CN1331964C - 可辐射固化的印刷介质和由其制得的转印制品以及制作陶瓷装饰品的方法 - Google Patents
可辐射固化的印刷介质和由其制得的转印制品以及制作陶瓷装饰品的方法 Download PDFInfo
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- CN1331964C CN1331964C CNB2004800052960A CN200480005296A CN1331964C CN 1331964 C CN1331964 C CN 1331964C CN B2004800052960 A CNB2004800052960 A CN B2004800052960A CN 200480005296 A CN200480005296 A CN 200480005296A CN 1331964 C CN1331964 C CN 1331964C
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Abstract
本发明涉及一种基于热塑性聚合物和至少一种可辐射聚合的单体化合物的可辐射固化的印刷介质。通过含杂环的化合物使装饰品达到兼有反应性和柔性的组合特性。优选的单体化合物含1,3-二氧杂环戊烷环、1,3-二氧杂环己烷环和1,4-二氧杂环己烷环,并且丙烯酰基或甲基丙烯酰基以酯的方式连接在羟甲基周围。此外本发明还提供含印刷介质的转印制品和装饰制剂。
Description
技术领域
本发明涉及一种新型可辐射固化的印刷介质,该介质含塑性聚合物粘合剂和至少一种可辐射固化的单体化合物,其特征在于具有改进的柔性。本发明还涉及应用本发明的可辐射固化的印刷介质制得的转印制品以及制作陶瓷装饰品的方法,其中,将含本发明的可辐射固化的印刷介质的装饰制剂涂布于待装饰的基材上,经辐射固化并接着在通常的条件下焙烧。
背景技术
已知有各种用于制作陶瓷装饰品的直接或间接的印刷方法,转印技术也属于间接印刷方法。为了装饰,将通常含有形成装饰品的组分如颜料、颜料混合物、颜料前体、贵金属化合物或金属粉末以及液态或膏状印刷介质的装饰制剂印制在基材或转印载体上。在辐射固化性印刷介质情况下,在施加装饰层后,用辐射源特别是紫外光(UV)源进行固化。最后以本来已知的方法焙烧涂布于基材上的装饰层。
应用可辐射固化的印刷介质日趋重要,因为由此可减少或避免在装饰过程中由溶剂的挥发所产的环境问题。目前已知的适于制备转印制品的可辐射固化的印刷介质的缺点是,它们通常具有不合要求的柔性和/或不合要求的反应性。虽然在如用紫外光辐射固化时,印刷介质的高反应性会导致快速固化,从而保持无粘性的表面,但随着含这类可辐射固化的印刷介质的转印制品存放时间的延长,会导致转印制品的脆化,以致在使用中会自身破裂并由此产生装饰缺陷。另一方面,由于可辐射固化的印刷介质的组成中具有高含量的柔性化单体,所以具有耐久的柔性,但会在通常的辐射条件下得到具有过高表面粘性的装饰品;这种转印制品是不能用的,因为该图片是不可套印的,也是不可叠置的。虽然其组成很不相同的可辐射固化的印刷介质是已知的,但是对于可辐射固化的印刷介质所提出的这样或那样的需求或各种需求的组合,仍然尚待解决。
DE-3048823提到一种用紫外光辐射可固化的树脂组合物,其由特定的饱和共聚酯、由每分子中含有一个可聚合双键的化合物和每分子中含两个或多个可聚合双键的化合物组成的可聚合组分和至少一种光敏剂组成;此外该树脂组合物还含其它合成树脂,如有机的异氰酸酯化合物、颜料、流动助剂和热聚合阻聚剂。可聚合组分优选包括约10~70重量%的单丙烯酸酯和/或单甲基丙烯酸酯、5~50重量%的一种或多种含至少两个可聚合双键的丙烯酸酯或甲基丙烯酸酯和20~70重量%的分子量大于500的一种或多种二丙烯酸酯或二甲基丙烯酸酯。该系统中含一种或多种由苯偶姻、蒽醌、二苯酮、呫吨酮和噻吨酮中的化合物作为光引发剂。
