CN1051294C - 施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器 - Google Patents

施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器 Download PDF

Info

Publication number
CN1051294C
CN1051294C CN95102053A CN95102053A CN1051294C CN 1051294 C CN1051294 C CN 1051294C CN 95102053 A CN95102053 A CN 95102053A CN 95102053 A CN95102053 A CN 95102053A CN 1051294 C CN1051294 C CN 1051294C
Authority
CN
China
Prior art keywords
ink
substrate
ester
die
paper tinsel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN95102053A
Other languages
English (en)
Other versions
CN1119176A (zh
Inventor
M·E·卡门
B·帕泰尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RADIATION CURABLE PIGMENTED COMPOSITIONS
Original Assignee
RADIATION CURABLE PIGMENTED COMPOSITIONS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RADIATION CURABLE PIGMENTED COMPOSITIONS filed Critical RADIATION CURABLE PIGMENTED COMPOSITIONS
Publication of CN1119176A publication Critical patent/CN1119176A/zh
Application granted granted Critical
Publication of CN1051294C publication Critical patent/CN1051294C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0054—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485—Pigments
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S215/00—Bottles and jars
    • Y10S215/06—Resin-coated bottles
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • 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.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • 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.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer

Abstract

用热印记箔施彩底物的方法，包括下列步骤：a)以预定的设计图案将一种含有阳离子辐照固化的环脂肪环氧化物施涂到底物上，所述油墨当其固化结合到底物上时是可操作的，b)用辐照将底物上的油墨固化，以使油墨组合物结合到底物上，c)用印模将热印记箔片压到底物上，该印模加热到足以使热印记箔部分粘合到底物的加热固化的油墨设计图案上而不粘合到无油墨区，和d)除去印模，以留下粘合到油墨设计图案上的箔部分。

