CN1114666A - 可辐照固化的有色组合物 - Google Patents
可辐照固化的有色组合物 Download PDFInfo
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- CN1114666A CN1114666A CN95102054A CN95102054A CN1114666A CN 1114666 A CN1114666 A CN 1114666A CN 95102054 A CN95102054 A CN 95102054A CN 95102054 A CN95102054 A CN 95102054A CN 1114666 A CN1114666 A CN 1114666A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
- B44C1/14—Metallic leaves or foils, e.g. gold leaf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1729—Hot stamping techniques
-
- C—CHEMISTRY; METALLURGY
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Abstract
一种包括一种可辐照固化组分和一种吡咯并吡咯或异二氢吲哚颜料的有色颜料组合物;一种用有色油墨组合物对底物施彩的方法;和一种用热印记箔和有色油墨组合物施彩的方法。
Description
本申请是1992年1月24日递交的U.S专利申请系列号824,968的部分继续申请。
本发明属于可辐照固化的油墨组合物领域。
工业陶瓷和玻璃器皿常常用筛网印刷,胶板印刷(offsetprinting)或其它直接施涂技术将一个彩色油墨图案涂到底物的表面上来施彩。施彩后的底物然后焙烧以烧掉油墨中的有机组分并使该图案结合到玻璃上。这种方法耗时又耗能,需昂贵的操作费并需要大的厂房。此外,在焙烧前,涂敷的施彩物极易因手工操作产生的磨擦和划痕而损坏,因而许多被废弃掉。
辐照可固化粘合剂是本领域公知的且较其它类型油墨好,因为辐照固化容易进行且便宜,仅需要一个能发射所需波长光的灯,或在没有光聚合引发剂情况下使用电子束即可,它也不需要很大的厂房。此外可完全消除烘箱中的有害物和能耗。可辐照固化的油的一个要缺陷是加重金属颜料如隔、铬,锰等到油墨组合物中将妨碍辐照固化。具体地说,红和黄颜料吸收与紫外光(4—400nm)或光化辐射线(200—600nm)相同波长的光。由于环境上对重金属的关注,镉和铬目前备受检查,因此不希望在施彩时使用它们。此外,用有机颜料着色的油墨常常呈现出差的着色(如红色常常看上去像棕色或洋红色),因而不能被工业施彩接收。
因此,需要可辐照固化的油墨,它易于固化,有着鲜艳可辩认工业施彩可接收的红和黄色,且无环境危害。
本发明涉及一种有色油墨组合物,包括
a)一种可辐照固化的组分,该组分当直接施涂到一种底物上时是可操作的,当固化时,粘接到该底物上;和
b)一种选自吡咯并吡咯、异二氢吲哚酮和它们的混合物的颜料;
本发明也涉及一种施涂彩色施彩物到底物上的方法,包括:
a)以预定的设计图案将一种有色油墨组合物施涂到底物上,所述组合物包括一种可辐照固化的组分和一种选自吡咯并吡咯,异二氢吲哚酮和它们的混合物的颜料,所述油墨当固化粘到底物上时是可操作的,
b)通过将油墨暴光在辐射线下将其固化在底物,由于辐射固化粘接油墨到底物上。
本发明也涉及一种用有色油墨和热印记箔对底物施彩的方法,包括
a)以预定的设计图案将一种有色油墨组合物施涂到底物上,所述组合物包括一种可辐照固化的组分和一种选自吡咯并吡咯,异二氢吲哚酮和它们的混合物的颜料,所述油墨当固化粘到底物上时是可操作的,
b)通过将油墨暴光在辐射线下将其固化在底物上,由于辐射固化粘接油墨到底物上,
c)用印模将热印记箔板压到底物上,印模加热到足以使箔部分粘到底物的加热固化的油墨设计图案上而不粘到底物无油墨区域上的温度,和
d)除去印模,留下结合到油墨设计图案上的箔部分。