在前面提到的DE-3048823中,也可应用丙烯酸四氢糠酯作为单官能团的丙烯酸,即其醇组分含杂环的丙烯酸。然而,由该文献无法得出通过使用杂环丙烯酸酯可以产生某些优点的启示。
由DE-3819414中披露了适用于装饰玻璃、陶器和瓷器的有光泽的贵金属制剂,该制剂含有可溶性有机贵金属化合物、多环丙烯酸酯如异冰片基丙烯酸酯和/或二环戊二烯基丙烯酸酯和光引发剂。此外,该制剂还含有其它可聚合的化合物,其中有N-乙烯基吡咯烷酮。含有可溶性有机贵金属化合物的介质的其它组分是具有丙烯酸酯基和/或甲基丙烯酸酯基的低聚物。
JP-141473(1984)也涉及陶瓷制品的贵金属装饰品,其中不仅该图像层介质而且覆盖层均含可辐射固化组分。
在试图克服辐射固化介质的缺点的尝试中,EP-52763和EP-52764A1建议应用一种印刷介质,该介质含多官能团的丙烯酸树脂的预聚物如丙烯酸酯化的聚酯、单官能团丙烯酸酯、二官能团丙烯酸酯和三官能团丙烯酸酯、具有确定聚合度的聚甲基丙烯酸甲酯和光引发剂。按EP-0106628A1还可由上述介质得到其它的改进型辐射固化印刷介质,这时该介质主要由完全聚合的热塑性树脂和辐射固化稀释剂组成,并且可略去多官能团的丙烯酸树脂或丙烯酸化的聚酯,同时无燃烧特性方面的缺点。
按US-4666756可得到使用可辐射固化介质制备的并具有改进的柔性的转印制品,这是由于制备转印制品所用的印刷介质含寡聚亚烷基二醇的二丙烯酸酯或二甲基丙烯酸酯。但这类系统的反应性经常是不合要求的,以致由此制备的装饰膜需要过长的固化时间和/或仍保持粘性。
发明内容
本发明的目的是提供另一种具有改进特性的可辐射固化的印刷介质。
本发明的另一目的是实现兼有反应性和柔性的特性组合,使由此制备的转印制品在长期存放后具有足够的柔性,以致可得到无缺陷的装饰品。
本发明的再一目的是提供一种转印制品,该制品在通常的辐射固化条件下呈非粘性固化,并由此是可套印和可叠置的。通过权利要求的可辐射固化的印刷介质来实现上述的目的以及源自下列描述的其它目的。
由此本发明的目的是提供一种用于制备陶瓷装饰品的可辐射固化的印刷介质,该介质包含热塑性聚合物粘合剂和至少一种选自含杂环的烯烃化合物的可辐射固化的单体化合物,其中该聚合物粘合剂在单体化合物中是可溶的,其特征在于,所述杂环为4~8元环并含一个或多个氮原子和/或氧原子作为杂原子,至少一个可辐射聚合的乙烯基、丙烯酰基或甲基丙烯酰基直接或经1~6元的桥联单元连结在杂环上,邻接环杂原子的碳原子具有至少一个可离去的氢原子,并且不采用N-乙烯基吡咯烷酮以及(甲基)丙烯酸四氢糠酯作为可聚合的单体化合物。
从属权利要求涉及本发明的印刷介质的优选实施方案。
其它权利要求涉及使用本发明的印刷介质的转印制品以及应用本发明的印刷介质制作陶瓷装饰品的方法。
具体实施方式
本发明的必要特征在于,可辐射固化的印刷介质含至少一种可辐射固化的单体化合物,该单体化合物具有杂环和至少一个位于邻接杂原子的碳原子上的可离去的氢。鉴于前面所评述的现有技术,该类可聚合的单体化合物不采用N-乙烯基吡咯烷酮以及(甲基)丙烯酸四氢糠酯。
可聚合的单体化合物的杂环可含一个或多个选自氮和/或氧的杂原子。特别优选是含一个或二个氧原子的化合物、含一个或二个氮原子的化合物或含一个氧原子和一个氮原子的化合物。该杂环可以是饱和的或部分不饱和的,但不是杂芳环,因为在杂芳环的情况下,邻接杂原子的碳原子不含可离去的氢原子。当邻接杂原子的碳原子含至少一个可离去的氢原子,并且在另一原子上连接具有可辐射聚合的乙烯基、丙烯酰基或甲基丙烯酰基的取代基时,该杂环可含其它取代基,特别是含1~12个碳原子的烷基,如特别优选甲基乙基、正丙基和异丙基、烷氧基如甲氧基、乙氧基、甲氧乙氧基和含多于一个醚桥基的烷氧基、腈基、乙氧羰基和氨基甲酸基。
优选的可聚合单体化合物含选自以下范围:
(i)二氢-2-H-吡喃和四氢-2-H-吡喃、1,3-二氧杂环戊烷、1,3-二氧杂环己烷和1,4-二氧杂环己烷、苯并二氢呋喃和异苯并二氢呋喃、2-H-苯并吡喃、1-H-异苯并吡喃、苯并二氢吡喃和异苯并二氢吡喃、苯并3-环氧庚二烯(3-Benzoxepin),