Description

施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器
本申请是1992年11月24日递交的美国专利申请系列号824，968的部分继续申请。
本发明属于在玻璃和陶瓷底物上施涂施彩印记的领域
热印记是从热塑性底物上的聚酯载体向有色或金属化表面的热传递。加热的印模或辊子用来施加压力到热印记箔上。压力使得箔的有色或金属化部分与塑料底物接触。热和压力的结合软化了塑料底物并活化了箔，使其结合到底物上。当箔除去后，仅仅进行了热印记的区域结合到塑料底物上。垂直印记或辊涂机器用于该操作。垂直印记机器有一个加热的青铜、不锈钢或聚硅氧烷橡胶的印模以转印一个特定模型的区域。辊涂方法使用聚硅氧烷橡胶辊子或弧形印模以在连续或间歇法中施涂箔。热传递可在约107℃下进行。
热印记是一种向热塑性底物上施涂施彩物的有效而廉价的方法。热印记不能用在玻璃上因为玻璃熔点远比大多数热塑性物料高。
通常施彩物以金或银叶、彩色图案或印记的形式用类似于在陶瓷上上釉的方法施涂到玻璃上。有色或金属油墨施彩物用各种方法如丝网法，印刷法等施涂到玻璃容器上。容器然后经历极高的炉温度焙烧施彩物。遗憾的是这种方法费时耗能又昂贵，由于操作炉的高温和气体，因而必须考虑安全问题。
这样极需一种用于在玻璃底物上施涂施彩物的简单、经济和极安全的方法。
本发明涉及用热印记箔施彩底物的方法，包括下列步骤：
a)以预定的设计图案将一种含有阳离子辐照固化的环脂肪环氧化物施涂到底物上，所述油墨当其固化结合到底物上时是可操作的。
b)用辐照将底物上的油墨固化，以使油墨组合物结合到底物上，
c)用印模将热印记箔片压到底物上，该印模加热到足以使热印记箔部分粘合到底物的加热固化的油墨设计图案上而不粘合到无油墨区，和
d)除去印模，以留下粘合到油墨设计图案上的箔部分。
术语“印模”表示任何能加热到足以使热印记箔粘合到固化油墨图案上的温度并能将热印记压到热印记箔底物上的物体。适宜的印模包括在常规印记机器中的青铜、不锈钢或聚硅氧烷橡胶印模，手涂辊，聚硅氧烷橡胶辊，弧形印模等。
术语“底物”表示能施彩的玻璃、陶瓷或瓷底物包括容器、施彩物、雕像、花瓶、窗子、瓷砖等。
术语“热印记箔”通常表示一个层压片，它包括下列顺序的载体材料(常为聚酯，纤维素乙酸酯或其它能脱模的材料)，脱模膜，和施彩或有色涂层。施彩涂层通常是彩色或金属涂层。金属涂层可以是真正的金、银或上彩后看上去像金或银或有全息光性能的铝。有色层最常用真空金属化方法涂敷。更具体地说，热印记箔可定义为一个多层编织网，它包括以下列顺序的支撑膜载体，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。在通常的热印记法中，箔的热熔粘合层用加热的印模压到底物上。热熔粘合层粘合到底物上且热量使脱模层从保护顶涂层上将支撑膜载体脱膜从而留下叠放在底物表面上的保护顶涂层。脱模涂层或者是蜡或蜡类材料或加热时熔化从而使保护顶涂层从脱模支撑层中脱模的热塑料物料，包括乙烯—乙酸乙烯酯(EVA)，丙烯酸类塑料，聚氯乙烯(PVC)，聚酰胺，或描述在美国专利5,104,719(它以参考文献并入本文)中的类似的热塑性材料。保护顶涂层通常是一些清漆，它能保护有色或金属化层。最后一层是热熔粘合层，它可为各种物质，且选择的使其在加热时能粘合到其施涂的底物上。通常热塑性材料如EVA，PVC等也是适宜的热熔粘合物。
术语“光化辐射线”意味着波长为4-600nm的光。
术语“紫外线”表示波长4-400nm，优选325-365nm的光。
油墨组合物包括一种阳离子辐照固化的环脂肪环氧化物，优选每分子有至少两个环氧基的环脂肪环氧化物。聚环脂肪环氧化物也是适宜的如由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制得的物质。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中公开的环脂肪环氧化物是适宜的，所有这些专利都作为参考文献并入本文。优选的是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-甲基环己酸酯等。
特别优选的环脂肪环氧化物是阳离子UV-固化环脂肪环氧化物，它们是由Union Carbide Chemicals and Plastics Company，Danbury，CT以商标名如Cyracure UVR 6110，6100，6379，6351和6200销售。建议使用约10-90％，优选约35～90％的阳离子UV固化环脂肪环氧化物。
油墨组合物可含有分子量小于850和粘度小于60泊的含多元醇的酯以控制粘度。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的低聚物。适宜的含多元醇的酯公开在U.S.Patentno.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 Polyols特别是TONE Polyol 310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。
