Title of Invention	"AN ULTRAVIOLET RADIATION CURABLE INK COMPOSITION FOR INKJET APPLICATION ON THE PAINTED AUTOMOTIVE PARTS"
Abstract	An UV curable composition which exhibits a relative low viscosity and is curable at a high sensitivity, forming a coating of superior adhesion and hardness, and its use on the base coat painted automotive parts which are lacquered by conventional taping lacquer. The invention concerns coatings curable by ultraviolet radiation, which may be printed on to polymer substrates to provide a thermal drop-on-demand ink-jet receptive layer. The novelty of the invention lies in the ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or leveling additives, substrate wetting additives, defoamers, slip additives, organic solvents, for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it.

Title of Invention

"AN ULTRAVIOLET RADIATION CURABLE INK COMPOSITION FOR INKJET APPLICATION ON THE PAINTED AUTOMOTIVE PARTS"

Abstract

An UV curable composition which exhibits a relative low viscosity and is curable at a high sensitivity, forming a coating of superior adhesion and hardness, and its use on the base coat painted automotive parts which are lacquered by conventional taping lacquer. The invention concerns coatings curable by ultraviolet radiation, which may be printed on to polymer substrates to provide a thermal drop-on-demand ink-jet receptive layer. The novelty of the invention lies in the ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or leveling additives, substrate wetting additives, defoamers, slip additives, organic solvents, for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it.