本发明基于下列发现:有机颜料如吡咯并吡咯和异二氢吲哚酮颜料(分别为红和黄色)能合并到用作施彩的可辐照固化的组合物中以提供红和黄色,该组合物明亮,逼真且能很好地结合到底物上并很容易在底物上直接固化。底物可以是玻璃、塑料、陶瓷且可包括容器如瓶子,杯子盘子,眼镜,花瓶,雕像,其它装饰玻璃容器,玻璃或陶瓷板,瓷砖等。
可辐照固化的组合物含一种可辐照固化的组分,该组分可以是单体,低聚物或低分子量均聚物,共聚物,三聚物,接枝共聚物或嵌段共聚物,只要该组分暴露到电子束或光化或紫外线辐照下可固化(可聚合)即可,可辐照固化组分必须在固化后能结合到涂敷的底物,粘合程度要作为施彩商业上可接受。这意味着油墨必须永久性结合到底物上,以使其在底物的有效寿命期间足以维持在底物上。例如,当底物是一个含铁搪瓷体(nail enamel)的容器,油墨必须在整个铁搪瓷体有效寿命期间维持在该容器上并能耐溶剂和在铁搪瓷体中的其它成分。在本发明优选的实施方案中,可辐照固化组分用波长为4到400,优选325—365nm紫外线(UV)辐照来固化。
适宜的单体包括环氧化物,环脂肪环氧化物,氯乙烯,苯乙烯,丙烯酸乙酯,乙酸乙烯酯,官能性丙烯酸类单体如丙烯酸羟烷酯或甲基丙烯酸羟烷酯,丁酸乙烯酯,乙烯基甲基醚,甲基丙烯酸甲酯,丙烯酸异冰片基酯,丙烯腈或其混合物。
适宜的聚合物包括上述单体的低聚物,均一或共聚物,三聚物,接枝共聚物,条件是它们的分子量应小于约50000,否则难以进行聚合。
优选的是阳离子UV固化的每分子至少有2个环氧基的环氧化物及聚合物如表氯醇和苯酚的反应产物或酚甲醛树脂,二环氧树脂,环氧化油,和优选环氧化聚烯烃。这类环氧化物包括酚醛清漆环氧化物,各种类型的缩水甘油醚包括双酚二缩水甘油醚,丁二醇二缩水甘油醚等。含侧链环氧基的均聚物和共聚物也是适宜的例如由丙烯酸缩水甘油酯和/或甲基丙烯酸缩水甘油酯本身或与其它烯属不饱和单体如氯乙烯,乙酸乙烯酯,苯乙烯,丙烯酸羟乙酯,丙烯酸羟丙酯等制得的物质。优选的是阳离子UV固化的环脂肪环氧化物,包括公开在U.S、patent Nos.3,027,357,3,890,194,2,890,197,3,031,434,3,125,595,3,201,360和5,204,930中公开的,所有这些专利都作为参考文献并入本文,特别包括3,4—环氧基环己酸3,4—环氧基环己基甲基酯,双—(3,4—环氧基—环己基甲基)—己二酸酯,乙烯基环己烷二环氧化物,双(2,3—环氧基环苯基)醚,环氧化丁二烯,2,3—环氧基—2—甲基环己基—甲基—3,4—环氧基—2—甲基环己羧酸酯等。
特别优选的可辐照固化的组分是阳离子UV—固化环脂肪环氧化物,它们是由Union Carbide Chemicals and Plastics company,Dan-bury,CT以Cyracure商标名如Cyracure UVR6110,6100,6379,6351和6200销售。
通常辐照可固化组分约占整个组合物的约10—95%(重量),优选15—70%(重量),更优选35—85%(重量)。
可辐照固化的组分也可含有分子量小于850和粘度小于60泊的含多元醇的酯。这些含多元醇的酯用酯交换或醇酸树脂领域公知的方法制备。适宜的含多元醇的酯公开在U.S.Patent no.3,994,851中,该专利以参考文献并入本文,含多元醇的酯是多元羧酸(如己二酸,壬二酸,马来酸,富马酸,琥珀酸或戊二酸)和多元醇(如乙二醇,新戊二醇,二乙二醇,三羟甲基单烯丙基醇,1,6—己二醇等)的反应产物,由Union Carbide以商标名TONE Polyvls特别是TONE Polyol310销售的聚己酸内酯多元醇或三羟甲基丙烷聚己酸内酯是优选的,建议使用约1—20%(重量),优选3—15%的含多元醇酯。