油墨组合物也可包括粘合促进剂，它是增加环脂肪环氧化物与底物粘合力的试剂。如果底物是玻璃，硅烷是玻璃优良的粘合剂并促进油墨与底物的粘合。公开在美国专利5,221,560中(它以对比文献并入本文)的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，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。
如果油墨组合物用UV或光化射线而不是用电子束固化，希望加能催化环脂肪环氧化物聚合的光引发剂。如果使用电子束，无须使用光引发剂。羰基化合物如酮及其衍生物特别适宜作光引发剂；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。其它光敏鎓盐是特别好的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。优选的光引发剂是三芳基鏻盐，特别是由Union Carbide以商标名Cyracure UVI 6974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。
其它组分也可加到油墨中包括稳定剂，惰性填料，润湿剂，平整剂等。如果有这些组分约占整个组合物的约1-15％(重量)。
本发明优选的油墨组合物包括：
35-85％阳离子UV固化环脂肪环氧化物，
3-15％含多元醇酯
3-15％消泡剂。
此外，优选的组合物含3-15％光引发剂，和它可含1-10％硅烷。
本发明的油墨组合物能用各种方法包括丝网或网印刷，胶板印刷(Offset printing)或任何其它涂敷方法涂到底物上。丝网印刷是优选的，因为它适用于在线生产。对于油墨涂到诸如雕像或其它用丝网涂敷不易进行的精制施彩物品的情况，涂刷或其它类似手工涂敷器的手工涂敷可使用。
在油墨组合物涂到底物上后，用可将其固化的辐射线将其固化。虽然光化射线，优选UV辐射线是适合环氧化物的固化剂，但电子束也可用来固化环脂肪环氧化物。为进行环氧化物和多元醇的聚合，将施彩底物用UV光固化足够时间通常为1-30分钟，优选2-25分钟，取决于油墨涂到底物上的厚度。UV输送器如由Fusion Systems制备的适合这种用途。UV输送器包括安装在紫外灯的传输带。当底物放在移动的传输时，它被灯辐照。很明显，当固化时间很长时，底物可重复经过几个相连的输送器或经过同一个输送器几次。传输器的设定应使底物经适当的时间通过以使油墨固化和粘合到底物上。
在油墨被固化和粘合到底物上后，将底物用热印记箔印记。具体地说，用加热的印模将箔压到底物上足够时间以使热印记箔粘合到固化的油墨图案上但不粘合到底物无油墨区。通常印模应加热到250-400，优选250-350°F以使箔粘合到固化油墨图案上。将印模压到底物上一定时间，从不到1秒钟到几分钟，这取决于所用印模，印模温度和具体的环脂肪环氧化物。当加热后的印模除去后，将热印记箔剥下。热印记箔部分，特别是热熔粘合层和金属化或有色层和保护顶涂层(如果有的话)以所述顺序粘到固化的油墨图案上以使热熔粘合层粘到固化容器表面的设计图案上，随后是着色涂层和保护顶涂层。保护顶涂层可含或可不含脱模涂层部分，它用来将载体层从保护顶涂层上脱模。
涂到底物上的施彩物极耐用且能经受在手工操作中的各种条件。
                     实施例1
亮色油墨组合物制备如下
                        克             W/W％Cyracure UVR 6110           50             72.73Polyol 310                  6.25           9.10Cyracure UVI 6974           5.00           7.27BYK-053                     7.5            10.90
将所述组分混合直至溶解。
                      实施例2
用印有施彩图案的每英寸有255条纤维的网将实施例1的油墨组合物丝网印到玻璃制的容器上。将玻璃容器用5分钟经过300瓦/30英尺/分钟的UV传输器以固化油墨。用加热到250°F的印模将金热印记箔(Crown Royal Leaf，Paterson，NJ)压到容器上几秒钟。将印模除去留下只粘到油墨图案上的箔部分，从而获得与金叶有相同外观的金色施彩图案。
                    实施例3
用细尖头貂毛刷将实施例1的油墨组合物手工涂一个简单图案到陶瓷碗一侧。将该碗用约4分钟经过300瓦/300英尺/分钟UV传输器以进行UV辐照。将银全息热印记箔用加热到300°F的印模印到固化油墨图案上几秒钟。除去印模，热印记箔的部分粘到固化油墨图案上，得金属银施彩物。