Full Text	FORM 2 THE PATENTS ACT, 1970 COMPLETE SPECIFICATION (SECTION 10) TITLE : AN ULTRAVIOLET RADIATION CURABLE INK COMPOSITION FOR INKJET APPLICATION ON THE PAINTED AUTOMOTIVE PARTS OR PAINTED POLYMER AUTOMOTIVE SUBSTRATES FOR DECORATION AND TEXT PRINTING PURPOSE WITH CLEAR TOPCOAT. APPLICANT : KANSAI NEROLAC PAINTS LTD., a Company registered under the Companies Act, 1956 having address at Nerolac House, Ganpatrao Kadam Marg, Lower Parel, Mumbai -400 013, India. Indian National The following specification particularly describes the invention and the manner in which it is to be performed. FIELD OF THE INVENTION The present invention relates to an UV curable composition which exhibits a relative low viscosity and is curable at a high sensitivity, forming a coating of superior adhesion and hardness, and its use on the base coat painted automotive parts which are lacquered by conventional taping lacquer. The invention concerns coatings curable by ultraviolet radiation, which may be printed on to polymer substrates to provide a thermal drop-on-demand ink-jet receptive layer. Radiation curable ink compositions that include a curable component having a functionality that is greater than two, is present in the ink composition in an amount greater than 50 percent 6y weight, ana' has a molecular weight in the range of about 400 g/mole to about 10,000 g/mole; a component that has a functionality that is less than or equal to 2; and an initiator component. A solvent component, pigment, a surface tension modifier and other materials also can be included. The radiation curable inks are employed in ink jet printers and are particularly suited for use in printing on large-scale substrates. The printed images described herein have good adhesion to polymeric substrates such as styrene-based, polycarbonates, polyolefins, polyethylene terephthalate glycol ester, acryliC and others. A composition of an ultraviolet light curable jettable ink which includes a colorant, a photoinitiating system, and monomers and flow additives used for printing onto the painted automotive base coat for decoration purpose and exposing the marking to ultraviolet radiation after at least two second. BACKGROUND OF THE INVENTION In general, ink containing a substantial amount of organic liquids would produce undesirable emissions during the printing process. such emissions are substantially avoided, however, with energy curable inks. Energy curable inks use low viscosity reactive materials to attain the desired viscosity. The reactive materials have reactive groups that are cured after printing with radiation, such as UV radiation or electron beams. First, faster cure times offer substantial economic benefits. Furthermore, heat sensitive materials can be safely coated and cured with UV light without thermal degradation of heat sensitive substrates. Additionally, UV light is a relatively low cost of energy due to its widespread availability. Advantages of UV curable inks: Faster cure time offers substantial economic benefits. Heat sensitive material can be safely coated and cured with UV light without thermal degradation of heat sensitive substrates. Additionally UV light is a low cost of energy due to its widespread availability. Radiation curable inks are printed onto numerous substrates, both rigid and flexible. These include polymeric substrates, such as various types of PVC as well as polystyrene (usually modified), polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyolefines, polyesters, and others. The appearance of the printed image is affected by "jettable" characteristics of the ink, such as ink viscosity, droplet formation, satellite formation, drying or curing time and other properties that relate to the ejection of the ink from the print head, droplet travel and impact onto substrate. The low viscosity reactive materials in energy curable inks may include monoethylenically and polyethylenically unsaturated monomers and oligomers. The energy curable inks may also include unreactive oligomers and polymers. Because monofunctional monomers are particularly low in viscosity, ink jet inks to date have included substantial amounts of monofunctional monomers. Therefore, a need continues to exist for radiation-curable ink compositions that adhere well to multiple substrates, form printed images having good appearance, improved hardness and good flexibility and that are capable of withstanding outdoor weather conditions. The invention generally relates to radiation-curable ink compositions for inkjet printing, to methods for using them and to printed displays produced by curing the ink compositions on a substrate. In one embodiment, the invention is directed to radiation-curable ink compositions for inkjet printing on multiple substrates. Prior art: Ink-jet printing is a technique which puts a number of constraints on the nature of the ink which is used. These constraints include low viscosity (usually less than 50 cP or, for continuous operation, less than 10 cP at 25.degree. C), sufficient surface tension that the jet can produce the necessary large number of small droplets, and (at least for continuous operation) sufficient conductivity that the droplets can be directed as desired onto a substrate to be printed. The ink must be a homogeneous liquid capable of rapid conversion to a dry printed area on the substrate. Inks for use in piezoelectric drop-on-demand ink-jet printing traditionally comprise a mixture of fatty acids, fatty esters and oil-soluble dyes. Such inks should be slow-drying, to prevent clogging of the nozzles; this constraint results in the process being suitable only for surfaces where the ink may dry through absorption On non-absorbent surfaces, the ink remains wet for an undesirably long period of time. Ink compositions available in market are composed of different monomers, oligomers, pigments, additives and photoinitiators. These compositions tried for printing with inkjet printing machine. These inks found to be inferior in terms of curing, consistency in printing. The printed images have poor water resistant, have poor flexibility characteristics as well as hardness of these images is found to be not up to the mark. In some cases curing of the inks is not possible even after changing different line conditions of the printing process. These UV ink compositions are costlier than the described invention. Hence we can get economical advantage with the better performance properties. Comparable study of performance properties is given in the table no.1 Ink compositions of the invention are compatible with ink jet printing systems, in particular systems designed to produce logos and text art displays. They have favorable dot gain characteristics and result in good quality printed images that exhibit good adherence to many of the substrates being used in outdoor displays. In addition, the printed images are water resistant, have good flexibility characteristics as well as improved hardness, The invention further provides an ink jet printing method in which an ink jet printer prints the ink jet ink of the invention onto a substrate which is base coat painted metal parts. The use of this UV curable ink is for decoration i.e. printing of company logos and text for decoration purpose. For example : US patent 6,593,390 describes development of a radiation curable ink jet ink which is essentially free of non-reactive diluent and yet has the desired viscosity, surface tension, volatility, stability and drying rate and produces print of acceptable quality. Inks according to the invention thus can be printed without difficulty from ink jet printers to give good quality print on a variety of substrates including such disparate materials as paper and non-adsorbent materials e.g. metal. They are of particular interest, however, in printing on plastics which are difficult to print on, e.g. polyolefins such as polyethylene and polypropylene The inks may be employed for printing on to a wide variety of substrates, both absorbent and non-absorbent including paper, glass, plastic and metal, e.g. steel, copper and aluminium, but claimed that suitable for printing on to plastics to provide a strongly bonded print of good definition and optical density, especially if the surface to be printed is pre-treated e.g. by flame, plasma etch or corona treatment to raise the surface energy. US patent 7365105: The patent describes radiation curable ink compositions