当可辐照固化的组分用UV或光化辐射线而不是用电子束固化时,希望加对辐射线敏感且暴露到该辐射线时能催化聚合该组分的光引剂。即使可辐照固化组分可用电子束固化,总是选择能用UV或光化辐射线固化的组分。如果电子束用来固化该组合物,有可能用光引发剂分散。羰基化合物如酮及其衍生物是特别适宜的;例如甲乙酮,二苯酮,苄基二甲基缩酮,1—羟基环己基苯基酮,2,2—二甲氧基—2—苯基乙酰苯,二乙氧基乙酰苯,和2—甲基—1—(甲硫基苯基)—2—(4—吗啉基)—1—丙酮是优良的光引发剂。其它光敏翁盐是特别好的UV活化光引发剂。当环氧化物暴露到UV辐射线时使用促进环氧化物固化的光敏鎓盐描述在U.S、patent Nos.4,058,401,4,138,255,4,161,478中,所有这些文献作为参考文献并入本文。在这些专利中提到的光敏鎓盐是良好的UV光引发剂。三芳基鏻盐是优选的,特别是由Union Carbide以商标名CyracureUVI6974销售的三芳基鏻盐。如果有光引发剂,建议其量为约1—20%,优选3—15%(重量)。
消泡剂也可加到该组合物中。消泡剂使油墨平滑地涂到底物上而无气泡和不平整。各种消泡剂都是适宜的,但优选聚烷基丙烯酸类如由Ciba—Geigy以商标名BYK—052和BYK—053销售的在干洗溶剂汽油中的聚乙烯基丁基醚。通常建议使用1—20%,优选3—15%的消泡剂。
可辐照固化的组分也可包括粘合促进剂,它是增加可辐照固化组分与底物粘合力的试剂。能用本发明油墨组合物施彩的底物包括玻璃,陶瓷,塑料,瓷砖等。如果底物是玻璃,硅烷是玻璃优良的粘合剂并促进可辐照固化组分与玻璃或陶瓷底物的粘合。公开在美国专利5,221,560(它以对比文献并入本文)丙烯氧官能硅烷是合适的。这类丙烯氧官能硅烷包括3—甲基丙烯氧基丙基三甲氧基硅烷,3—丙烯氧基丙基三甲氧基硅烷,2—甲基丙烯氧基乙基三甲氧基硅烷,2—丙烯氧基乙基三甲氧基硅烷,3—甲基丙烯氧基丙基三乙氧基硅烷,3—丙烯氧基丙基三甲氧基硅烷,3—丙烯氧基丙基三乙氧基硅烷,2—甲基丙烯氧基乙基三乙氧基硅烷,2—甲基丙烯氧基乙基三乙氧基硅烷,2—丙烯氧基乙基三乙氧基硅烷等、缩水甘油氧基官能硅烷也是适宜的。缩水甘油氧基硅烷包括3—缩水甘油氧基丙基三甲氧基硅烷,2—缩水甘油氧基乙基三甲氧基硅烷,3—缩水甘油氧基丙基三乙氧基硅烷,2—缩水甘油氧基乙基三乙氧基硅烷,3—缩水甘油氧基丙基三甲基硅烷等。缩水甘油氧基硅烷是优选的特别是3—缩水甘油丙基三甲基硅烷。约1—10%(重量)的粘合促进剂将改进组合物与底物的粘合作用。
可加到可辐照固化组合物中的其它组分包括稳定剂,惰性填料,润湿剂,平整剂等。如果有这些组分,其量占整个组合物重量的1—15%。
用于将可辐照固化组合物着色的颜料是来自吡咯并吡咯和异二氢吲哚酮化学族的有机颜料。吡咯并吡咯为红色,异二氢吲哚为黄色。适宜的吡咯并吡咯描述在美国专利4,451,585,4,579,949,4,791,204,4,666,455,5,074,918,4,783,540,4,632,704,4,914,211,4,585,878中,所有这些专利以参考文献并入本文。吡咯并吡咯通式如下其中R1和R2各自独立地为烷基,芳烷基,芳基,取代或未取代的碳环或杂环芳基;R3和R4各自独立地为H,取代或未取代烷基,烷氧基羰基,芳酰基,苯基,苯甲酰基,苄基,芳烷基,芳基,链烷酰基,C5-6环烷基,链烯基链炔基,氨基甲酰基,烷基氨基甲酰基,芳基氨基甲酰基,或烷氧基羰基,和X是O或S。
优选的是其中R1和R2各自独立地为苯基或萘基,R3和R4为氢,和X是O的化合物。特别优选的是2,5—二氢—3,6—二—4—氯苯基吡咯并[3,4—C]吡咯—1,4—二酮,其CAS号为84632—65—5且俗名为C.I颜料红254。该颜料可从Ciba—Geigy PigmentsDivision,Newport DE以商标名Irgazin DPP Red 80购买。其它以商标名Irgazin销售的Ciba—Geigy红颜料也是适宜的。
黄色颜料是异二氢吲哚酮族颜料。适宜的异二氢吲哚酮描述在美国专利3,884,975,3,867,404,4,978,768,4,400,507,3,897,439和4,262,120,和5,194,088,所有这些专利以参考文献并入本文。优选的异二氢吲哚酮是四氯氰基苯甲酸烷基酯,特别是2,3,4,5—四氯—6—氰基苯甲酸甲酯与2—甲基—1,3—苯二胺和甲醇钠的反应产物,该颜料组分的俗名为C.I颜料黄109且可从Ciba—Geigy Pigments Division,Newpont,DE以商标名lrgazinyellow 2GLTE商购。由Ciba—Geigy制造的Irgazin Yellow系列的其它颜料也是适宜的。