Claims (17)

1.一种用热印记箔施彩底物的方法，包括下列步骤：
a)以预定的设计图案将一种含有阳离子辐照固化的环脂肪环氧化物的油墨组合物施涂到底物上，所述油墨当其固化结合到底物上时是可操作的，
b)用辐照将底物上的油墨固化，以使油墨组合物结合到底物上，
c)用印模将热印记箔片压到底物上，该印模加热到足以使热印记箔部分粘合到底物的加热固化的油墨设计图案上而不粘合到无油墨区，和
d)除去印模，以留下粘合到油墨设计图案上的箔部分。
2.权利要求1的方法，其中环脂肪环氧化物是用紫外线辐照固化。
3.权利要求2的方法，其中油墨是用丝网涂敷到底物上。
4.权利要求3的方法，其中热印记箔包括以下列次序的载体材料，脱模膜和施彩涂层。
5.权利要求4的方法，其中热印记箔包括多层编织网，所述网包括以下列次序的支撑膜载体，脱模涂层，保护顶涂层，着色涂层和热熔粘合层。
6.权利要求5的方法，其中印模加热到至少250°F。
7.权利要求6的方法，其中油墨组合物还包括1-20％的含多元醇的酯。
8.权利要求7的方法，其中油墨组合物还包括1-10％的消泡剂。
9.一种可辐照固化的聚合物组合物，  包括：
10-90％的可阳离子辐照固化的环脂肪环氧化物，
1-20％的含多元醇的酯，和
1-20％的消泡剂。
10.权利要求9的组合物，其中含多元醇的酯是多元酸和多元醇的反应产物。
11.权利要求10的组合物，其中含多元醇的酯的分子量小于850，粘度小于60泊。
12.权利要求11的组合物，其中含多元醇的酯是聚己酸内酯多元醇。
13.权利要求9的组合物，还包括1-15％的颜料。
14.权利要求9的组合物，其中消泡剂是聚乙烯基丁基醚。
15.权利要求9的组合物，其中可阳离子辐照固化的环脂肪环氧化物选自3，4-环氧基环己酸3，4-环氧环己基甲基酯，己二酸二-(3，4-环氧基环己基甲基)酯，乙烯基环己烷二环氧化物，双(2，3-环氧基苯基)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-甲基环已酸酯，和它们的混合物。
16.一种具有内表面和外表面的玻璃、陶瓷或瓷容器，其中：
a)所述外表面有一个结合到其上的固化粘合油墨部分涂层图案，所述油墨是可阳离子辐照固化的环脂肪环氧化物，所述图案没有完全覆盖整个所述外表面，和
b)油墨图案完全被一个多层编织网覆盖，所述编织网包括下列从油墨设计图案向外顺序的(i)热熔粘合层，(ii)着色涂层和(iii)保护顶涂层，所述编织网粘合上固化粘合油墨且仅仅覆盖所述油墨而不延及到所述外表面无油墨区。
17.权利要求16的容器，其中多层编织网包括以下列顺序的(i)热熔粘合层，(ii)着色层，(iii)保护涂层，(iv)脱模涂层和(v)支撑膜载体。
CN95102053A 1994-02-22 1995-02-20 施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器 Expired - Fee Related CN1051294C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US199,415 1994-02-22
US08/199,415 US5487927A (en) 1992-01-24 1994-02-22 Decorating method and products

