的一项测试,它是测定调色剂与涂层的粘着程度。调色剂的粘着性对通常用作复印纸的商品多功能纸而言是重要的。在本测试中,采用Xerox复印机将测试图案拷贝到纸上,用5磅滚筒使测试区域起褶痕,然后将所得调色剂损失的图案与一套标准作比较。对调色剂损失程度进行评级,从1,最好或没有调色剂损失,到10,最差或调色剂严重损失。
在亮度测试中,采用Technidyne S-4亮度计测试涂覆过的纸的TAPPI亮度。将结果与未涂覆的基纸作比较。
实施例
下列非限制性实施例仅用于说明本发明的优选实施方案,而不应理解为是对本发明的限制,本发明的范围在所附权利要求书中作了明确的限定。
实施例1
在起始温度为50℃下通过机械搅拌将1份石灰与5份水混合进行制备氢氧化钙的浆体。将该浆体混合约10分钟,用水稀释到1份石灰15份水之比,然后用60目的筛子过筛以除去粗砂。
从装在30升的不锈钢反应器里的桨体中沉淀碳酸钙,该反应器配备了带有两个涂了沥青的叶片式透平叶轮的可变速搅拌器、加热和冷却夹套、使含有二氧化碳的气体导入叶轮的碳酸化用的不锈钢管道以及监测悬浮液pH的探测器。
在420rpm下搅拌的同时,将上述制备的26升氢氧化钙浆体添加到反应器中。然后在该浆体中加入6克有机膦酸盐(Briquest 221-50A,双-(亚甲基膦酸)乙醇胺,Albright & Williams Americas,Inc.,Richmond VA),以相当于氢氧化钙浆体的碳酸钙计,相当于0.1%(重量)的Briquest。然后添加1升含有95.0克Al2SO4·16H2O的溶液。将该浆体的温度调节到9.5℃,在615rpm下搅拌的同时,按2.3S.C.F.M.的速率通入含二氧化碳的气体(气流中含28%(体积)的CO2)。在冷却下,使氢氧化钙浆体的碳酸化持续36分钟,直至达到该浆体的最低电导率表明碳酸钙已沉淀完全为止。该浆体的最终温度为15.8℃。经测定,所得碳酸钙的比表面积为115m2/g。
实施例2
按照与实施例1中所述的相同方式,采用相同的装置,在0.1%(重量)的Briquest和3.15%(重量)的Al2SO4·16H2O存在下通过用含有二氧化碳的气体碳酸化氢氧化钙浆体进行碳酸钙沉淀。在35分钟内,当达到最低的电导率时,碳酸化完全。该浆体的最终温度为16.7℃,pH为11.65。PCC的比表面积为102.3m2/g。用325目的筛子将PCC浆体过筛,然后将其送回到反应器中 在搅拌的同时,添加45克Briquest 221-50A,以存在的PCC的重量计,相当于0.7%(重量)的Briquest。将pH调节到9.5,并将该浆体加热到80℃,在80℃下热老化PCC5小时。最终产品的比表面积为82.4m2/g。
实施例3
按照与实施例2中所述的相同方式,在0.1%(重量)的Briquest和3.15%(重量)的Al2SO4·16H2O(其中两者的百分数均以相当于氢氧化钙的碳酸钙计)的存在下,将氢氧化钙浆体碳酸化。碳酸化的时间为39分钟,最终pH为10.9,得到具有比表面积为115.1m2/g的PCC。在搅拌该混合物的同时,以PCC的重量计,添加0.7%(重量)的Briquest 221-50A。用325目的筛子将该浆体过筛,然后返回到反应器中,加热到80℃2小时。最终产品的比表面积为81.6m2/g。
实施例4