本组合物中颜料组分占整个组合物的约1—50%(重量),优选约15—35%。红色或黄色颜料可单独或混合使用以获得所需的适当的色调。使用5—50%,优选10—40%红色颜料和0.5—20%,优选1—12%黄色颜料的混合物可获得特别好的红色色调。
优选的本发明有色油墨组合物包括约15—40%的颜料和55—85%可辐照固化的组分。具体地说,本组合物包括:
15—40%的异二氢吲哚酮或吡咯并吡咯颜料,
35—85%可辐照固化组分,优选阳离子UV固化的环脂肪环氧
化物。
3—15%含多元醇酯。
上述组合物优选再含3—15%(重量)的光引发剂和/或3—15%(重量)的消泡剂。
如果有色油墨组合物用来施彩玻璃或陶瓷,可加入约1—10%的硅烷以提高对玻璃底物的粘合力。
本发明也包括一种对玻璃,塑料,或陶瓷底物施彩的方法,它通过将本发明的油墨组合物以预定的设计图案涂到底物上并通过将其用UV或光化辐射线辐照固化来施彩。虽然有色组合物可涂到整个底物表面上,优选涂敷的预定设计图案在底物上留下一些无油墨区域。油墨可用各种方法包括筛网印刷,胶板印刷,手工涂等来涂敷。在油墨涂敷后,将底物用常规的UV光源发出UV或光化辐射线的光来辐照。电子束可用来代替UV发射器。调整UV发射器以使底物以一定的时间通过从而完全固化油墨组合物并使其结合到底物上。如果需要,底物可经过发射器一次或多次以完成所要求的固化。适当的时间随所用底物而变化,但通常用1—30分钟,更优选3—25分钟完成固化。在底物从发射器中出来后,油墨被完全固化和结合到底物表面上,从而根据所用颜料获得坚固、明亮,动人的红色或黄色。
此外,本发明的有色油墨当筛网印到暗色底物上时,呈现极优异的不透光性,即使使用很小目的筛网(310到320目)。当通常的无机基印刷油墨被丝网印刷到暗色底物上时,通常需涂敷2—3次,因为油墨无足够不透光性且黑色塑料完全显示出来。在这些情况下,施彩者常常将首先在暗色容器上筛印白色标标记并在其上筛印有色油墨以实现适当的施彩。最出人意料的是本发明的无机基油墨呈现出与经过多次涂敷常规无机颜料油墨所获得的等价的色彩,即使不比其更好。即使使用很细的筛网,本发明的油墨组合物在暗色底物上呈现出极优异的不透光性,仅需一次涂敷。这既省时又降低了成本。
在本发明另一个优选的实施方案中,有可能提供一个施彩后的底物,在其有色油墨热印记部分有两个色调效果。例如底物如容器能用预定设计图案用丝网印刷法将油墨组合物印到底物上,然后用电子束或适当的辐射线固化。然后用一压模将热印记箔层压到底物上,压模应加热到足以使热印记箔粘到印刷的油墨设计图案上而不粘到底物无油墨部分。热印记箔通常是层压片,包括载体材料(通常为聚酯或类似的能脱模的材料),在载体材料和后续的施彩涂层间的脱模膜,后续的施彩涂层通常为有色或金属化涂层,最常用铝或上色铝。该箔片可在一个或多个金属层和载体材料之间含其它任选层如一个或多个保护层,热熔粘合层等。更具体地说,热印记箔可定义为一个多层织网物,该织网物包括支撑膜载体,脱模涂层,一个或多个保护顶涂层,一个或多个有色涂层和热熔粘合层(以所述顺序)、热印记箔片然后用压到底物上的热熔粘合层压到容器上。压模—可为标准的热印记压模或手工压模—被加热到足以使热印记箔的热熔粘合层粘到底物的油墨施彩部分的温度。通常这一温度为约250—400°F。高于这一温度将使热印记箔变差或使油墨分解。热量的使用使热印记箔的粘合面粘到底物油墨图案上而不粘到无油墨区。当除去压模时,箔层压片部分粘到油墨施彩部分而不粘到底物无油墨区。具体地说,粘到底物上有色油墨设计图案上的是热印记箔的热熔粘合层,着色涂层和保护顶涂层(以所述顺序)。脱模涂层部分可以或可以不粘到保护底涂层上,因为脱模涂层是利用热来熔化并使支撑层从保护顶涂层脱模下来且一些剩余物仍存在。
在底物上的有色油墨能够按需要全部或部热热印记以在底物上获得悦人的双色调金属/彩色图案。此外,当底物是塑料时,油墨设计图案能涂敷和固化,热印记箔能用加热的印模涂到容器的任何部分,包括油墨设计图案,因为塑料比较低的熔点,可直接将热印记箔粘到塑料上无须中间油墨层。
下面将用说明性实施例进一步描述本发明。
实施例1
本发明的有色油墨组合物制备如下:
克 W/W%Cyracure UVR 6110(Union Carbide) 50.00 50.63Polyol 310(Union Carbide) 6.25 6.33Cyracure UVI 6974 5.00 5.06BYK-053(Union Carbide) 7.5 7.59Ingazan Red DPP 80(Ciba Geigy) 25.00 25.32Irgazan Yellow 2GLTE(Ciba Geigy) 5.00 5.07
将前三个组分混在一起并加入颜料组分。将油墨利用丝网印刷法转印到玻璃容器上。将玻璃容器进行UV辐照约5分钟以进行固化。固化后的油墨是深红色,具有平滑表面而无不规则,且很好地
结合到玻璃上。
实施例2
本发明的有色油墨组合物制备如下:
克 W/W%Cyracure UVR 6110(Uinion Carbide) 50.00 50.63Polyol 310(Union Carbide) 6.25 6.33Cyracure UVI 6974 5.00 5.06BYK-053(Union Carbide) 7.5 7.59Irgazan Yellow 2GLTE(Ciba Geigy) 30.00 30.39
将前三个组分混在一起并加入颜料组分。将油墨利用丝网印刷
法转印到玻璃容器上。将玻璃容器进行UV辐照约5分钟以进行固
化。固化后的油墨是亮黄色,具有平滑表面而无不规则,且很好地
结合到玻璃上。
实施例3
本发明的有色油油墨组合物制备如下:
克 W/W%Cyracure UVR 6110(Union Carbide) 50.00 50.63Polyol 310(Union Cubide) 6.25 6.33Cyracure UVI 6974 5.00 5.06BYK-053(Union Carbide) 7.5 7.59Irgazan Red DPP 80(Ciba Geig) 30.00 30.39
将前3个组分混在一起并加入颜料组分。用其有印记的每英寸有320条纤维的丝网将油墨转印到黑色塑料(聚乙烯)上。将容器用300瓦/分钟的发射器UV辐照5分钟以进行固化。固化的油墨是深红色的有平滑表面而无不规整且很好地结合到容器上。此外,红油墨在黑色塑料上是不透光的且呈现逼真的红色。
实施例4
用其上印有施彩图案的255条(每平方英寸255条纤维)的丝网将实施例1的油墨组合物转印到玻璃瓶上。用300瓦/30英尺/分钟的UV发射器对油墨施彩的玻璃瓶UV辐照7分钟以进行固化。用加热到250°F的印模将热印记金箔(Crown Royal Leaf,Paterson,NJ)压到容器的施彩部分几秒钟。除去印模后,热印记箔层压层的脱模层将支撑膜载体脱模留下结合到固化油墨设计图案上的箔金属层压部分,得金属金外观。
实施例5
用细尖头黑貂毛刷将实施例1的油墨组合物手工将一个花纹图案刷到清洁的聚乙烯塑料容器上。将容器通过300瓦/30英尺/分钟的UV发射器5分钟以进行UV辐照。油墨图案平滑固化且为艳深红色。
实施例6
用其上印有玫瑰图案的255条(每平方英寸255条纤维)的丝网将实施例1的组合物丝网印到黑色塑料聚乙烯瓶上。将瓶子经过300瓦/30英尺/分钟的UV发射器进行UV固化8分钟。油墨玫瑰图案是深红色的。然后玫瑰图案优先用加热印模将热印记金箔层压到玫瑰图案上,加热印模有一个图案,当其以精确图像重合压到玫瑰图案上时以提供了包金的玫瑰花瓣。印模加热到约300°F,热印记箔压到玫瑰图案上约几秒钟以进行图像重合。玫瑰图案永久性地结合到容器上且适合商业用途。
实施例7
有色油墨组合物制备如下:
55g Ebecryl 6700(芳香氨基甲酸乙酯甲基丙烯酸甲酯)Radcure
Specialties,Atlanta,Georgia
20g 302丙烯酸四氢呋喃酯(Sartomer Exton PA),
20g 506丙烯酸异冰片酯#506(Sartomer),
0.5g BYK—052,
5.0g Irgacure
25g Irgazan Red DPP80
5g Irgazan Yellow 2 GLTE
前4个组分混在一起并加入颜料。用丝网法将油墨转印到玻璃容器上。将玻璃容器UV辐照约8/分钟以进行固化。固化的油墨是浓红色并有光滑表面而无不规则。