Publications (2)

Publication Number Publication Date
CN1119176A CN1119176A (zh) 1996-03-27
CN1051294C true CN1051294C (zh) 2000-04-12

Family

ID=22737392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95102053A Expired - Fee Related CN1051294C (zh) 1994-02-22 1995-02-20 施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器

Country Status (22)

Country Link
US (3) US5487927A (zh)
EP (2) EP0668170B1 (zh)
JP (1) JP2889146B2 (zh)
KR (1) KR950031544A (zh)
CN (1) CN1051294C (zh)
AT (2) ATE194634T1 (zh)
AU (2) AU683968B2 (zh)
BR (1) BR9500677A (zh)
CA (1) CA2141915C (zh)
DE (2) DE69508452T2 (zh)
DK (1) DK0668170T3 (zh)
ES (2) ES2150191T3 (zh)
FI (1) FI950822A (zh)
GR (1) GR3030237T3 (zh)
HK (2) HK1009141A1 (zh)
IL (1) IL112393A (zh)
NO (1) NO950650L (zh)
NZ (1) NZ270524A (zh)
PT (1) PT825218E (zh)
SG (1) SG49241A1 (zh)
TW (1) TW321666B (zh)
ZA (1) ZA951324B (zh)

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5626702A (en) * 1991-05-17 1997-05-06 Holotex Limited Process for production of flexible laminate
US5981629A (en) * 1995-03-31 1999-11-09 Cork; Michael S. Epoxy system for bonding to unsanded polymer-coated fiberglass surfaces
NL1000614C2 (nl) * 1995-06-20 1996-12-23 Leer Koninklijke Emballage Werkwijze voor het vervaardigen van een gelamineerd produkt.
US5656336A (en) * 1996-03-08 1997-08-12 Revlon Consumer Products Corporation Glass decorating method using bis-phenol-a epoxy resins and related compositions and articles
US5900096A (en) * 1996-09-03 1999-05-04 Zemel; Richard Method of transferring metal leaf to a substrate
US5891289A (en) * 1996-09-16 1999-04-06 Zemel; Richard S. Method of transferring metal leaf to a substrate
JP2001513717A (ja) * 1997-03-06 2001-09-04 フォーカル デザイン ストゥーディオス リミテッド 圧力および／または熱付与形画像転写シート
GB9706427D0 (en) * 1997-03-27 1997-05-14 Pearson David Glass treatment process and apparatus
US6093455A (en) * 1997-05-23 2000-07-25 Deco Patents, Inc. Method and compositions for decorating glass
GB2328215A (en) * 1997-08-16 1999-02-17 Simon Ellis A printing ink used in the process of foil stamping
AU4754697A (en) * 1997-10-15 1999-05-03 Revlon Consumer Products Corporation Apparatus and method for screen printing radiation curable compositions
US6283022B1 (en) 1997-10-17 2001-09-04 Deco Patents, Inc. Apparatus and method for direct rotary screen printing radiation curable compositions onto cylindrical articles
GB2353532B (en) * 1998-03-23 2001-08-01 Api Foils Ltd Hot dieless foiling
US6489375B2 (en) * 1998-07-07 2002-12-03 Sun Chemical Corporation Low VOC cationic curable lithographic printing inks
DE69930831T2 (de) * 1998-07-07 2006-11-30 Sun Chemical Corp. Kationisch härtbare lithographische druckfaben mit einem geringen gehalt an fl üchtigen organischen verbindungen
US6562172B1 (en) 1998-08-17 2003-05-13 Deco Patents, Inc. Glass decorating method using ink compositions containing N-vinyl lactams
US6514586B1 (en) * 1998-08-28 2003-02-04 Kun Lee Hwang Hot stamping foil
US6361640B1 (en) 1998-08-31 2002-03-26 Deco Patents, Inc. Edge decorated articles and method of making same using hot stamping foils
US6504559B1 (en) 1998-09-14 2003-01-07 Gerald W. Newton Digital thermal printing process
US6214414B1 (en) * 1999-07-22 2001-04-10 Ppg Industries Ohio, Inc. Method for forming a sequence of crosslinked pigmented coatings on ceramic substrates
FR2800011B1 (fr) 1999-10-22 2001-12-07 Oreal Procede de marquage a chaud et structure multicouche pour la mise en oeuvre d'un tel procede