(ii)吡咯啉和吡咯烷、咪唑啉和咪唑烷、哌啶、二氢吲哚和异二氢吲哚、1,2-二氢喹啉和四氢喹啉、1,2-二氢异喹啉和四氢异喹啉、哌嗪、全氢嘧啶,和
(iii)吗啉、全氢-1,3-噁嗪、4H-二氢-3,1-苯并噁嗪、1,3-嗯唑啉、1,3-噁唑烷。
按另一实施方案,该可聚合单体化合物的杂环是5元~7元内酰胺环,特别是戊内酰胺环和己内酰胺环,此外也可是乙内酰脲环。该可聚合的基团直接或经含1~4个碳原子的桥键连接在内酰胺的氮上是适宜的。该可聚合基团优选含有选自乙烯基取代基、丙烯酰基取代基、甲基丙烯酰基取代基、(甲基)丙烯酰氧基-(C1~C4)-烷基取代基或(甲基)丙烯酰基-氨基-(C1~C4)-烷基取代基的基团。(甲基)丙烯酰基表示丙烯酰基或甲基丙烯酰基。
按另一优选实施方案,该杂环包括1,3-二氧杂环戊烷环、1,3-二氧杂环己烷环或1,4-二氧杂环己烷环。特别优选的含杂环的可聚合化合物是三羟甲基乙烷单缩甲醛单(甲基)丙烯酸酯和三羟甲基丙烷单缩甲醛单(甲基)丙烯酸酯。
另一些特别优选的可聚合化合物是戊内酰胺、己内酰胺和乙内酰脲以及选择性地具有甲基取代基的衍生物,该具有甲基取代基的衍生物含直接连接在内酰胺的氮上的可聚合基团。
该热塑性聚合物粘合剂可包括不同的物质,其中有聚合物和共聚物、缩聚物和加聚树脂。这种粘合剂的聚合度或缩聚度的选择要确保与该含杂环的单体化合物有足够的兼容性。作为该粘合剂优选考虑下列通式的丙烯酸酯和甲基丙烯酸酯的聚合物和/或共聚物:
CH2=CR1-COOR2
其中R1为H或CH3和R2为H、总共含1~20个碳原子的烷基、环烷基、芳烷基或芳基。可示例性地提到(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄酯和(甲基)丙烯酸苯酯。特别优选是(甲基)丙烯酸甲酯和(甲基)丙烯酸正丁酯的共聚物。该聚合物粘合剂还可含其它可聚合的化合物如乙烯、苯乙烯、丁二烯、异丁烯、异戊二烯、乙酸乙烯酯、异丁基、异丁基乙烯基醚和丙烯腈。
除这类通过一个或多个可聚合的单体化合物聚合所得的粘合剂外,还可单独使用或与上述聚合物结合使用另一些相容性树脂,例如聚酯树脂和异氰酸酯树脂,只要这些树脂相互具有足够的相容性即可。
在印刷介质中,该热塑性聚合物粘合剂与该可辐射聚合的杂环的单体化合物的重量比为≥1∶20,特别是1∶10至1∶2。通过这两个最重要组分的重量比可控制该印刷介质的性能范围。为改进该印刷介质的性能,其它可辐射聚合的单体也可以是该印刷介质的组分,所述其它可辐射聚合的单体带有一个或多个(特别是一个或二个)可聚合的乙烯基、丙烯酰基或甲基丙烯酰基。这类可聚合化合物的实例是:苯乙烯衍生物,如甲基苯乙烯和氯苯乙烯;(甲基)丙烯酸烷基酯,如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯或(甲基)丙烯酸异丙酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、丙烯酸-2-羟乙基酯;聚氧亚烷基二醇单(甲基)丙烯酸酯,如聚乙二醇单(甲基)丙烯酸酯和聚丙二醇单(甲基)丙烯酸酯;和(甲基)丙烯酸四氢糠酯。
还可应用含二个或多个可聚合双键的可光致聚合的化合物来进一步改变该印刷介质的性能,所述可光致聚合的化合物如乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、二甘醇二(甲基)丙烯酸酯或三甘醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯和季戊四醇四(甲基)丙烯酸酯。为进一步改性,该印刷介质还可含消泡剂、增塑剂、触变剂和已知的其它添加剂。