实施例8
油墨组合物制备如下:
27克氨基甲酸乙酯甲基丙烯酸酯
55份高沸点甲基丙烯酸酯
5份丙烯酸
5份甲基丙烯酸羟乙酯
5份光引发剂
3份硅烷
25份Irgazan Red DPP 80将所得的油墨组合物涂到清洁的聚乙烯塑料容器上并进行5分钟UV辐射。该油墨是亮红色且很好地结合到容器上。
虽然本发明结合优选的实施方案进行了描述,但本发明的范围不受这些特定形式限制,相反各种变型、改进和等价方案都可包括在用后附的权利要求定义的本发明的范围内。
Claims (32)
1.一种有色油墨组合物,包括:a)一种可辐照固化的组分,该组分当直接施涂到一种底物上时是可操作的,当固化时,粘接到该底物上;和b)一种选自吡咯并吡咯、异二氢吲哚酮和它们的混合物的颜料
2.权利要求1的有色油墨组合物,含10—95%(重量)的可辐照固化的组分。
3.权利要求2的有色油墨组合物,含1—50%(重量)的颜料。
4.权利要求3的有色油墨组合物,其中可辐照固化组分通过光化辐照固化。
5.权利要求3的有色油墨组合物,其中可辐照固化组分通过紫外线辐照固化。
6.权利要求5的有色油墨组合物,其中可辐照固化组分是分子量低于50000的单体或聚合物。
7.权利要求5的有色油墨组合物,其中可辐照固化组分是一种单体。
8.权利要求7的有色油墨组合物,其中单体是环氧化物,环脂肪烃环氧化物,氯乙烯,苯乙烯,丙烯酸乙酯,乙酸乙烯酯,丙烯酸羟基烷酯,甲基丙烯羟基烷酯,丁酸乙烯酯,乙烯基甲基醚,甲基丙烯酸甲酯,丙烯酸异冰片酯,丙烯腈或它们的混合物。
9.权利要求8的有色油墨组合物,其中单体是一种阳离子UV—固化的环脂肪烃环氧化物。
11.权利要求11的有色油墨组合物,它还包括1—20%的一种含多元醇的酯,该酯分子量小于850和粘度小于60泊。
12.权利要求11的有色油墨组合物,其中含多元醇的酯是多元酸和多元醇的反应产物。
13.权利要求12的有色油墨组合物,其中含多元醇的酯是聚己酸内酯多元醇。
14.权利要求13的有色油墨组合物,还包括3—15%的光引发剂。
15.权利要求14的有色油墨组合物,其中油墨组合物包括:15—40%的一种选自异二氢吲哚酮,吡咯并吡咯和它们的混合物的颜料,35—85%的阳离子UV—固化的环脂肪环氧化物,3—15%的光引发剂,它为三芳基鏻盐,1—20%的多烷基丙烯酸类消泡剂,3—15%的聚己酸内酯多元醇。
16.权利要求15的有色油墨组合物,其中颜料选自2,5—二氢—3,6—二—4—氯苯基—吡咯并[3,4—C]吡咯—1,4—二酮,2,3,4,5—四氯—6—氰基—苯甲酸甲酯与2—甲基—1,3—苯二胺和甲醇的反应产物,和它们的混合物。
17.权利要求16的有色油墨组合物,其中阳离子固化环脂肪环氧化物选自:3,4—环氧基环己酸3,4—环氧基环己基甲基酯,双—(3,4—环氧基—环己基甲基)—己二酸酯,乙烯基环己烷二环氧化物,双(2,3—环氧基环苯基)醚,环氧化丁二烯,2,3—环氧基—2—甲基环己基—甲基—3,4—环氧基—2—甲基环己酸酯。
18.权利要求17的有色油墨组合物,其中多烷基丙烯酸类消泡剂是聚乙烯基丁基醚。
19.权利要求18的有色油墨组合物,其中聚己酸内酯多元醇是三羟甲基丙烷聚己酸内酯。
20.一种在底物上涂敷彩色施彩物的方法,包括:a)以预定的设计图案将一种有色油墨组合物施涂到底物上,所述组合物包括一种可辐照固化的组分和一种选自吡咯并吡咯,异二氢吲哚酮和它们的混合物的颜料,所述油墨当固化粘到底物上时是可操作的,b)通过将油墨暴光在辐照下将其固化在底物,由于辐射固化:粘接油墨到底物上。
21.权利要求20的方法,其中有色油墨组合物包括10—95%的可辐照固化的组分。
22.权利要求21的方法,其中有色油墨组合物包括1—50%颜料。
23.权利要求22的方法,其中可辐照固化组分用UV辐照固化。
24.权利要求23的方法,其中可辐照固化组分是阳离子UV—固化环脂肪环氧化物。
25.权利要求24的方法,其中颜料选自:2,5—二氢—3,6—二—4—氯苯基—吡咯并[3,4—C]吡咯—1,4—二酮,2,3,4,5—四氯—6—氰基—苯甲酸甲酯与2—甲基—1,3—苯二胺和甲醇钠的反应产物;和它们的混合物。