US6524674B1 (en) * 2000-02-24 2003-02-25 Glass Unlimited Of High Point, Inc. Glass panel with simulated metal strip
CZ20002811A3 (cs) * 2000-08-02 2002-02-13 Irisa, Výrobní Dru®Stvo Způsob výroby vánočních ozdob a přípravky pro jejich upevňování při provádění tohoto způsobu
JP2004514014A (ja) * 2000-11-09 2004-05-13 スリーエム　イノベイティブ　プロパティズ　カンパニー 屋外用途に特に適した耐候性でインクジェット可能な放射線硬化性流体組成物
DE10103884B4 (de) * 2001-01-30 2006-05-04 Richard Mayer Buchbindermeister Gmbh Verfahren zur erhabenen Beschichtung von Trägermaterialien
FR2820348B1 (fr) * 2001-02-07 2003-10-24 Oreal Film et procede de marquage a chaud
US6684770B2 (en) 2001-06-29 2004-02-03 Deco Patents, Inc. Apparatus and method for direct rotary printing compositions onto cylindrical articles
US6671087B2 (en) 2002-04-09 2003-12-30 Premakaran T. Boaz Reflector assembly for UV-energy exposure system
FR2846970B1 (fr) * 2002-11-08 2006-08-11 Desarrollo Del Grafting S L Procede de traitement de surface par photopolymerisation pour obtenir des proprietes biocides
US7094307B2 (en) * 2003-01-06 2006-08-22 Joan Morris Methods for coating surfaces with metal and products made thereby
US20040144479A1 (en) * 2003-01-23 2004-07-29 Peter Cueli Preparation of novel physical transfer elements such as hot stamping foil and methods for using the same in producing chemically resistant bonds
US20040161564A1 (en) * 2003-02-14 2004-08-19 Truog Keith L. Dry paint transfer laminate
CN100358729C (zh) * 2003-04-25 2008-01-02 乐金电子(天津)电器有限公司 电子产品门面标识语印刷构造以及印刷方法
DE102004004713A1 (de) * 2004-01-30 2005-09-01 Leonhard Kurz Gmbh & Co. Kg Sicherheitselement mit partieller Magnetschicht
WO2006064884A1 (ja) * 2004-12-15 2006-06-22 Kuraray Co., Ltd. 活性エネルギー線硬化性樹脂組成物およびその用途
US8197058B2 (en) 2005-10-21 2012-06-12 Agfa Graphics Nv Set of curable liquids and methods for inkjet printing
EP1940982A1 (en) 2005-10-21 2008-07-09 Agfa Graphics Nv Curable inkjet ink set and methods for inkjet printing
EP1940981A1 (en) 2005-10-21 2008-07-09 Agfa-Gevaert N.V. Method for preparing tamperproof id documents
US20090114796A1 (en) * 2007-11-01 2009-05-07 Shao-Chiu Lin Multipurpose ceramic cake mold
DE102008000721A1 (de) 2008-03-18 2009-09-24 Evonik Degussa Gmbh Strahlenhärtbare Formulierungen
KR100892451B1 (ko) * 2008-03-24 2009-04-10 한종묵 열경화성수지 식기의 표면 장식방법
CN103296445B (zh) * 2012-02-29 2016-09-28 深圳光启创新技术有限公司 超材料的制造方法
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
DE102012009773A1 (de) * 2012-05-16 2013-11-21 Heinz-Glas Group Holding HGGH GmbH & Co. KGaA Verfahren und Vorrichtung zum Bedrucken eines Werkstücks aus Glas mit einer Heißprägefolie unter Verwendung eines Prägestempels
US9630385B2 (en) * 2012-11-08 2017-04-25 Toray Plastics (America), Inc. Releasable polyester metal transfer film
CN105848917B (zh) * 2013-10-14 2019-12-06 康宁股份有限公司 在基材上印刷装饰图案的方法
DE102013111378A1 (de) 2013-10-15 2015-04-16 Marabu Gmbh & Co. Kg Verfahren zur Dekoration von Substraten sowie dekoriertes Substrat
JP6424894B2 (ja) * 2014-08-06 2018-11-21 コニカミノルタ株式会社 ラテックスインク、これを用いた箔画像形成方法、積層体、および壁紙
US9796191B2 (en) 2015-03-20 2017-10-24 Corning Incorporated Method of inkjet printing decorations on substrates
CZ305847B6 (cs) * 2015-04-29 2016-04-06 Heinz Glas Decor S.R.O. Způsob reliéfního zdobení předmětů ze surového nebo zpracovaného skla
GB201509080D0 (en) 2015-05-27 2015-07-08 Landa Labs 2012 Ltd Coating apparatus
CN116568523A (zh) * 2020-10-16 2023-08-08 艾利丹尼森零售信息服务有限公司 可雕刻热传递标签及装饰

