US 20140378585A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0378585 A1 Let al. (43) Pub. Date: Dec. 25, 2014 (54) INKJET INK COMPOSITION FOR PRINTING CSK 5/3465 (2006.01) RREMOVABLE TRACE MARKSON CSK 5/4I (2006.01) SUBSTRATES FOR ENHANCING PRODUCT CSK 5/23 (2006.01) AUTHENTICITY AND TRACEABILITY (52) U.S. Cl. CPC ................ C09D 1 1/322 (2013.01); C08K 5/41 (71) Applicant: Kwai Sang NG, Hong Kong (CN) (2013.01); C08K 5/235 (2013.01); C08K 5/3465 (2013.01); C08K 5/18 (2013.01) (72) Inventors: PEI LI, Hong Kong (CN); Kin Man USPC ............................................. 524/90; 524/159 HO, Hong Kong (CN); Chun Ho YAM, Hong Kong (CN); Kwai Sang NG, Hong (57) ABSTRACT SN Siu Sun CHAN, Hong Provided herein is an inkjet ink composition for printing 9. irremovable color trace marks on polymer substrates. The composition disclosed herein comprises a Surface colorant, a (73) Assignee: Kwai Sang NG, Hong Kong (CN) hydrophobic colorant capable of staining the polymer Sub strates disclosed herein, a hydrophobic colorant carrier which (21) Appl. No.: 14/308,708 provides good solubility for the hydrophobic colorant, a 1-1. binder and an ink solvent system. Printing with the composi (22) Filed: Jun. 18, 2014 tion disclosed herein on multilayered plastic packaging pro O O vides a double layered print. The surface colorants can be Related U.S. Application Data removed by an organic solvent, while the hydrophobic colo (60) Provisional application No. 61/837,378, filed on Jun. rant can stain the nonporous Substrates, giving a watermark of 20, 2013. the Surface print or an inner layer trace marks, which are highly resistance against chemical and physical stress. The Publication Classification composition disclosed herein also allows color tuning of the trace marks. Attempt to remove the printed information by (51) Int. Cl. any physical or chemical means will leave irremovable color C09D II/322 (2006.01) trace marks, thus allowing consumers to detect tampered CSK 5/IS (2006.01) goods. US 2014/0378585 A1 Dec. 25, 2014 NKUET INK COMPOSITION FOR PRINTING applied to those fast moving consumer goods (FMCG) Such RREMOVABLE TRACE MARKSON as dairy products, beverages, and food products. Therefore, SUBSTRATES FOR ENHANCING PRODUCT there is a great demand for an affordable and reliable anti AUTHENTCITY AND TRACEABILITY counterfeiting technique for FMCG packaging. 0006. In last decade, indelible inkjet ink formulations have PRIOR RELATED APPLICATIONS been scarcely developed and used in printing codes or mark ings of industrial products from high speed production line 0001. This application claims the benefit under 35 U.S.C. with the “continuous inkjet' (CIJ) printing technology. For S119(e) of U.S. Provisional Patent Application No. 61/837, example, U.S. Pat. No. 5,449,400 has disclosed an anti-coun 378, filed on Jun. 20, 2013, which is incorporated herein by terfeiting ink composition for invalidating bank notes or simi reference in its entirety. lar valuables by staining them permanently. 0007 U.S. Pat. No. 5,847.024 has described an anti-coun FIELD OF THE INVENTION terfeiting non-yellowing watermark ink on papers. 0002 This invention provides an inkjet ink composition 0008 U.S. Pat. No. 7,297.201 has described an inkjet ink for printing irremovable color trace marks on Substrates Such composition that forms indelible images on porous or semi as polymer Substrates which may be nonporous and/or hydro porous Substrate such as paper or postage stamps. The inkjet phobic. The inkjet ink composition disclosed herein com ink composition comprises (i) a hydrophobic colorant carrier, prises a surface colorant which may be one or more dyes (ii) a first colorant that is soluble in the carrier; (iii) a second and/or pigments, a hydrophobic colorant capable of staining colorant comprising a pigment, which is dispersed in the the polymer substrates disclosed herein, a hydrophobic colo carrier. The solubility difference between different colorants rant carrier which provides good solubility for the hydropho makes the resulting marks highly resistance against any bic colorant, a binder, an ink solvent system and one or more chemical attacks. optional additives. 0009 U.S. Pat. No. 7,081,158 has disclosed an ink formu lation containing more than 70% by weight of propylene BACKGROUND OF THE INVENTION carbonate as a solvent. The ink formulation has a high pen 0003 Inkjet printing is a well-known technique for print etration capacity on paper Substrates such as letters and postal ing or marking information (e.g., manufacturing and/or expi articles. Propylene carbonate functions as a penetrant to carry ration dates, lot numbers, manufacturing locations, etc.) or the dyes passing through the Substrate into inner layer of the images on packages of consumer products Such as dairy prod substrate. The substrate then serves as a barrier to endow the ucts, beverages, Snacks, food products, plastic bottles, PVC penetrated dyes with good resistance to any physical and pipes, electrical wirings, etc. Such markings provide manu chemical stress. facturers with useful information for tracking products from (0010 U.S. Pat. No. 7,833,334 has disclosed an improved their production lines to retail locations where they are being propylene carbonate-based ink formulation based on the U.S. sold to consumers. Product traceability is an important issue Pat. No. 7,081,158. The formulation renders its good adhe in protecting public health and managing Supply chain sion ability and extends its application to various Substrates, because it allows a manufacturer or public agency to quickly Such as, metal, plastics, glass, etc. and accurately identify any contaminated goods, and then 0011 To address the moisture sensitive issue of the pro remove them from the marketplace. pylene carbonate-based ink, U.S. Pat. No. 8,282,724 has dis 0004. In recent years, the spread of counterfeit goods and closed a water-free ink composition, wherein the inkjet ink the number of infringing goods increase significantly. Resell composition contains organic compounds that are capable of ing of spoiled or lost inventory and contaminated products dissociating the ionizable species. The presence of these ion also happens frequently, thus threatening public health. One izable species overcomes the problem of low ink conductivity of the causes of these issues is attributed to the fact that arising from the absence of water for dissolving the conduc current markings on packaging printed by inkjet printing tive salt. technology are not permanent. The marks can be easily 0012 All of the inkjet ink compositions disclosed by the removed by either physical or chemical methods. In fact, this above patent references are mainly for printing indelible or is a well-known and a long standing problem to the industries anti-counterfeit markings on paper and postage stamps. They for products with markings on plastic Surfaces. Therefore, in are not for printing indelible or anti-counterfeit markings on order to protect the product information and provide product nonporous polymer Substrates. Such as low density poly(eth traceability, there is an urgent need to develop printing sys ylene), high density poly(ethylene), poly(phenyl ether), poly tems that are capable of printing irremovable or indelible olefin, poly(propylene), ethylene-vinyl acetate copolymers, markings on plastic-based packaging materials. epoxy resins, and the like. As mentioned earlier, the marks 0005 To tackle the counterfeit issue, a range of anti-coun produced by the current inkjet ink can be easily removed by terfeit technologies have been developed up to now. For phar either physical or chemical methods. maceutical industries, well-known and widely used anti 0013. It is one of the objectives of the present invention to counterfeit technologies include holograms and radio overcome the disadvantages and problems mentioned above. frequency identification (RFID). However, holograms techniques can be easily reproduced and counterfeited. SUMMARY OF THE INVENTION Nowadays, the RFID technologies are regarded as the most 0014. The aforementioned needs are met by various promising technologies for trace and track of the pallets and aspects disclosed herein. In one aspect, provided herein is an packages. The Sophisticated RFID system allows tracing and inkjet ink composition for printing one or more irremovable securing the pharmaceutical supply chain. However, RFID color trace marks on a nonporous polymer Substrate, wherein still cannot prevent package tampering and intelligent hack the inkjet ink composition comprises a Surface colorant, a ing. Furthermore, RFID technologies are very expensive to be hydrophobic colorant, a hydrophobic colorant carrier, an ink US 2014/0378585 A1 Dec. 25, 2014 Solvent, a binder, and an additive. In some embodiments, the 0023. In certain embodiments, the hydrophobic colorant hydrophobic colorant has a solubility higher than 0.2 g/100 stains the nonporous polymer Substrate to form the one or mL of the hydrophobic colorant carrier. more irremovable color trace marks, and is impervious to any 0.015. In certain embodiments, the surface colorant com chemical and physical alternations. In some embodiments, prises a metal complex dye, a pigment-based colorant or a the color of the one or more irremovable color trace marks is combination thereof. In some embodiments, the Surface colo same as or different from the color of the surface print. In rant is present in an amount from 0.1% to 10% by weight, further embodiments, the color of the one or more irremov based on the total weight of the inkjet ink composition. able color trace marks is selected from the group consisting of 0016. In some embodiments, the hydrophobic colorant red, yellow, orange, green, blue, black, and combinations comprises one or more nonionic hydrophobic colorants. In thereof. certain embodiments, the hydrophobic colorant is selected 0024. In some embodiments, the nonporous polymer sub from the group consisting of anthraquinone-based colorants, strate is selected from the group consisting of polyolefins aZo-based colorants and combinations thereof.