26.权利要求25的方法,其中有色油墨组合物用丝网法涂到底物上。
27.权利要求26的方法,其中底物是玻璃、塑料和陶瓷制品。
28.权利要求27的方法,其中底物是容器。
29.一种用有色油墨和热压印箔对底物施彩的方法,包括:a)以预定的设计图案将一种有色油墨组合物施涂到底物上,所述组合物包括一种可辐照固化的组分和一种选自吡咯并吡咯,异二氢吲哚酮和它们的混合物的颜料,所述油墨当固化粘到底物上时是可操作的,b)通过将油墨暴光在辐照线下将其固化在底物,由于辐射固化:粘接油墨到底物上,c)用印模将热印记箔板压到底物上,印模加热到足以使箔部分粘到底物的加热固化的油墨设计图案上,而不粘到底物无油墨区域上的温度,和d)除去印模,留下粘到油墨设计图案上的箔部分。
30.一种有内表面和外表面的容器,其中外表面有一个以预定设计图案结合到其上的固化粘合油墨涂层,该油墨是一个有色组合物,该组合物包括I)一种可辐照固化的组分,该组分当直接施涂到一种底物上时是可操作的,当固化时,粘接到该底物上;II)一种选自吡咯并吡咯、异二氢吲哚酮和它们的混合物的颜料。
31.权利要求30的容器,它为玻璃容器。
32.权利要求30的容器,它为塑料容器。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/199,414 US5571359A (en) | 1992-01-24 | 1994-02-22 | Radiation curable pigmented compositions |
US199414 | 1994-02-22 |
Publications (1)
Publication Number | Publication Date |
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CN1114666A true CN1114666A (zh) | 1996-01-10 |
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ID=22737387
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CN95102054A Pending CN1114666A (zh) | 1994-02-22 | 1995-02-20 | 可辐照固化的有色组合物 |
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US (1) | US5571359A (zh) |
EP (1) | EP0668332A3 (zh) |
JP (2) | JPH0841403A (zh) |
KR (1) | KR950032525A (zh) |
CN (1) | CN1114666A (zh) |
AU (1) | AU691852B2 (zh) |
BR (1) | BR9500676A (zh) |
CA (1) | CA2141914A1 (zh) |
FI (1) | FI950821A (zh) |
IL (1) | IL112392A0 (zh) |
NO (1) | NO950649L (zh) |
SG (1) | SG49895A1 (zh) |
TW (1) | TW350039B (zh) |
ZA (1) | ZA951325B (zh) |
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- 1995-01-19 IL IL11239295A patent/IL112392A0/xx unknown
- 1995-02-06 CA CA002141914A patent/CA2141914A1/en not_active Abandoned
- 1995-02-07 AU AU11608/95A patent/AU691852B2/en not_active Ceased
- 1995-02-07 TW TW084100970A patent/TW350039B/zh active
- 1995-02-17 ZA ZA951325A patent/ZA951325B/xx unknown