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57152992A (en) * 1981-03-19 1982-09-21 Kamaya Kagaku Kogyo Kk Decoration of brilliant metallic letter and picture, etc.
JPS59184746A (ja) * 1983-04-01 1984-10-20 Koa Glass Kk ガラス表面における光輝性メタリツク文字或いは図柄等の加飾方法

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125592A (en) * 1964-03-17 Preparation of polymerizable vinylated
US2890197A (en) * 1957-04-04 1959-06-09 Union Carbide Corp Composition comprising a diepoxide, a polycarboxylic acid and a polyhydric compound
US3027357A (en) * 1958-07-15 1962-03-27 Union Carbide Corp Cross-linking carboxyl containing polymers
US3031434A (en) * 1958-08-11 1962-04-24 Glidden Co Method of curing epoxy components and heat-curable epoxy compositions
NL259331A (zh) * 1959-12-24
US3117009A (en) * 1962-01-16 1964-01-07 R R Boelter Company Inc Method and apparatus for producing a starter culture for making cheese and the like
US3235395A (en) * 1962-03-27 1966-02-15 Walter G Scharf Transfers for metallic coatings
CH424823A (de) * 1965-09-02 1966-11-30 Interservice S A Verfahren zum Anbringen einer Bedruckung aus Metallpulver an Gegenständen
US3994851A (en) * 1972-10-26 1976-11-30 Ppg Industries, Inc. High solids polyester coating composition
JPS5523222B2 (zh) * 1972-12-28 1980-06-21
US3890194A (en) * 1974-04-11 1975-06-17 Rca Corp Method for depositing on a substrate a plurality of epitaxial layers in succession
US4161478A (en) * 1974-05-02 1979-07-17 General Electric Company Photoinitiators
US4058401A (en) * 1974-05-02 1977-11-15 General Electric Company Photocurable compositions containing group via aromatic onium salts
JPS51118507A (en) * 1975-04-10 1976-10-18 Toyoji Hirahara Marking method for plastic molds
GB1552046A (en) * 1977-02-02 1979-09-05 Ciba Geigy Ag Film adhesives
US4138255A (en) * 1977-06-27 1979-02-06 General Electric Company Photo-curing method for epoxy resin using group VIa onium salt
US4321087A (en) * 1978-12-21 1982-03-23 Revlon, Inc. Process for making metallic leafing pigments
US4219377A (en) * 1979-03-14 1980-08-26 Minnesota Mining And Manufacturing Company Photocurable epoxy composition having improved flexibility comprising vinyl terminated acrylonitrile-butadiene polymer
US4421904A (en) * 1979-08-03 1983-12-20 General Electric Company Ultraviolet curable silicone coating compositions
JPS5715299A (en) * 1980-07-02 1982-01-26 Panafacom Ltd Memory access control system of doubled memory
EP0106628B1 (en) * 1982-10-08 1987-01-07 Johnson Matthey Public Limited Company Printing ink
US4874798A (en) * 1983-02-07 1989-10-17 Union Carbide Corporation Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials and substituted cycloaliphatic monoepoxide reactive diluents
US4593051A (en) * 1983-02-07 1986-06-03 Union Carbide Corporation Photocopolymerizable compositons based on epoxy and polymer/hydroxyl-containing organic materials
US4707535A (en) * 1983-10-27 1987-11-17 Union Carbide Corporation Low viscosity adducts of a poly(active hydrogen) organic compound and polyepoxide
US4717605A (en) * 1984-05-16 1988-01-05 Merck Patent Gesellschaft Mit Beschrankter Haftung Radiation curable adhesives
CA1312040C (en) * 1985-12-19 1992-12-29 Joseph Victor Koleske Conformal coatings cured with actinic radiation
JPH0688449B2 (ja) * 1986-07-09 1994-11-09 株式会社日野樹脂 ガラス製被転写体の連続加飾加工印刷方法
CA1305823C (en) * 1986-08-29 1992-07-28 Union Carbide Corporation Photocurable blends of cyclic ethers and cycloaliphatic epoxides
JPS63131674A (ja) * 1986-11-20 1988-06-03 Semiconductor Energy Lab Co Ltd 無線放送電子新聞
US4964938A (en) * 1987-04-13 1990-10-23 Dymax Corporation Bonding method using photocurable acrylate adhesive containing perester/tautomeric acid adhesion promoter
US4847329A (en) * 1987-06-30 1989-07-11 Union Carbide Corporation (N-substituted carbamoyloxy)alkanoyloxyalkyl acrylate polymers and compositions made therefrom
FR2625450B1 (fr) * 1988-01-05 1992-05-07 Corning Glass Works Article muni d'un revetement anti-adherent presentant une adhesion audit substrat et une durabilite ameliorees, sa fabrication et composition mise en oeuvre
US5221560A (en) * 1989-02-17 1993-06-22 Swedlow, Inc. Radiation-curable coating compositions that form transparent, abrasion resistant tintable coatings
DE69030981T2 (de) * 1989-03-30 1997-10-23 Toyo Boseki Strahlungshärtbares Harz und dieses enthaltende Zusammensetzung
US5010118A (en) * 1989-06-22 1991-04-23 General Electric Company UV curable non-toxic epoxysilicone release coating compositions
US5104719A (en) * 1989-08-30 1992-04-14 Revlon, Inc. Heat activated, quick release decals and associated methods
JP3097867B2 (ja) * 1990-03-07 2000-10-10 ダウ・コ−ニング・コ−ポレ−ション エポキシド及びコロイドシリカを含有する放射線硬化性保護塗料組成物
DE4013298C2 (de) * 1990-04-26 1998-11-12 Mannesmann Sachs Ag Befestigung eines Schwungrades an der Kurbelwelle einer Brennkraftmaschine
DE4102340A1 (de) * 1991-01-26 1992-07-30 Bayer Ag Lichtleitfasern und verfahren zu ihrer herstellung
US5266715A (en) * 1991-03-06 1993-11-30 Ciba-Geigy Corporation Glass coating with improved adhesion and weather resistance
US5194088A (en) * 1991-07-08 1993-03-16 Ciba-Geigy Corporation Process for conditioning organic pigments
US5334412A (en) * 1991-12-23 1994-08-02 Ferro Corporation Enamel for use on glass and a method of using the same
US5391247A (en) * 1992-01-24 1995-02-21 Revlon Consumer Products Corporation Hot stamping glass
JPH06317075A (ja) * 1993-05-01 1994-11-15 Yukitoshi Kosaka 温室ドアーの密接装置
CA2096921C (en) * 1993-05-25 1998-08-11 Melvin E. Kamen Hot stamping glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57152992A (en) * 1981-03-19 1982-09-21 Kamaya Kagaku Kogyo Kk Decoration of brilliant metallic letter and picture, etc.
JPS59184746A (ja) * 1983-04-01 1984-10-20 Koa Glass Kk ガラス表面における光輝性メタリツク文字或いは図柄等の加飾方法