按照与实施例2中所述的相同方式,在0.7%(重量)的Briquest 221-50A和3.15%(重量)的Al2SO4·16H2O(两者的百分数均以相当于氢氧化钙的碳酸钙计)的存在下,将氢氧化钙浆体碳酸化。每批操作达到最低电导率的时间为36分钟,最终pH为11.4。PCC的比表面积为99.1m2/g。将该浆体通过325目的筛子,返回到反应器中,搅拌,以PCC的重量计,添加0.15%(重量)的Briquest 221-50A。将该浆体的pH调节到9.5,并将该浆体加热到80℃。在80℃下热老化PCC2小时,得到具有比表面积为63.8m2/g的PCC。
实施例5
将体积为0.6升和固体含量为20.2%(以碳酸钙和水的总重计的碳酸钙浆体放入装有1.7千克0.7-0.9mm玻璃珠的1.5升不锈钢介质研磨机中,其中所述碳酸钙是具有比表面积为11.57m2/g和平均粒度为1.35微米的偏三角面体PCC。该介质研磨机装有可变速的机械搅拌器。在搅拌速度为2450rpm下,将该浆体研磨10分钟。磨细的产品具有的比表面积为15.59m2/g,平均粒度为0.35微米。
实施例6
将体积为0.6升和固体含量为18.7%(以碳酸钙和水的总重计)的碳酸钙浆体放入装备了可变速机械搅拌器,装有1.7千克0.7-0.9mm玻璃珠的1.5升不锈钢介质研磨机中,其中所述碳酸钙是具有比表面积为26.07m2/g和平均粒度为0.88微米的偏三角面体PCC。在搅拌速度为2450rpm下,将该浆体研磨10分钟。磨细的PCC产品具有的比表面积为30.11m2/g,平均粒度为0.26微米。
将实施例1-6的热老化和介质研磨机磨细了的PCC与适宜的粘合剂配制制剂,按上述方法将测试纸片涂以6g/m2的制剂。干燥后,将人工制作的纸片用于测试纯黑色光密度、复合光密度、散开、渗透、干燥时间以及水溶性。上述这些测试的结果均列于表1。
表1
实施例号 | 1 | 1 | 1 | 2 | 2 | 2 | 3 | 4 | 5 | 6 |
粘合剂 | 淀粉 | PVOH | PVOH | 淀粉 | PVOH | PVOH | 淀粉 | 淀粉 | 淀粉 | 淀粉 |
粘合剂%(重量) | 30 | 15 | 30 | 30 | 15 | 30 | 30 | 30 | 30 | 30 |
复合黑色光密度 | 0.98 | 0.9 | 0.9 | 1.22 | 1.11 | 1.22 | 1.15 | 1.14 | 1.02 | 1.03 |
纯黑色光密度 | 1.17 | 1.34 | 1.31 | 1.31 | 1.36 | 1.54 | 1.22 | 1.25 | 1.53 | 1.4 |
散开 | 106.2 | 101.3 | 100.2 | 108.4 | 101.6 | 100.8 | 107.7 | 106.6 | 101 | 103.5 |
渗透率 | 30.3 | 34.5 | 32.7 | 8.4 | 25.7 | 21.8 | 20.9 | 12.1 | 19.1 | 23.3 |
干燥时间 | 0 | 0 | 0 | 22 | 0 | 17 | 11 | 21 | 104 | 50 |
水溶性 | 0 | 0.02 | 0.02 | 0.15 | 0.02 | 0.07 | 0.08 | 0.12 | 0.45 | 0.32 |
当与未涂覆的典型商品纸比较时,上述这些结果表现出显著的改进,所述未涂覆的商品纸通常具有的复合黑色光密度约为0.9、纯黑色光密度约为1.28、散开约为108、渗透率约为38%、干燥时间约为38以及水溶性约为0.17。通过比较,优质价高的、涂覆了的商品纸具有复合黑色光密度约为1.2、纯黑色光密度约为1.56、散开约为98、渗透率约为28%、干燥时间约为12而水溶性接近0。因此,根据本发明生产的喷墨记录纸,特别是采用以实施例2中生产的PCC为基础的制剂涂覆过的纸,在喷墨打印质量上可与目前能买到的优质价高的商品纸媲美。
很明显,虽然本文中所公开的本发明非常适合于实现上述目的,然而应该理解到本领域中的技术人员可能会想出许多改进和实施方案。本发明人的意图是,所附权利要求书覆盖了上述所有的改进和实施方案,因为它们属于本发明的实质和范围。
Claims (17)
1.一种制备沉淀碳酸钙颜料的方法,该方法包括生成沉淀碳酸钙颗粒的浆体,将有机膦酸盐类化合物添加到该浆体中,将该浆体加热以热老化其中的沉淀碳酸钙颗粒并生成改进了的颜料。
2.权利要求1的方法,其中该有机膦酸盐类化合物是含胺的磷酸衍生物,所添加的量为0.1-1%(重量)。
3.权利要求1的方法,其中该有机膦酸盐类化合物是双(亚甲基膦酸)乙醇胺,所添加的量为0.4-0.85%(重量)。
4.权利要求1、2或3的方法,其中将该沉淀碳酸钙颗粒老化足够的时间以使BET比表面积大于60m2/g。
5.权利要求1、2、3或4中任一项的方法,其中将该沉淀碳酸钙颗粒在至少75℃的温度下老化1-10小时。
6.权利要求1、2、3、4或5中任一项的方法,其中将该沉淀碳酸钙颗粒在80-85℃的温度下老化约2-5小时。
7.每当采用前述权利要求中任一项的方法制得的热老化过的碳酸钙颗粒。
8.一种生产喷墨记录纸的方法,该方法包括:采用包括根据权利要求7的热老化过的碳酸钙颗粒和粘合剂的涂料涂覆纸基材料的至少一面以生成喷墨记录纸。
9.权利要求8的方法,其中将该涂料涂覆在纸基材料的每一面上。
10.权利要求8或9的方法,其中在造纸工艺过程中通过造纸机将该涂料涂覆在纸上。
11.权利要求8、9或10的方法,其中该粘合剂是聚乙烯醇或淀粉。
12.生产具有增强性能的喷墨记录纸的方法,该方法包括:
a)将沉淀碳酸钙颜料磨细以产生具有增强该颗粒与油墨结合能力的表面形态和化学性质的颗粒;
b)采用包括所述磨细的沉淀碳酸钙颜料颗粒和粘合剂的涂料涂覆纸基材料的至少一面以生成喷墨记录纸。
13.权利要求12的方法,其中该颗粒被磨细到具有BET比表面积至少为15m2/g。
14.一种喷墨记录纸,该记录纸包括其上具有包括热老化过的沉淀碳酸钙颜料、磨细的沉淀碳酸钙颜料、或其混合物以及粘合剂的涂层的纸基材料。
15.权利要求14的喷墨纸,其中采用介质研磨机磨细的沉淀碳酸钙颜料具有BET比表面积至少约为15m2/g。
16.权利要求14或15的喷墨纸,其中该热老化过的沉淀碳酸钙颜料具有BET比表面积至少约为60m2/g。
17.权利要求14、15或16的喷墨记录纸,其中该粘合剂是聚乙烯醇或淀粉。
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CN103608185B (zh) * | 2011-06-03 | 2016-08-31 | Omya国际股份公司 | 制造经涂覆基底的方法 |
TWI579429B (zh) * | 2011-06-03 | 2017-04-21 | 歐米亞國際公司 | 製造經塗覆基質的方法 |
CN104203827A (zh) * | 2012-03-30 | 2014-12-10 | 欧米亚国际集团 | 在碱性条件下具有改善稳定性的分散的含碳酸钙的材料 |
CN104203827B (zh) * | 2012-03-30 | 2016-01-06 | 欧米亚国际集团 | 在碱性条件下具有改善稳定性的分散的含碳酸钙的材料 |
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