- 1995-02-17 BR BR9500676A patent/BR9500676A/pt not_active Application Discontinuation
- 1995-02-20 CN CN95102054A patent/CN1114666A/zh active Pending
- 1995-02-21 NO NO950649A patent/NO950649L/no not_active Application Discontinuation
- 1995-02-21 KR KR1019950003297A patent/KR950032525A/ko not_active Application Discontinuation
- 1995-02-22 EP EP95301170A patent/EP0668332A3/en not_active Withdrawn
- 1995-02-22 JP JP7033233A patent/JPH0841403A/ja active Pending
- 1995-02-22 SG SG1996008624A patent/SG49895A1/en unknown
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1999
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1484680B (zh) * | 2000-11-09 | 2011-09-07 | 3M创新有限公司 | 特别适合户外用途的耐候性可辐照固化可喷墨的液体组合物 |
CN103296441A (zh) * | 2012-02-29 | 2013-09-11 | 深圳光启创新技术有限公司 | 新型超材料及其制作工艺 |
CN103296441B (zh) * | 2012-02-29 | 2021-10-19 | 深圳光启高等理工研究院 | 新型超材料及其制作工艺 |
CN112028893A (zh) * | 2020-09-29 | 2020-12-04 | 天津理工大学 | 一种吡咯并吡咯结构的光引发剂及其制备方法和应用 |
CN112028893B (zh) * | 2020-09-29 | 2023-01-06 | 天津理工大学 | 一种基于吡咯并吡咯结构的光引发剂配制的光聚合体系和应用 |
Also Published As
Publication number | Publication date |
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IL112392A0 (en) | 1995-03-30 |
NO950649D0 (no) | 1995-02-21 |
TW350039B (en) | 1999-01-11 |
SG49895A1 (en) | 1998-06-15 |
KR950032525A (ko) | 1995-12-22 |
NO950649L (no) | 1995-08-23 |
FI950821A (fi) | 1995-08-23 |
EP0668332A2 (en) | 1995-08-23 |
AU1160895A (en) | 1995-08-31 |
CA2141914A1 (en) | 1995-08-23 |
JPH0841403A (ja) | 1996-02-13 |
JP2000129162A (ja) | 2000-05-09 |
FI950821A0 (fi) | 1995-02-22 |
ZA951325B (en) | 1995-10-23 |
EP0668332A3 (en) | 1996-09-18 |
BR9500676A (pt) | 1995-10-24 |
AU691852B2 (en) | 1998-05-28 |
US5571359A (en) | 1996-11-05 |
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