Also Published As

Publication number Publication date
PT825218E (pt) 2000-12-29
ES2150191T3 (es) 2000-11-16
EP0668170A2 (en) 1995-08-23
US5520973A (en) 1996-05-28
CA2141915A1 (en) 1995-08-23
IL112393A (en) 1997-07-13
HK1009141A1 (en) 1999-05-28
NO950650D0 (no) 1995-02-21
HK1012311A1 (en) 1999-07-30
DE69508452T2 (de) 1999-07-08
DE69508452D1 (de) 1999-04-29
CN1119176A (zh) 1996-03-27
ES2128659T3 (es) 1999-05-16
US5487927A (en) 1996-01-30
ATE194634T1 (de) 2000-07-15
EP0668170B1 (en) 1999-03-24
DE69518016D1 (de) 2000-08-17
KR950031544A (ko) 1995-12-18
NZ270524A (en) 1996-10-28
FI950822A (fi) 1995-08-23
AU4927897A (en) 1998-02-19
DE69518016T2 (de) 2001-03-22
SG49241A1 (en) 1998-05-18
AU683968B2 (en) 1997-11-27
JPH0839997A (ja) 1996-02-13
AU695195B2 (en) 1998-08-06
ZA951324B (en) 1996-03-06
EP0668170A3 (en) 1997-03-12
IL112393A0 (en) 1995-03-30
CA2141915C (en) 2000-05-30
GR3030237T3 (en) 1999-08-31
NO950650L (no) 1995-08-23
JP2889146B2 (ja) 1999-05-10
FI950822A0 (fi) 1995-02-22
EP0825218B1 (en) 2000-07-12
DK0668170T3 (da) 1999-05-25
AU1160795A (en) 1995-08-31
US5708047A (en) 1998-01-13
ATE177997T1 (de) 1999-04-15
BR9500677A (pt) 1995-10-24
TW321666B (zh) 1997-12-01
EP0825218A1 (en) 1998-02-25

Similar Documents

Publication Publication Date Title
CN1051294C (zh) 施彩底物的方法、可辐照固化的聚合物组合物及施彩的容器
CN1114666A (zh) 可辐照固化的有色组合物
US6093455A (en) Method and compositions for decorating glass
CN1153685C (zh) 制造经装饰的基材的方法
CN101003043A (zh) 制备具有择优耐磨表面的通用塑料制品的方法
WO2016191663A1 (en) Pressure-sensitive label
CN103666296A (zh) 双面粘接膜及其制造方法
JP2004138671A (ja) 再帰反射性物品の製造方法および再帰反射性物品
EP1316434A2 (en) Process for making weather proof and chemical-resistant outdoor signs and signs made thereby
WO1995033626A1 (en) Process for making curable decals
CN1750926A (zh) 装饰箔
JP3634191B2 (ja) 化粧塗装箔およびその製造方法
JP4212660B2 (ja) 化粧板の製造方法
JP2002020704A (ja) 転写シート、その製造方法およびそれを用いた塗膜形成方法
CN211000567U (zh) 一种可追溯多显色效果热转印膜
EP4201696A1 (en) A method of creating a textured layer on a decorative panel
JP4406975B2 (ja) 化粧無機質板
EP2024187B1 (en) A printing process
JP4381712B2 (ja) 意匠性建材の製造方法
JPH10278197A (ja) 化粧シート及びその製造方法
JPS6157199B2 (zh)
CA1307233C (en) Radiation cured coating containing glitter particles and process therefor
JPS6343349B2 (zh)
JPH04305500A (ja) グラフィックプリント板の製造法
CN1569483A (zh) 用塑料类专用转印膜对实木热转印装饰的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee