CN101626903A - 具有底涂层的激光敏感记录材料 - Google Patents
具有底涂层的激光敏感记录材料 Download PDFInfo
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- CN101626903A CN101626903A CN200880007425A CN200880007425A CN101626903A CN 101626903 A CN101626903 A CN 101626903A CN 200880007425 A CN200880007425 A CN 200880007425A CN 200880007425 A CN200880007425 A CN 200880007425A CN 101626903 A CN101626903 A CN 101626903A
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Abstract
本发明提供了激光敏感记录材料,其包括被记录层和底涂层涂布的基底,其中记录层包含受到激光辐照产生的热处理时发生颜色变化的体系,以及其中底涂层包含颜料,前提是记录层的受到激光辐照产生的热处理时发生颜色变化的体系不包含有机隐色染料和有机显色剂,其制备方法,标记该激光敏感记录材料的方法,以及经标记的激光敏感记录材料。
Description
本发明涉及激光敏感记录材料,其制备方法,标记该激光敏感记录材料的方法,以及经标记的激光敏感记录材料。
包装材料通常需要标记上一些信息,例如标识、条形码、截止日期或批号。对此,一种实现方法是以组合物涂布包装材料,在热处理时该组合物形成可见标记。
本发明的目的是提供包括记录层和底涂层的激光敏感记录材料,其中记录层在受到激光辐照提供的热处理时发生颜色变化,以及其中底涂层增强激光辐照的作用。例如,当产生的颜色密度在指定的辐照功率和时间的组合下增加时,或者当在较低辐照功率和/或较少时间的组合下可获得所产生颜色的指定密度时,增强了激光辐照的作用。
该目的通过权利要求1的激光敏感记录材料、权利要求5和6的方法以及权利要求7的经标记的激光敏感记录材料来解决。
本发明的激光敏感记录材料包括被记录层和底涂层涂布的基底,其中记录层包含受到激光辐照产生的热处理时发生颜色变化的体系,以及其中底涂层包含颜料,前提是记录层的受到激光辐照产生的热处理时发生颜色变化的体系不包含有机隐色染料(organic leuco dye)和有机显色剂(organiccolour developer)。
有机隐色染料为这样的有机化合物,其可具备两种形式,其中一种是无色的。
有机隐色染料的实例为苯酞(phthalide)、氮杂苯酞(azaphthalide)、荧烷(fluoran)、三芳基甲烷、苯并噁嗪、喹唑啉、螺噁嗪、螺吡喃、螺异苯并呋喃、醌、噻嗪或噁嗪或其混合物。
苯酞的实例为结晶紫内酯(3,3-双(对二甲基氨基苯基)-6-二甲基氨基苯酞)、3,3-双(对二甲基氨基苯基)苯酞、3,3-双(1-乙基-2-甲基吲哚-3-基)苯酞、3,3-双(1-辛基-2-甲基吲哚-3-基)苯酞、3-(4-二乙基氨基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-苯酞、7-(N-乙基-N-异戊基氨基)-3-甲基-1-苯基-螺[4H-苯并吡喃[2,3-c]吡唑-4(1H)-3′苯酞、3,6,6′-三(二甲基氨基)螺-[芴-9,3′-苯酞]、3,6,6′-三(二乙基氨基)螺[芴-9,3′-苯酞]、3,3-双-[2-(对二甲基氨基苯基)-2-(对甲氧基苯基)乙烯基-4,5,6,7-四溴苯酞、3,3-双-[2-(对二甲基氨基苯基)-2-(对甲氧基苯基)乙烯基-4,5,6,7-四氯苯酞、3,3-双[1,1-双(4-吡咯烷基苯基)乙烯-2-基]-4,5,6,7-四溴苯酞和3,3-双-[1-(4-甲氧基苯基)-1-(4-吡啶基苯基)乙烯-2-基]-4,5,6,7-四氯苯酞。
氮杂苯酞的实例为3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞、3-(4-二乙基氨基-2-乙氧基苯基)-3-(1-辛基-2-甲基吲哚-3-基)-4-氮杂苯酞和3-(4-N-环己基N-乙基氨基-2-甲氧基苯基)-3-(1-乙基-2-甲基吲哚-3-基)-4-氮杂苯酞。
荧烷的实例为3-二(乙基)氨基-6-甲基-7-(叔丁氧基羰基)苯胺基荧烷、3-二乙基氨基-7-二苄基氨基荧烷、3-二丁基氨基-7-二苄基氨基荧烷、3-二乙基-氨基-6-甲基-7-(二苄基氨基)荧烷、3-二乙基氨基-6-甲基荧烷、3-二乙基氨基-6-氯-7-甲基荧烷、3-二乙基氨基-6-甲基-7-氯荧烷、3-二乙基氨基-7-叔丁基荧烷、3-二乙基氨基-7-羧基乙基荧烷、3-二乙基氨基-7-甲基荧烷、3-二乙基氨基-6,8-二甲基荧烷、3-二乙基氨基-7-氯荧烷、3-二丁基氨基-6-甲基-荧烷、3-环己基氨基-6-氯荧烷、3-二乙基氨基-苯并[a]荧烷、3-二乙基氨基-苯并[c]荧烷、3-二甲基氨基-6-甲基-7-苯胺基荧烷、3-二乙基氨基-6-甲基-7-苯胺基荧烷、3-二乙基氨基-6-甲基-7-(2,4-二甲基苯胺基)荧烷、3-二乙基氨基-6-甲基-7-(3-氟甲基苯胺基)荧烷、3-二乙基氨基-6-甲基-7-(2-氯苯胺基)-荧烷、3-二乙基氨基-6-甲基-7-(对氯苯胺基)荧烷、3-二乙基氨基-6-甲基-7-(2-氟苯胺基)荧烷、3-二乙基氨基-6-甲基-7-(对辛基苯胺基)荧烷、3-二乙基氨基-7-(对辛基苯胺基)荧烷、3-二乙基氨基-6-甲基-7-(对甲基苯胺基)荧烷、3-二乙基氨基-6-乙氧基乙基-7-苯胺基荧烷、3-二乙基氨基-6-甲基-7-(3-甲基苯胺基)荧烷、3-二乙基-氨基-7-(3-氟甲基苯胺基)荧烷、3-二乙基氨基-7-(2-氯苯胺基)荧烷、3-二乙基-氨基-7-(2-氟苯胺基)荧烷、3-二乙基氨基-6-氯-7-苯胺基荧烷、3-二丁基氨基-6-甲基-7-苯胺基荧烷、3-二丁基氨基-6-甲基-7-(2,4-二甲基苯胺基)荧烷、3-二丁基-氨基-6-甲基-7-(2-氯苯胺基)荧烷、3-二丁基氨基-6-甲基-7-(4-氯苯胺基)-荧烷、3-二丁基氨基-6-甲基-7-(2-氟苯胺基)荧烷、3-二丁基氨基-6-甲基-7-(3-三氟甲基苯胺基)荧烷、3-二丁基氨基-6-乙氧基乙基-7-苯胺基荧烷、3-二丁基氨基-6-氯-苯胺基荧烷、3-二丁基氨基-6-甲基-7-(4-甲基苯胺基)荧烷、3-二丁基氨基-7-(2-氯苯胺基)荧烷、3-二丁基氨基-7-(2-氟苯胺基)荧烷、3-二戊基氨基-6-甲基-7-苯胺基荧烷、3-二戊基氨基-6-甲基-7-(4-2-氯苯胺基)荧烷、3-二戊基-氨基-7-(3-三氟甲基苯胺基)荧烷、3-二戊基氨基-6-氯-7-苯胺基荧烷、3-二戊基氨基-7-(4-氯苯胺基)荧烷、3-吡咯烷基-6-甲基-7-苯胺基荧烷、3-哌啶基-6-甲基-7-苯胺基荧烷、3-(N-甲基-N-丙基氨基)-6-甲基-7-苯胺基荧烷、3-(N-甲基-N-环己基氨基)-6-甲基-7-苯胺基荧烷、3-N-乙基-N-环己基氨基)-6-甲基-7-苯胺基荧烷、3-(N-乙基-N-乙基氨基)-7-苯胺基荧烷、3-(N-乙基-对甲苯胺基)-氨基-6-甲基-7-苯胺基荧烷、3-(N-乙基-对甲苯胺基)氨基-7-甲基荧烷、3-(N-乙基-N-异戊基氨基)-6-甲基-7-苯胺基荧烷、3-(N-乙基-N-异戊基氨基)-7-(2-氯苯胺基)-荧烷、3-(N-乙基-N-异戊基氨基)-6-氯-7-苯胺基荧烷、3-(N-乙基-N-四氢化糠基-氨基)-6-甲基-7-苯胺基荧烷、3-(N-乙基-N-异丁基氨基)-6-甲基-7-苯胺基荧烷、3-(N-丁基-N-异戊基氨基)-6-甲基-7-苯胺基荧烷、3-(N-异丙基-N-3-戊基氨基)-6-甲基-7-苯胺基荧烷、3-(N-乙基-N-乙氧基丙基氨基)-6-甲基-7-苯胺基荧烷、2-甲基-6-对-(对二甲基氨基苯基)氨基苯胺基荧烷、2-甲氧基-6-对-(对二甲基-氨基苯基)氨基苯胺基荧烷、2-氯-3-甲基-6-对-(对苯基氨基苯基)氨基-苯胺基荧烷、2-二乙基氨基-6-对-(对二甲基氨基苯基)氨基苯胺基荧烷、2-苯基-6-甲基-6-对-(对苯基氨基苯基)氨基苯胺基荧烷、2-苄基-6-对-(对苯基氨基-苯基)氨基苯胺基荧烷、3-甲基-6-对-(对-二甲基氨基苯基)氨基苯胺基荧烷、3-二乙基氨基-6-对-(对二乙基氨基苯基)氨基苯胺基荧烷、3-二乙基氨基-6-对-(对二丁基-氨基苯基)氨基苯胺基荧烷和2,4-二甲基-6-[(4-二甲基氨基)苯胺基]荧烷。
苯并噁嗪的实例为2-苯基-4-(4-二乙基氨基苯基)-4-(4-甲氧基苯基)-6-甲基-7-二甲基氨基-3,1-苯并噁嗪和2-苯基-4-(4-二乙基氨基苯基)-4-(4-甲氧基苯基)-8-甲基-7-二甲基氨基-3,1-苯并噁嗪。
喹唑啉的实例为4,4′-[1-甲基亚乙基)双(4,1-亚苯氧基-4,2-喹唑啉二基)]双[N,N-二乙基苯胺]。三芳基甲烷的实例为双(N-甲基二苯基胺)-4-基-(N-丁基咔唑)-3-基-甲烷。
螺吡喃的实例为1′,3′,3′-三甲基螺[2H-1-苯并吡喃-2,2′-二氢吲哚]、1,3,3-三甲基螺[二氢吲哚-2,3′-[3H]萘并[2,1-b][1,4]噁嗪]和1′,3′,3′-三甲基螺[2H-1-苯并噻喃-2,2′-二氢吲哚]。螺异苯并呋喃的实例为6′-(二戊基氨基)-3′-甲基-2′-(苯基氨基)-螺[异苯并呋喃-1(3H),9′-[9H]呫吨]-3-酮和螺[异苯并呋喃-1(3H),9′-[9H]呫吨]-3-酮-6′-(二乙基氨基)-3′-甲基-2′-(3-甲苯基-氨基)。
醌的实例为苏木精。噁嗪的实例为3,7-双(二甲基氨基)-10-苯甲酰基吩噁嗪。噻嗪的实例为3,7-双(二甲基氨基)-10-苯甲酰基吩噁嗪。
在EP 0 366 461 A1中第13页第8至51行提到有机隐色染料的其它实例。
有机显色剂的实例为酚类化合物,例如4,4′-异亚丙基二酚(双酚A)、双(4-羟基苯基)醋酸丁酯、2,2-双(4-羟基苯基)-4-甲基戊烷、2,2-双(4-羟基苯基)丙烷、4,4′-二羟基二苯砜、2,4′-二羟基二苯砜、双(3-烯丙基-4-羟基苯基)砜、4-羟基-4′-甲基二苯砜、1,1-双(4-羟基苯基)-1-苯基乙烷、1,4-双[α-甲基-α-(4′-羟基苯基)乙基]苯、4-[(4-(1-甲基乙氧基)苯基)-磺酰基]苯酚和N-(2-羟基苯基)-2-[(4-羟基苯基)硫代]乙酰胺;具有脲基团或脲基基团的化合物,例如N-(对甲苯磺酰基)-N′-(3-对甲苯磺酰氧基)苯基)脲、N-对甲苯基磺酰基-N′-苯基脲、4,4′-N-对甲苯基磺酰基-N′-对丁氧基苯基脲和双[(4-甲基-3-苯氧基羰基氨基苯基)脲基]二苯基甲烷以及芳族羧酸的锌盐,例如4-[2-(对甲氧基苯氧基)-乙基氧基]水杨酸锌、4-[3-(对甲苯基磺酰基)丙氧基]水杨酸锌和5-[对-(2-对甲氧基苯氧基乙氧基)枯基]水杨酸锌。
EP 0 366 461 A1中第13页第53行至第16页第30行提到了有机显色剂的其它实例。
所述颜料通常吸收和/或反射激光辐照的特定波长。
颜料可以是有机的或无机的。
有机颜料的实例为聚苯乙烯树脂、脲醛树脂和空心塑料颜料。