在印刷介质中所含组分的用量比可在宽的范围内变化。优选印刷介质含有:至少2重量%,特别是5~40重量%的热塑性粘合剂,该粘合剂可由一个或多个组分组成,并且特别是甲基丙烯酸酯聚合物或甲基丙烯酸酯共聚物;5~95重量%,特别是10~90重量%的一种或多种含杂环的可聚合单体;和0~85重量%,特别是0~70重量%的其它可辐射聚合的单体。该印刷介质除含上述聚合物和可聚合的单体外,还含一种或多种有效量的光引发剂。示例性的光引发剂是:缩酮,如苄基二甲基缩酮;苯偶姻,如苯偶姻甲基醚、苯偶姻乙基醚;蒽醌,如1-氯蒽醌和2-乙基蒽醌;苯并苯酚,如二苯酮、对二甲基氨基二苯酮;苯基乙基酮,如2-羟基-2-甲基丙酰苯;二苯并环庚酮;含硫化合物,如二甲基二硫醚、四甲基秋兰姆二硫醚;和噻吨酮。
该前述的添加剂以有效量使用,通常为小于15重量%,特别是小于10重量%。
本发明的另一目的是提供一种可辐射固化的装饰制剂,该装饰制剂含本发明的印刷介质和选自颜料、金属粉末、颜料前体、贵金属化合物的装饰性组分,这些装饰性组分悬浮和/或溶于该印刷介质中,需要时还可含粒状的成分以增加颜料的体积浓度(PVK)。
与装饰有关的组分的选择是本专业技术人员熟知的,可以根据所需的效果如色彩、光泽性和耐磨性以及耐酸性和耐碱性来确定这类组分。这些与装饰有关的组分的使用量也如此选定。在用于陶瓷装饰品的装饰制剂中所含的其它组分包括助熔剂,该助熔剂主要包含选自玻璃料、形成玻璃的氧化物的前体和硅酸盐的物质的组合。氧化物中也可存在偶联氧化物,在焙烧装饰时,该偶联氧化物使装饰层在例如玻璃和陶瓷等基材上产生优良的附着性。
可辐射固化的贵金属制剂含有:例如10~50重量%,特别是30~45重量%的元素态金;0.1~20重量%,特别是1~5重量%的助熔剂;和30~80重量%的本发明的印刷介质。需要时还可存在可溶性贵金属化合物。为了借助于直接和间接的印刷方法、采用这类制剂得到表面质量良好的具有美感的装饰品,使用提高颜料的体积浓度的试剂来代替基于硅酮的流动助剂是合适的。该提高颜料的体积浓度的试剂是特定的有机化合物,例如未交联的或交联的有机聚合物,该化合物在印刷介质中不可溶且不可膨胀,但在装饰品的焙烧中可以完全烧尽(参见EP-A-01121227)。
含无机颜料和玻璃料作为助熔剂的装饰制剂可主要含1~50重量%的无机颜料、1~50重量%的玻璃料和10~90重量%(特别是20~40重量%)的本发明的印刷介质。
本发明的另一目的是提供一种用于制备陶瓷装饰品的转印制品,该转品制品包括:柔性载体材料,如转印纸;可用水或加热活化的分离层;分离层上的图像层;和图像层上的覆盖层。按本发明,该图像层和/或覆盖层含有与之其相关的权利要求中的可辐射固化的印刷介质。
转印技术是用于装饰性陶瓷基材的熟知的常用方法。将转印载体上的图像层和装饰层(需要时还可以有其它层,如偶合层和特效赋予层)移动到待装饰的基材上,然后焙烧该装饰品。
为了制备陶瓷装饰品,将含有本发明的印刷介质的可辐射固化的膏状装饰制剂通过直接或间接的印刷方法,特别是丝网印刷方法涂于待装饰的基材上。通过用紫外光线或其它高能射线辐照该装饰层使其固化。然后将涂布在陶瓷基材(还包括玻璃)上的装饰品在根据该基材和装饰制剂的组成进行调整的装饰品焙烧条件下进行焙烧。
本发明的印刷介质的特征是具有优良的可辐射固化性,并兼有下列所需的特性:高反应性和由此导致的可快速固化性、装饰层的非粘性、装饰层的高柔性,使得可以获得轮廓分明的无缺陷的装饰品。该印刷介质一个特别的优点是,由此制备的转印制品甚至经长期保存后仍保持其柔性,并且不出现所担扰的脆化和由此产生装饰品破裂。这种特性的组合是通过过去所知的含反应性的双官能团和增柔化单官能团单体的印刷介质所不能达到的。
实施例
应用实施例1和对比例2的紫外介质,以10重量份的颜料对7~9重量份介质的比例,由此制备陶瓷颜料膏。通过控制介质粘度(甲基丙烯酸酯聚合物的含量)可以使该膏制剂的比例达10∶2至10∶20。
通过在适当的转印纸(如Meta Consort,Hoffmann&Engelmann)上进行丝网印刷,得到转印制品,接看用紫外灯固化。这时紫外光剂量应达200~600mJ/cm2(取决于颜料),应当用作为转印漆(例如80450,费柔公司)的紫外固化性透明涂层覆盖紫外印刷品。
在陶瓷装饰品上制作转印图像的一般程序参看:A.Huber,“Decoration of porcelain,earthenware&bone china”,CFI,Jan.,1996。
下面的表给出本发明的介质的组成和一些现有技术中的介质。
表1
实施例1(B1) | ||
杂环单体,单官能团 | 三羟甲基丙烷缩甲醛丙烯酸酯 | 60% |
甲基丙烯酸甲酯/甲基丙烯酸正丁酯共聚物 | Degalan P24 | 22% |
甘油-脂肪酸酯(触变剂) | Thixatrol ST | 2% |
邻苯二甲酸酯增塑剂 | Edenol 344 | 6% |
光引发剂 | Darocure 1173 | 5% |
增效剂 | Quantacure EPD | 2% |
光引发剂 | Quantacure ITX | 3% |
对比例1(VB1) | ||
线性单体,单官能团 | 二甘醇乙基醚丙烯酸酯 | 30% |
线性单体,双官能团 | 二丙二醇二丙烯酸酯 | 30% |
甲基丙烯酸甲酯/甲基丙烯酸正丁酯共聚物 | Degalan P24 | 22% |
甘油-脂肪酸酯(触变剂) | Thixatrol ST | 2% |
邻苯二甲酸酯增塑剂 | Edenol 344 | 6% |
光引发剂 | Darocure 1173 | 5% |
增效剂 | Quantacure EPD | 2% |
光引发剂 | Quantacure ITX | 3% |
对比例2(VB2) | ||
线性单体,单官能团 | 二甘醇乙基醚丙烯酸酯 | 60% |
甲基丙烯酸甲酯/甲基丙烯酸正丁酯共聚物 | Degalan P24 | 22% |
甘油-脂肪酸酯(触变剂) | Thixatrol ST | 2% |
邻苯二甲酸酯增塑剂 | Edenol 344 | 6% |
光引发剂 | Darocure 1173 | 5% |
增效剂 | Quantacure EPD | 2% |
光引发剂 | Quantacure ITX | 3% |
对比例3(VB3) | ||
线性单体,双官能团 | 二丙二醇二丙烯酸酯 | 60% |
甲基丙烯酸甲酯/甲基丙烯酸正丁酯共聚物 | Degalan P24 | 22% |
甘油-脂肪酸酯(触变剂) | Thixatrol ST | 2% |
邻苯二甲酸酯增塑剂 | Edenol 344 | 6% |
光引发剂 | Darocure 1173 | 5% |
增效剂 | Quantacure EPD | 2% |
光引发剂 | Quantacure ITX | 3% |
应用表1的介质制备的转印制品的特性列于表2。
表2
介质编号 | 转印制品的老化 | 反应性(固化) | 柔性/装饰品质量 |
B1 | 6小时 | 好 | 好/好 |
5天 | 好 | 好/好 | |
1个月 | 好 | 好/好 | |
VB1 | 6小时 | 好 | 好/好 |
5天 | 好 | 一般/轮廓不清楚 | |
1个月 | 好 | 脆/严重的装饰品缺陷 | |
VB2 | 6小时 | 非常好 | 好 |
5天 | 因交联而下降 | 完全脆化/在应用时装饰品破裂 | |
VB3 | 6小时 | 固化不够,粘性表面 | 好 |
5天 | 附着性下降 | 好 |
Claims (10)
1.一种用于制备陶瓷装饰品的可辐射固化的印刷介质,该介质包含热塑性聚合物粘合剂和至少一种选自含杂环的烯烃化合物的可聚合的单体化合物,所述聚合物粘合剂在该单体化合物中是可溶的,所述杂环为5~6元环并含多个氧原子作为杂原子,其特征在于,至少一个可聚合的乙烯基、丙烯酰基或甲基丙烯酰基直接或经1~6元的桥联单元连结在杂环上,邻接环杂原子的碳原子具有至少一个可离去的氢原子,所述可聚合的单体化合物包括1,3-二氧杂环戊烷环、1,3-二氧杂环己烷环或1,4-二氧杂环己烷环和(甲基)丙烯酰氧基-(C1~C4)-烷基取代基或(甲基)丙烯酰基-氨基-(C1~C4)-烷基取代基。
2.如权利要求1所述的印刷介质,其特征在于,所述可聚合的单体化合物是三羟甲基乙烷单缩甲醛单(甲基)丙烯酸酯或三羟甲基丙烷单缩甲醛单(甲基)丙烯酸酯。
3.如权利要求1所述的印刷介质,其特征在于,所述热塑性聚合物粘合剂和所述可聚合的杂环单体化合物的重量比为1∶20至1∶2。
4.如权利要求1所述的印刷介质,其特征在于,所述印刷介质还具有含量最高为85重量%的其它可聚合的单体。
5.如权利要求1所述的印刷介质,其特征在于,所述印刷介质含有:2重量%~40重量%的热塑性粘合剂;5~95重量%的具有杂环的可聚合单体;和0~85重量%的其它可聚合的单体。
6.如权利要求1所述的印刷介质,其特征在于,所述印刷介质含1~20重量%的光引发剂。
7.如权利要求1所述的印刷介质,其特征在于,所述印刷介质还含有总量最高为15重量%的选自消泡剂、邻苯二甲酸酯增塑剂和触变剂中的一种或多种添加剂。
8.一种可辐射固化的装饰制剂,该装饰制剂含有印刷介质和选自颜料、金属粉末、颜料前体、贵金属化合物的装饰性组分,这些组分悬浮和/或溶于该印刷介质中,其特征在于,所述装饰制剂含有对于印刷膏适量的如权利要求1~7任一项所述的印刷介质。
9.一种用于制作陶瓷装饰品的转印制品,该制品包括柔性载体材料、可用水或加热活化的分离层、分离层上的图像层和图像层上的覆盖层,其特征在于,所述图像层和/或覆盖层是用如权利要求1~7任一项所述的可辐射固化的印刷介质制备的,或者该图像层是用如权利要求8所述的装饰制剂制备的。
10.一种制作陶瓷装饰品的方法,该方法包括:将可辐射固化的装饰制剂通过直接或间接的印刷方法涂于待装饰的基材上,通过用紫外光线辐照使该装饰层固化,并在装饰品的焙烧条件下焙烧该装饰层,其特征在于,将如权利要求8所述的装饰制剂印刷到陶瓷基材或转印载体上,在转印方法中,将所述装饰品以贴花图案的形式从转印载体上剥离并转印到陶瓷基材上。
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- 2004-01-29 AT AT04706180T patent/ATE382667T1/de not_active IP Right Cessation
- 2004-01-29 WO PCT/EP2004/000800 patent/WO2004076569A1/de active IP Right Grant
- 2004-01-29 DE DE200450005824 patent/DE502004005824D1/de not_active Expired - Lifetime
- 2004-01-29 CN CNB2004800052960A patent/CN1331964C/zh not_active Expired - Fee Related
- 2004-01-29 PT PT04706180T patent/PT1597326E/pt unknown
- 2004-01-29 EP EP20040706180 patent/EP1597326B1/de not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
CN1753957A (zh) | 2006-03-29 |
DE10308971A1 (de) | 2004-09-09 |
WO2004076569A1 (de) | 2004-09-10 |
US7968175B2 (en) | 2011-06-28 |
ATE382667T1 (de) | 2008-01-15 |
PT1597326E (pt) | 2008-04-08 |
EP1597326A1 (de) | 2005-11-23 |
DE502004005824D1 (de) | 2008-02-14 |
EP1597326B1 (de) | 2008-01-02 |
US20060134554A1 (en) | 2006-06-22 |
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