空心塑料颜料的典型实例为具有由丙烯酸基树脂、苯乙烯基树脂或偏二氯乙烯基树脂制成的外壳的颗粒。典型地,空心塑料颜料基于体积的空洞百分比为约50至99%。空心塑料颜料在热处理时可膨胀或不可膨胀。不可膨胀空心塑料颜料的平均外径可以在0.5至10μm的范围,优选1至5μm。可膨胀空心塑料颜料的平均外径可以在0.1至5μm的范围。当包含可膨胀空心塑料颜料的底涂层经历热处理时,该颗粒可以膨胀至在1至30μm范围内的平均外径。热处理时可膨胀的空心塑料颜料的实例为具有偏二氯乙烯基树脂外壳和作为填充物的丁烷气的颗粒。
无机颜料的实例为高岭土、煅烧高岭土、云母、氧化铝、氢氧化铝、硅酸铝、滑石、无定形二氧化硅、胶体二氧化硅、二氧化钛、碳酸钙(研磨和沉淀的)、硅酸钙和硫酸钡。
优选地,该颜料为无机颜料。
更优选地,该颜料选自高岭土、煅烧高岭土、云母、氧化铝、氢氧化铝、硅酸铝、滑石、无定形二氧化硅和胶体二氧化硅。
最优选的颜料选自煅烧高岭土、氢氧化铝、滑石和无定形二氧化硅。
优选地,底涂层还可包含聚合物粘结剂。
聚合物粘结剂的实例为丙烯酸类聚合物、苯乙烯类聚合物及其氢化产物、乙烯基类聚合物及其衍生物、聚烯烃及其氢化或环氧化产物、醛聚合物、环氧化物聚合物、聚酰胺、聚酯、聚氨酯、砜基聚合物和天然聚合物及其衍生物。该聚合物粘结剂也可以是聚合物粘结剂的混合物。
丙烯酸类聚合物可以是从至少一种丙烯酸类单体或从至少一种丙烯酸类单体和至少一种其它的烯不饱和聚合物如苯乙烯类单体、乙烯类单体、烯烃单体或马来酸类单体形成的聚合物。
丙烯酸类单体的实例为(甲基)丙烯酸或其盐、(甲基)丙烯酰胺、(甲基)丙烯腈、(甲基)丙烯酸C1-6烷基酯如(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯或(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、取代的(甲基)丙烯酸C1-6烷基酯如甲基丙烯酸缩水甘油酯和甲基丙烯酸乙酰乙酰氧基乙酯、(甲基)丙烯酸二(C1-4烷基氨基)C1-烷基酯如丙烯酸二甲基氨基乙基酯或丙烯酸二乙基氨基乙基酯、或者由C1-6烷基胺、取代的C1-6烷基胺如2-氨基-2-甲基-1-丙磺酸、铵盐、或二(C1-4烷基氨基)C1-6烷基胺和(甲基)丙烯酸形成的酰胺及其C1-4烷基卤加合物。
苯乙烯类单体的实例为苯乙烯、4-甲基苯乙烯和4-乙烯基联苯。乙烯类单体的实例为乙烯醇、氯乙烯、偏二氯乙烯、乙烯基异丁基醚和乙酸乙烯酯。烯烃单体的实例为乙烯、丙烯、丁二烯和异戊二烯及其氯化或氟化衍生物,如四氟乙烯。马来酸类单体的实例为马来酸、马来酸酐和马来酰亚胺。
丙烯酸类聚合物的实例为聚(甲基丙烯酸甲酯)和聚(甲基丙烯酸丁酯),以及例如Ciba以商品名LE15、LS20和LS24销售的羧化丙烯酸共聚物、Ciba以商品名LS26和C44销售的苯乙烯丙烯酸共聚物、以及Ciba以商品名E11销售的聚丙烯酸类聚合物。
苯乙烯类聚合物可以是从至少一种苯乙烯类单体和至少一种乙烯类单体、烯烃单体和/或马来酸类单体形成。苯乙烯类聚合物的实例为苯乙烯丁二烯苯乙烯嵌段聚合物、苯乙烯乙烯丁二烯嵌段聚合物、苯乙烯乙烯丙烯苯乙烯嵌段聚合物和苯乙烯-马来酸酐共聚物。
乙烯基类聚合物可以是从至少一种乙烯类单体或从至少一种乙烯类单体和至少一种烯烃单体或马来酸类单体形成的聚合物。乙烯基类聚合物的实例为聚氯乙烯、聚乙烯醇、聚醋酸乙烯酯、部分水解的聚醋酸乙烯酯以及甲基乙烯醚-马来酸酐共聚物。其衍生物的实例为羧基改性的聚乙烯醇、乙酰乙酰基改性的聚乙烯醇、双丙酮改性的聚乙烯醇和硅改性的聚乙烯醇。
聚烯烃可以是从至少一种烯烃单体或从至少一种烯烃单体或马来酸类单体形成的聚合物。聚烯烃的实例为聚乙烯、聚丙烯、聚丁二烯和异丙烯-马来酸酐共聚物。
醛聚合物可以是从至少一种醛单体或聚合物和至少一种醇单体或聚合物、胺单体或聚合物和/或脲单体或聚合物形成的聚合物。醛单体的实例为甲醛、糠醛和丁缩醛。醇单体的实例为苯酚、甲酚、间苯二酚和二甲苯酚。聚醇的实例为聚乙烯醇。胺单体的实例为苯胺和三聚氰胺。脲单体的实例为脲、硫脲和双氰胺。醛聚合物的实例为从丁缩醛和聚乙烯醇形成的聚乙烯醇缩丁醛。
环氧化物聚合物可以是从至少一种环氧化物单体和至少一种醇单体和/或胺单体形成的聚合物。环氧化物单体的实例为表氯醇和缩水甘油。醇单体的实例为苯酚、甲酚、间苯二酚、二甲苯酚、双酚A和二醇。环氧化物聚合物的实例为苯氧基树脂,其从表氯醇和双酚A形成。
聚酰胺可以是从至少一种具有酰胺基团或氨基以及羧基的单体或从至少一种具有两个氨基基团的单体和至少一种具有两个羧基基团的单体形成的聚合物。具有酰胺基团的单体的实例为己内酰胺。二胺的实例为1,6-二氨基己烷。二羧酸的实例为己二酸、对苯二酸、间苯二酸和1,4-萘二甲酸。聚酰胺的实例为聚己二酰己二胺和聚己内酰胺。
聚酯聚合物可以是从至少一种具有羟基以及羧基的单体或从至少一种具有两个羟基基团和至少一种具有两个羧基基团或内酯基团的单体形成的聚合物。具有羟基以及羧基基团的单体的实例为己二酸。二醇的实例为乙二醇。具有内酯基团的单体的实例为己内酯。二羧酸的实例为对苯二酸、间苯二酸和1,4-萘二甲酸。聚酯的实例为聚对苯二甲酸乙二酯。所谓的醇酸树脂也认为是属于聚酯聚合物。
聚氨酯可以是从至少一种二异氰酸单体和至少一种多元醇单体和/或多胺单体形成的聚合物。二异氰酸单体的实例为己二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯。
砜基聚合物的实例可以是聚芳砜、聚醚砜、聚苯砜和聚砜。聚砜为从4,4-二氯二苯基砜和双酚A形成的聚合物。
天然聚合物的实例为淀粉、纤维素、明胶、酪素(caesin)和天然橡胶。衍生物的实例为氧化淀粉、淀粉-醋酸乙烯酯接枝共聚物、羟乙基纤维素、羟丙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素。
这些聚合物粘结剂为现有技术中已知并且可通过已知方法如通过从适合的单体开始聚合而生产。
优选地,聚合物粘结剂选自由丙烯酸类聚合物、苯乙烯类聚合物、乙烯基类聚合物及其衍生物、聚烯烃、聚氨酯和天然聚合物及其衍生物组成的组。
更优选地,聚合物粘结剂选自由丙烯酸类聚合物、苯乙烯丁二烯共聚物、苯乙烯马来酸酐共聚物、聚乙烯醇、聚醋酸乙烯酯、部分水解的聚醋酸乙烯酯、甲基乙烯醚-马来酸酐共聚物、羧基改性的聚乙烯醇、乙酰乙酰基-改性的聚乙烯醇、双丙酮改性的聚乙烯醇和硅改性的聚乙烯醇、异丙烯-马来酸酐共聚物、聚氨酯、纤维素、明胶、酪素、氧化淀粉、淀粉-醋酸乙烯酯接枝共聚物、羟乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素组成的组。
最优选地,该聚合物粘结剂为苯乙烯丁二烯共聚物和/或聚乙烯醇。
底涂层还可包含其它的组分。其它组分的实例为稳定剂、表面活性剂、不溶粘料、润滑剂、UV吸收剂、IR吸收剂、pH调节剂、抗氧化剂、防烟剂、分散剂、流变改性剂、润湿剂、荧光增白剂和生物杀灭剂。优选的其它组分为UV吸收剂、IR吸收剂、pH调节剂、抗氧化剂、防烟剂、分散剂、流变改性剂、润湿剂和生物杀灭剂。
稳定剂的实例为2,2′-亚甲基-双(4-甲基-6-叔丁基苯酚)、2,2′-亚甲基-双(4-乙基-6-叔丁基苯酚)、4,4′-亚丁基-双(3-甲基-6-叔丁基苯酚)、4,4′-硫代-双(2-叔丁基-5-甲基苯酚)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-环己基苯基)丁烷、双(3-叔丁基-4-羟基-6-甲基苯基)砜、双(3,5-二溴-4-羟基苯基)砜、4,4′-亚硫酰基双(2-叔丁基-5-甲基苯酚)、2,2′-亚甲基双(4,6-二叔丁基苯基)磷酸酯及其碱金属盐、铵盐和多价金属盐、4-苄氧基-4′-(2-甲基缩水甘油基氧基)二苯基砜、4,4′-二缩水甘油基氧基二苯基砜、1,4-二缩水甘油基氧基苯、4-[α-(羟甲基)苄氧基]-4-羟基二苯基砜、对硝基苯甲酸的金属盐、苯二甲酸单苄酯的金属盐、肉桂酸的金属盐、2,2′,3,3′-四氢-3,3,3′,3′-四甲基-1,1′-螺双-(1H-茚)-6,6′-二醇及其混合物。
表面活性剂的实例为二辛基磺化琥珀酸钠、十二烷基苯磺酸钠、月桂基硫酸钠和脂肪酸金属盐。
不溶粘料的实例为乙二醛、脲醛树脂、三聚氰胺-甲醛树脂、聚酰胺树脂、聚酰氨基-表氯醇树脂、己二酸二酰肼、硼酸、硼砂、碳酸锆铵、碳酸锆钾和乳酸锆铵。
润滑剂的实例为硬脂酰胺、亚甲基双硬脂酰胺、聚乙烯蜡、巴西棕榈蜡、石蜡、硬脂酸锌、硬脂酸钙及其混合物。优选的润滑剂为硬脂酸锌。
UV吸收剂的实例为2-羟基-4-甲氧基二苯甲酮。
无机IR吸收剂的实例为金属的氧化物、氢氧化物、硫化物、硫酸盐和磷酸盐,金属例如为铜、铋、铁、镍、锡、锌、锰、锆和锑,包括氧化锑(V)掺杂的云母和氧化锡(IV)掺杂的云母。
pH调节剂的可以是有机或无机酸,例如醋酸或盐酸,或者碱,如氢氧化钠。
防烟剂的实例为八钼酸铵。
生物杀灭剂的实例为其包括氯甲基异噻唑啉酮和甲基异噻唑啉酮的混合物;410,其包括2-二溴-2,4-二氰基丁烷和1,2-苯并异噻唑啉-3-酮的组合;721M,其包括1,2-二溴-2,4-二氰基丁烷和2-溴-2-硝基-1,3-丙二醇的组合;以及TK 100,其包括2-(4-噻唑基)-苯并咪唑。
基于底涂层干重,底涂层可包含1至99%、优选40至98%、更优选60至97%、最优选80至96%干重的颜料。
基于底涂层干重,底涂层可包含1至80%、优选1至60%、更优选1至30%、最优选10至20%干重的粘结剂。
基于底涂层干重,底涂层可包含0.05至20%、优选0.05至10%、更优选0.1至5%干重的其它组分。
记录层可以是任何这样的记录层,其包括在热处理时发生颜色变化的体系,前提是该体系不包含有机隐色染料和有机显色剂。
在热处理时发生颜色变化的体系的实例为选自下组的体系:
A)含氧的铬、钼和钨化合物
B)酸与胺的盐或酸与胺的盐的混合物
C)酸衍生物
D)含有自由羰基的化合物和亲核体,或者含有自由羰基的化合物,该化合物被一个或多个亲核基团所取代
E)二氧化钛和
F)具有官能团的化合物和金属化合物或酸。
关于体系A:
含氧的铬、钼和钨化合物的实例为铬、钼和钨氧化物,单、二和多铬酸、钼酸和钨酸的碱金属盐、碱土金属盐、铵盐以及一-、二-、三-和四-C1-8烷基铵盐,杂多铬酸、钼酸和钨酸的碱金属盐、碱土金属盐、铵盐以及一-、二-、三-和四-C1-8烷基铵盐,过氧铬酸、钼酸和钨酸的碱金属盐、碱土金属盐、铵盐以及一-、二-、三-和四-C1-8烷基铵盐,以及含羟基的铬酸盐、钼酸盐和钨酸盐。优选地,含氧过渡金属化合物选自由单、二和多钼酸和钨酸的碱金属盐、铵盐以及一-、二-、三-和四-C1-8烷基铵盐组成的组。单、二和多钼酸和钨酸的碱金属盐和铵盐的实例为钼酸铵、钼酸钠、钼酸钾、二钼酸铵、七钼酸铵、八钼酸铵、十钼酸铵、钨酸铵、钨酸钠和钨酸钾。更优选地,其为八钼酸铵。
体系A还可包含选自有机酸、多羟基化合物和碱组成的组的添加剂,如PCT/EP/2006064299中所述。
有机酸的实例为甲酸、乙酸、丁酸、月桂酸、乳酸、2,6-己二烯酸、十一碳烯酸、抗坏血酸、草酸、琥珀酸、苹果酸、酒石酸、柠檬酸、富马酸、粘康酸、苯乙酸、对甲苯乙酸、4-联苯乙酸、4-甲氧基苯乙酸、扁桃酸、α-乙酰胺基肉桂酸、4-甲基肉桂酸、阿魏酸、反式肉桂酸和反式苯乙烯基乙酸。
多羟基化合物可选自碳水化合物如单糖、二糖和多糖,及其羰基被还原为羟基基团(因而称为糖醇)的衍生物组成的组。
单糖的实例为葡萄糖、甘露糖、半乳糖、阿拉伯糖、果糖、核糖、赤藓糖和木糖。二糖的实例为麦芽糖、纤维二糖、乳糖和蔗糖。多糖的实例为纤维素、淀粉、阿拉伯树胶、糊精和环糊精。糖醇的实例为内消旋赤藓糖醇、山梨糖醇、甘露醇和季戊四醇。
碱的实例为氢氧化钠、氢氧化钾、氢氧化镁、氢氧化钙、碳酸钠、碳酸钾、碳酸镁、碳酸钙、氨、三乙胺、二和三丁胺、二和三戊胺、二和三己胺、一、二和三乙醇胺、N,N-二甲基乙醇胺、乙二胺、1,2-和1,3-二氨基丙烷、苯胺、吗啉、哌啶、哌嗪和吡咯烷。
体系A还可包含成色剂。
关于体系B:
酸可以是无机的或有机的。无机酸的实例为硫酸、氟硫酸、氯硫酸、亚硝基硫酸、硫代硫酸、氨基磺酸、亚硫酸、甲脒亚磺酸、硝酸、磷酸、硫代磷酸、氟磷酸、六氟磷酸、多磷酸、亚磷酸、盐酸、氯酸、高氯酸、氢溴酸、氢碘酸和氢氟酸。有机酸的实例为基于硫的有机酸,如4-苯乙烯磺酸、对甲苯磺酸、苯磺酸、二甲苯磺酸、苯酚磺酸、甲磺酸、三氟甲磺酸、聚(4-苯乙烯磺酸)和包含4-苯乙烯磺酸单元的共聚物如聚(4-苯乙烯磺酸-co-马来酸),基于磷的有机酸,如苯膦酸、甲膦酸、苯次膦酸、二氢磷酸2-氨基乙酯、植酸、L-抗坏血酸-2-磷酸、二氢磷酸甘油酯、二亚乙基三胺五(亚甲基膦酸)(DTPMP)、己二胺四(亚甲基膦酸)(HDTMP)、次氮基三(亚甲基膦酸)和1-羟基亚乙基二膦酸,以及羧酸,例如酒石酸、二氯乙酸、三氯乙酸、草酸和马来酸。
优选地,该酸选自无机酸、基于硫的有机酸、基于磷的有机酸、羧酸及其混合物组成的组。更优选地,该酸选自硫酸、硫代硫酸、亚硫酸、磷酸、多磷酸、亚磷酸、盐酸、基于硫的有机酸、基于磷的有机酸、羧酸及其混合物组成的组。最优选地,该酸为硫酸或磷酸组成的组。
胺可具有式NR1R2R3,其中R1、R2和R3可相同或不同,并且为氢、C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基、芳烯基或芳基,或者R1为氢、C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基、芳烯基或芳基,以及R2和R3与式NR1R2R3胺的氮合起来形成5至7元环,其中C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基和芳烯基可以是未取代的,或者可被NR4R5R6、亚氨基、氰基、氰基氨基、羟基和/或C1-6烷氧基取代,并且芳基可以是未取代的,或被NR4R5R6、氰基、氰基氨基、羟基、C1-6烷基和/或C1-4烷氧基取代,其中R4、R5和R6可相同或不同,且为氢、C1-6烷基、C4-8环烷基或芳基。
C1-30烷基的实例为甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、肉豆蔻基、棕榈基、硬脂基和arachinyl。C2-30链烯基的实例为乙烯基、烯丙基、亚麻基、二十二碳六烯基(docosahexaenoyl)、二十碳五烯基、亚油基、花生四烯基和油基。C4-8环烷基的实例为环戊基和环己基。C5-8环烯基的实例为环己烯基。芳烷基的实例为苄基和2-苯乙基。芳基的实例为苯基、1,3,5-三嗪基或萘基。C1-6烷基的实例为甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基和己基。C1-4烷氧基的实例为甲氧基、乙氧基、丙氧基、异丙氧基和丁氧基。
优选的C1-30烷基为C1-10烷基,更优选的C1-30烷基为C1-6烷基。优选的C2-30链烯基为C2-10链烯基,更优选C2-6链烯基。上文给出了C1-6烷基的实例。C1-10烷基的实例为甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基和癸基。C2-10链烯基和C2-6链烯基的实例为乙烯基和烯丙基。
式NR1R2R3胺的实例为氨、三(羟甲基)氨基甲烷、胍、甲胺、乙胺、丙胺、丁胺、二乙胺、乙二胺、1,2-二氨基丙烷、乙醇胺、三乙醇胺、环己胺、苯胺、三聚氰胺、羟甲基三聚氰胺、吡咯、吗啉、吡咯烷和哌啶。
优选地,该胺具有式NR1R2R3,其中R1为氢且R2和R3如上文所定义。
更优选地,该胺具有式NR1R2R3,其中R1和R2为氢且R3如上文所定义。
最优选地,该胺为氨。
优选地,体系B包含硫酸铵、磷酸铵、磷酸氢二铵或磷酸二氢铵或硫酸铵与磷酸铵、磷酸氢二铵或磷酸二氢铵的混合物。
优选地,体系B还可包含成碳化合物。成碳化合物为在能量处理时形成碳的化合物。通常,成碳化合物具有高的碳和氧含量。
成碳化合物的实例为碳水化合物,例如单糖、二糖和多糖,以及其羰基基团被还原为羟基基团(因而称为糖醇)的衍生物。
单糖的实例为葡萄糖、甘露糖、半乳糖、阿拉伯糖、果糖、核糖、赤藓糖和木糖。二糖的实例为麦芽糖、纤维二糖、乳糖和蔗糖。多糖的实例为纤维素、淀粉、阿拉伯树胶、糊精和环糊精。糖醇的实例为内消旋赤藓糖醇、山梨糖醇、甘露醇和季戊四醇。
优选的成碳化合物为单糖和二糖。更优选的成碳化合物为蔗糖和半乳糖。最优选的成碳化合物为蔗糖。
体系B还可包含成色剂,尽管这不是优选的。
体系B的实例描述在PCT/EP/2006066064中。
关于体系C:
酸衍生物可以是酯、酰胺、酸酐和如上所述的酸的硫代酯,其中所有酸性OH基团都被OR7、NR8R9、OC(O)R10或SR11替代,其中R7、R8、R9、R10和R11可相同或不同,且可以是氢、C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基、芳烯基或芳基,其中C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基和芳烯基可以是未取代的,或被NR12R13R14、卤素、氰基、羟基和/或C1-6烷氧基取代,并且芳基可以是未取代的,或被NR12R13R14、卤素、氰基、羟基、C1-6烷基和/或C1-6烷氧基取代,其中R12、R13和R14可相同或不同,且为氢、C1-6烷基、C4-8环烷基或芳基,前提是R7不为氢。
卤素的实例为氯和溴。
酸衍生物的实例为对甲苯磺酸乙酯、对甲苯磺酸环己酯、氢膦酸二甲酯、甲基膦酸二甲酯和磷酸三甲酯。优选的酸衍生物为如上所述的酸的酯,其中所有酸性OH基团被OR7所取代。
体系C还可包含成色剂,尽管这不是优选的。
关于体系D:
含有自由羰基基团的化合物可以是任何含有能够与亲核体如胺反应的羰基基团的化合物。含有自由羰基基团的化合物的实例为醛、酮和还原性碳水化合物。
醛的实例为甲醛、乙醛、丙醛、丁醛、戊醛、己醛、苯甲醛、水杨醛和苯乙醛。
酮的实例为丙酮、丁酮、2-戊酮、3-戊酮、3-甲基-2-丁酮、1-苯基-2-丙酮、苯乙酮、二苯甲酮和抗坏血酸(维生素C)。
醛和酮也可分别以半缩醛和半酮缩醇的形式存在。半缩醛和半酮缩醇可由相应的醛和缩酮通过与1当量的醇反应而形成,所述醇例如为甲醇、乙醇、异丙醇、丙醇、丁醇、戊醇、苯酚、苯甲醇和环己醇。
还原性碳水化合物能够还原Tollens试剂。还原性碳水化合物的实例为醛糖、酮糖、还原性二糖和还原性多糖。
醛糖的实例为甘油醛、赤藓糖、苏阿糖、阿拉伯糖、核糖、木糖、来苏糖、葡萄糖、甘露糖、阿洛糖、阿卓糖、古洛糖、艾杜糖、半乳糖和塔罗糖。酮糖的实例为二羟基丙酮、赤藓酮糖、核酮糖、木酮糖、果糖、山梨糖和塔格糖。还原性二糖的实例为麦芽糖、纤维二糖和乳糖。
优选的含有自由羰基的化合物为抗坏血酸和葡萄糖。
所述亲核体可以是能够与该含有自由羰基基团的化合物的自由羰基基团反应的任何亲核体。例如,该亲核体可以是胺。
胺的实例为氨、三(羟甲基)氨基甲烷、胍、甲胺、乙胺、丙胺、丁胺、二乙胺、乙二胺、1,2-二氨基丙烷、乙醇胺、三乙醇胺、环己胺、苯胺、三聚氰胺、吡咯、吗啉、吡咯烷、哌啶和聚醚胺,例如Huntsmann以商品名销售的那些,如D-230,其为带有两末端氨基且分子量为230g/mol的聚丙二醇。
该胺还可以是氨基酸或氨基糖。
氨基酸的实例为4-氨基马尿酸和4-氨基苯甲酸以及“标准”氨基酸,它们为甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸、苯丙氨酸、酪氨酸、色氨酸、半胱氨酸、甲硫氨酸、丝氨酸、苏氨酸、赖氨酸、精氨酸、组氨酸、天冬氨酸、谷氨酸、天冬酰胺和谷氨酰胺。
氨基糖为含有氨基基团的碳水化合物,该氨基基团替换了不为糖苷羟基基团的羟基基团。氨基糖的实例为葡萄糖胺和半乳糖胺。
优选地,该胺为氨基酸。
可使用任何被一个或多个亲核基团所取代的含有自由羰基基团的化合物,例如该被一个或多个亲核基团所取代的含有自由羰基基团的化合物可以是以上列出的含有自由羰基基团的任何化合物,除了其被一个或多个亲核基团所取代。优选的亲核基团为氨基基团。被一个或多个氨基基团所取代的含有自由羰基基团的化合物的实例为氨基糖。氨基糖的实例在上文中列出。
体系D还可包含成碳化合物。
关于体系E:
二氧化钛可以是金红石、板钛矿或锐钛矿形式。优选地,二氧化钛为锐钛矿形式(也称为八面石),一种双棱椎体习性的四角形矿石。锐钛矿形式的二氧化钛可具有0.001至1000μm(1nm至1mm)范围内的粒度。优选地,粒度在0.01至10μm的范围内,更优选地,在0.01至1μm的范围内,最优选地,在0.01至0.5μm的范围内。
关于体系F:
例如在WO 2006/068205中,描述了包含具有官能团的化合物和金属化合物或酸的体系。具有官能团的化合物可以是多羟基化合物如羟丙基纤维素、甲基羟基纤维素或聚乙烯醇,或者带有卤素或酯官能团的化合物如聚氯乙烯或聚醋酸乙烯酯。金属化合物的实例为氯化镁、氢氧化镁、氧化钙和氧化锌。酸的实例为对甲苯磺酸。
在以上列出的在热处理时发生颜色变化的体系中,A、B、C、D和E是优选的。体系A、B、C和D是特别优选的。最优选的体系是体系B,酸和胺的盐或者酸和胺的盐的混合物。
记录层还可包含粘结剂。上文给出了粘结剂的实例。最优选地,用于记录层的聚合物粘结剂为聚乙烯醇或丙烯酸类聚合物,例如Ciba以商品名销售的那些,例如LE15、LS26、E11或C44。LS 26为核壳聚合物,由70重量份的起核心聚合物作用的55/45(w/w)苯乙烯/丙烯酸2-乙基己酯共聚物和30重量份的起外壳聚合物作用的苯乙烯/丙烯酸共聚物组成。对于记录层特别优选的是聚合物粘结剂。
优选地,记录层还可包含其它组分。其它组分的实例为颜料、稳定剂、润滑剂、UV吸收剂、IR吸收剂、pH调节剂、抗氧化剂、防烟剂、分散剂、流变改性剂、润湿剂、荧光增白剂和生物杀灭剂。上文给出了颜料、稳定剂、表面活性剂、不溶粘料、润滑剂、UV吸收剂、IR吸收剂、pH调节剂、抗氧化剂、防烟剂、分散剂、流变改性剂、润湿剂、荧光增白剂和生物杀灭剂的实例。
基于记录层的干重,记录层可包含10至90%、优选20至80%、更优选30至70%、最优选40至60%干重的在热处理时发生颜色变化的体系。
基于记录层的干重,记录层可包含10至90%、优选20至80%、更优选30至70%、最优选40至60%干重的粘结剂。
基于记录层的干重,记录层可包含0.05至20%、优选0.05至10%、更优选0.1至5%干重的其它组分。
底涂层和记录层的厚度通常分别选择为在0.1至1000μm的范围内。优选地,在1至500μm的范围内。更优选地,在1至200μm的范围内。最优选地,在1至20μm的范围内。
本发明的激光敏感记录材料还可包括层合层或罩光清漆(overprintvarnish)。如果选择层合层或罩光清漆的材料使得其不在成像激光的波长处吸收,则激光敏感记录层可穿过该层合层对成像而不损坏或标记层合材料。另外,理想的是选择层合材料或罩光清漆,使得其不会在激光处理前导致记录层着色。
基底可以是薄片或者任何其它三维体,其可以是透明的或者不透明的,并且其可具有平或不平的表面。具有不平表面的基底的实例为装满的纸袋,例如水泥纸袋。基底可由纸、卡纸板、金属、木材、织物、玻璃、陶瓷和/或聚合物制成。基底还可以是药片或食品。聚合物的实例为聚对苯二甲酸乙二酯、低密度聚乙烯、聚丙烯、双向拉伸聚丙烯、聚醚砜、聚氯乙烯聚酯和聚苯乙烯。优选地,基底由纸、卡纸板或聚合物制成。
本发明还包括制备本发明的激光敏感记录材料的方法,该方法包括以形成底涂层的组合物涂布基底,然后以形成记录层的组合物涂布的步骤。
形成底涂层的组合物通常包含颜料和任选的粘结剂和/或其它组分。优选地,其还包括溶剂。
形成记录层的组合物通常包含在热处理时发生颜色变化的体系和任选的粘结剂和/或其它组分。优选地,其还包括溶剂。
溶剂可以是水、有机溶剂或水和有机溶剂的混合物。
有机溶剂的实例为C1-4烷醇、C2-4多元醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜,其中C1-4烷醇和C2-4多元醇可以被C1-4烷氧基取代,以及它们的混合物。C1-4烷醇的实例为甲醇、乙醇、丙醇、异丙醇或丁醇、异丁醇、仲丁醇和叔丁醇。其C1-4烷氧基衍生物的实例为2-乙氧基乙醇和1-甲氧基-2-丙醇。C2-4多元醇的实例为乙二醇和甘油。C3-6酮的实例为丙酮和甲乙酮。C4-6醚的实例为二甲氧基乙烷、二异丙基乙基和四氢呋喃。C2-3腈的实例为乙腈。
更优选地,溶剂为水或水和有机溶剂的混合物。
优选地,有机溶剂选自C1-4烷醇、C2-4多元醇、C3-6酮、二甲基甲酰胺和二甲基乙酰胺组成的组,其中C1-4烷醇和C2-4多元醇可以被C1-4烷氧基取代。
优选地,水和有机溶剂的混合物中水/有机溶剂的比例至少为0.5/1,更优选地,至少1/1。
最优选地,溶剂为水。
可采用标准涂布法分别以形成底涂层和记录层的组合物涂布基底,例如刮涂机施涂、旋转施涂、喷涂、幕涂、浸涂、空气施涂、刮涂、刮板施涂或辊涂。也可通过各种印刷方法将组合物施加至基底,例如丝网印刷、凹版印刷、胶版印刷和弹性版印刷。如果基底为纸,则所述组合物也可在施胶机中施涂或者在造纸机的湿部施涂。
形成底涂层和记录层的组合物均可例如在环境温度或升高温度下干燥。理想的是,选择升高的温度以避免在暴露于激光处理前的图像形成。
标记本发明的激光敏感记录材料的方法也是本发明的一部分,该方法包括,将激光敏感记录材料的那些准备标记的部分暴露于激光辐照以便产生标记的步骤。
激光辐照可采用UV、可见光或IR激光器进行。IR激光器的实例为CO2激光器、Nd:YAG激光器或IR半导体激光器。
优选地,使用IR激光器。更有效地,Ir激光器具有780至1′000′000nm范围内的波长。甚至更优选地,IR激光器为CO2激光器或Nd:YAG激光器。最优选地,IR激光器为具有10′600nm波长的CO2激光器。
通常,IR激光器具体功率和线速取决于应用,并且选择为足以产生图像,例如,当IR激光器的波长为10′600nm,激光束的直径为0.35mm时,功率通常为0.5至4W,线速通常为300至2′000mm/s。
本发明的再另一方面为通过以上方法获得的经标记的激光敏感记录材料。
本发明组合物在安全/跟踪和追溯领域中在包装材料上标记数据的用途也是本发明的一部分。
在安全/跟踪和追溯领域中,本发明的激光敏感记录材料可采用高分辨率激光成像以产生非常小的代码,它们对于人眼来说时不可见或者几乎不可见。但是该图像可采用能给出特殊代码的设备(例如数码相机/扫描器、放大镜或者配备了相机的移动电话)解码。特定的高分辨率图像可通过计算机生成,并且可以是二维条形码的形式或其它模式。一经扫描,信息可输送至可靠的计算机(与移动电话无线连接),然后该计算机可给出具体的认证、生产日期、产地等信息。采用传统印刷方法极难复制这种高分辨率图像。
本发明的激光敏感记录材料具有的优点在于其增强了激光辐照的作用。例如,当产生的颜色密度在指定的辐照功率和时间的组合下增加时,或者当所产生颜色的指定密度可在较低辐照功率和/或较少时间的组合下得到时,增强了激光辐照的作用。
实施例
实施例1
底涂层组合物的制备
通过将以下成分以指定顺序混合来制备底涂层组合物:154g水、1gN40,其为丙烯酸钠盐共聚物的水溶液、100g颜料(见下表1)、30g 10重量%的聚乙烯醇水溶液和15g 50重量%的Dow胶乳DL950溶液(其为苯乙烯丁二烯胶乳)。实施例1a至1d的预涂层组合物通过添加水调节至固体含量为30重量%。
表1
实施例2
丙烯酸粘结剂的制备
向配备了机械搅拌器、冷凝器、氮气入口、温度探针和进料口的1升树脂罐中放入98.9g水和483.9g8078,一种低分子量苯乙烯丙烯酸共聚物的铵盐溶液。将内容物加热至85℃,并以氮气脱气30分钟。通过混合192.5g苯乙烯和157.5g丙烯酸2-乙基己酯制备单体相。通过将1.97g过硫酸铵溶解进63.7g水制备引发剂进料。当反应器达到温度并脱气后,将0.66g过硫酸铵添加到反应器。2分钟后,开始单体和引发剂供料,分别适当地供料3和4小时。在整个供料期间反应器内容物保持在85℃。供料结束后,反应器内容物在85℃再保持1小时,然后冷却至低于40℃,这时添加0.9g Acticide LG,一种含有氯化和未氯化的甲基异噻唑酮的生物杀灭剂。这产生49.2%固体、pH 8.3和Brookfield RVT粘度1100cPs的乳液聚合物。
实施例3A
记录层组合物A的制备
将硫酸铵(6.55g)和D-(+)-蔗糖(14.0g)溶解在水(33.7g)中。加入如实施例2所述制备的40.25g丙烯酸粘结剂,并将得到的白色乳液搅拌2小时。
实施例3B
记录层组合物B的制备
将硫酸铵(6.55g)、磷酸氢二铵(6g)和D-(+)-蔗糖(15.0g)溶解在水(33.7g)和25重量%的氨水(0.1g)的混合物中。加入如实施例2所述制备的40.25g丙烯酸粘结剂,并将得到的白色乳液搅拌2小时。
实施例4
具有底涂层和记录层的纸的制备
采用第3号K bar(K bar number 3)将实施例1a至1d的底涂层组合物施涂在基重约48g/m2的未预涂原纸上,以产生约24μm的湿膜。该膜在40℃干燥4分钟以形成底涂层。然后通过12μm涂布棒分别将如实施例3A和3B所述制备的记录层组合物A或B施涂至底涂层,接着在环境温度下干燥以生成记录层。作为对照,以记录层组合物A和B分别直接涂布未预涂原纸。通过以CO2IR激光器(波长:10′600nm,功率:2W,激光束直径:0.35mm,线速1000mm/s)处理经涂布的纸形成着色图像。将具有底涂层的纸获得的图像密度与不具有底涂层的对照进行比较。密度的增加(具有底涂层相对不具有底涂层)显示在下表2中。
表2
1+指密度增加,++指密度大大增加。
Claims (7)
1.一张激光敏感记录材料,其包括被记录层和底涂层涂布的基底,其中所述记录层包含受到激光辐照产生的热处理时发生颜色变化的体系,以及其中所述底涂层包含颜料,前提是所述记录层的受到激光辐照产生的热处理时发生颜色变化的体系不包含有机隐色染料和有机显色剂。
2.如权利要求1所述的激光敏感记录材料,其中所述底涂层还包含聚合物粘结剂。
3.如权利要求1或2所述的激光敏感记录材料,其中所述底涂层还包含其它组分。
4.一种制备权利要求1至3中任一项所述的激光敏感记录材料的方法,所述方法包括以形成所述底涂层的组合物涂布基底,然后以形成所述记录层的组合物涂布的步骤。
5.一种标记权利要求1至3中任一项所述的激光敏感记录材料的方法,所述方法包括将所述激光敏感记录材料的那些准备标记的部分暴露于激光辐照以便产生标记的步骤。
6.可通过权利要求5所述的方法获得的经标记的激光敏感记录材料。
7.权利要求1至3中任一项所述的激光敏感记录材料在安全/跟踪和追溯领域中在包装材料上标记数据的用途。
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EP07103770.9 | 2007-03-08 | ||
EP07103770 | 2007-03-08 |
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CN101626903A true CN101626903A (zh) | 2010-01-13 |
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US (1) | US20100279079A1 (zh) |
EP (1) | EP2117848A1 (zh) |
JP (1) | JP2010520093A (zh) |
KR (1) | KR20090118106A (zh) |
CN (1) | CN101626903A (zh) |
CA (1) | CA2679327A1 (zh) |
TW (1) | TW200838716A (zh) |
WO (1) | WO2008107345A1 (zh) |
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CN104053554A (zh) * | 2012-01-13 | 2014-09-17 | 惠普发展公司,有限责任合伙企业 | 印刷介质涂层 |
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2008
- 2008-02-27 KR KR1020097020915A patent/KR20090118106A/ko not_active Application Discontinuation
- 2008-02-27 US US12/528,352 patent/US20100279079A1/en not_active Abandoned
- 2008-02-27 CA CA002679327A patent/CA2679327A1/en not_active Abandoned
- 2008-02-27 CN CN200880007425A patent/CN101626903A/zh active Pending
- 2008-02-27 WO PCT/EP2008/052332 patent/WO2008107345A1/en active Application Filing
- 2008-02-27 JP JP2009552168A patent/JP2010520093A/ja not_active Withdrawn
- 2008-02-27 EP EP08717151A patent/EP2117848A1/en not_active Ceased
- 2008-03-06 TW TW097107813A patent/TW200838716A/zh unknown
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Also Published As
Publication number | Publication date |
---|---|
WO2008107345A1 (en) | 2008-09-12 |
US20100279079A1 (en) | 2010-11-04 |
KR20090118106A (ko) | 2009-11-17 |
EP2117848A1 (en) | 2009-11-18 |
JP2010520093A (ja) | 2010-06-10 |
TW200838716A (en) | 2008-10-01 |
CA2679327A1 (en) | 2008-09-12 |
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