and applications thereof. The radiation curable ink gives the printed images described herein have good adhesion to polymeric substrates such as styrene-based, polycarbonates, polyolefins, polyethylene terephthalate glycol ester, acrylic and others. But these ink compositions are found to be inferior on the base coat painted metal parts. For white ink consistency of printing and curing is found to be inferior. For black ink curing of print is inferior. Over this UV cured printed layer thermosetting acrylic or polyester based topcoat is applied. It is found that inter coat adhesion of base coat, printing layers and acrylic or polyester based topcoat is poor. This ink composition is found to be working well only on plastic parts. These prior art difficulties are overcome by new novel ink composition which is suitable for base coat (acrylic, alkyd, polyester) painted metal parts as well as on the plastic parts. In addition to good substrate adhesion, the inks adhere to one another when printed in layers. Over this UV cured printed layer thermosetting acrylic or polyester based topcoat is applied. It is found that inter coat adhesion of base coat, printing layers and acrylic or polyester based topcoat is better. Present Process of application of stickers on automotive parts: OBJECTIVE OF THE INVENTION: It is an object of the present invention to provide new radiation curable composition of radiation curable ink for printing on the base coat painted automotive parts. This radiation curable ink with relatively low viscosity and high curing sensitivity, capable of forming a strong and soft film even under various environments. It is also an object of the present invention to provide new UV curable ink for inkjet printing on painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it with better hardness as well as flexibility to provide proper adhesion to the base coat painted substrate as well as with the top coat layer. DETAILED DESCRIPTION OF THE INVENTION: Conventionally decorative text is applied by application of stickers on the different different substrates including metal, plastic, paper. The structural composition of the sticker then we can find different layers of the paper and plastic material. When we apply sticker on any substrate only printed part is utilized for application. After application of this remaining plastic coverings of the sticker are thrown away. This will be non value added waste to the environment. Disadvantages of stickers: • Costlier. • Generates Paper and Mastic waste. • Requirement of skilled person for application. Advantages of Inkjet printing • As a system Less costlier than stickers. • Environment friendly Process as there is no generation of paper and plastic wastes. • Customized process hence less chances of errors. By making use of radiation curable ink -jet ink is utilized for ink jet application on the painted automotive parts or painted polymer automotive substrates for Decorative image and text printing purpose with clear topcoat over it. Composition of Radiation curable ink: This radiation curable ink is divided in to two parts: 1) UV curable clear ink base : 2) Colourant dispersed in monomers or oligomers: The radiation curable ink-jet ink and the radiation curable liquid layer contain monomers and/or oligomers, which are polymerized by the curing means of the inkjet printer. Monomers, oligomers or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri- and higher functionality monomers, oligomers and/or prepolymers may be used. These components are curable, typically photo-curable, e.g. UV curable, and should adhere to the ink-receiver surface after printing and serve to bind the colorant. A mixture of two or more monomers of the same functionality is preferred, with particularly preferred a mixture of two di-functional monomers. The viscosity of the radiation curable ink-jet ink and the radiation curable liquid layer can be adjusted by varying the ratio between the monomers and oligomers. Any method of conventional radical polymerization, photo-curing system using photo acid or photo base generator, or photo induction alternating copolymerization may be employed. In general, radical polymerization and cationic polymerization are preferred, and photo induction alternating copolymerization needing no initiator may also be employed. Furthermore, a hybrid system of combinations of these systems is also effective. Description :- Preparation of a Radiation Curable Ink-Jet Ink blend particularly preferred for use as a radiation-curable compound in the radiation curable ink-jet ink and the radiation curable liquid layer are : Monomers: 2-phenoxy ethyl acrylate, Ethoxylated phenoxyl acrylate, 2-(2-Ehoxyethoxy)ethyl acrylate, cyclic trimethylol-propane formal acrylate, p-carboxyethyl acrylate, Lauryl acrylate, stearyl acrylate, isodecyl acrylate, C8-C10 acrylate, lauryl methacrylate, steryl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypivalyl hydroxypivalate diacrylate, 1,6-hexanediol diacrylate, Ethoxylated 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylen glycol diacrylate, polyethylene glycol (200) diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol (400) diacrylate ethoxylated bisphenol-A diacrylate, polyethylene glycol (600) diacrylate, 2-methyl-1,3-propanediol diacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate, 2-butyl-2-ethyI-1,3-propanediol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, ethoxylated bisphenol-A dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate phosphate Trifunctional monomers: Tris(2-Hydroxy Ethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerytritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, trimethylol propane trimethacrylate, ethoxylated trimethylolpropane timethacrylate Multifunctional Monomers: Pentaerytritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerytritol tetraacrylate, dipentaerytritol hexaacrylate, 2-phenoxy ethyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate. Also vinylamide such as N-vinylcaprolactam or N-vinylformamide; or acrylamide or a substituted acrylamide such as acryloylmorpholine; and amino functionalized polyetheracrylates Oligomers: 1) Urethne acrylate oligomers : (Afunctional, tetrafunctional, hexa functional, epoxy acrylate oligomers : bisphenol -A epoxy acrylate, polyester acrylate oligomers : Different functional polyester acrylate oligomers, chlorinated polyester acrylates, acrylic acrylate oligomers, polyether acrylate oligomers, reactive amine synergists, Specific functional oligomers : organic/ inorganic hybrid products. Ultraviolet radiation curable ink composition wherein UV curable ink blend monomer or oligomer is in an amount between 1. 0 to 99.0 %. Photo-Initiators : A catalyst called a photo-initiator typically initiates the polymerization reaction. The photo-initiator requires less energy to activate than the monomers and oligomers to form the polymer. The photo-initiator suitable for use in the radiation curable ink-jet ink and the radiation curable liquid layer may be a Norrish type I initiator, a Norrish type II initiator or a photo-acid generator. The photo-initiator absorbs light and is responsible for the production of free radicals or cations. Free radicals or cations are high-energy species that induce polymerization of monomers, oligomers and polymers and with polyfunctional monomers and oligomers thereby also inducing cross-linking. A preferred Norrish type l-initiator is selected from the group consisting of benzoinethers, benzil ketals, .alpha,..alpha.-dialkoxyacetophenones, .alpha.- hydroxyalkylphenones, .alpha.-aminoalkylphenones, acylphosphine oxides, acylphosphine sulphides, .alpha.-haloketones, .alpha.-halosulfones and .alpha.- halophenylglyoxalates. A preferred Norrish type ll-initiator is selected from the group consisting of benzophenones, thioxanthones, 1,2-diketones and anthraquinones. A preferred co- initiator is selected from the group consisting of an aliphatic amine, an aromatic amine and a thiol. Tertiary amines, heterocyclic thiols and 4-dialkylamino-benzoic acid are particularly preferred as co-initiator. Specific examples of photo-initiators may include, but are not limited to, the following compounds or combinations thereof: benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1- one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one or 5,7-diiodo-3--butoxy-6-fluorone, diphenyliodonium fluoride and triphenylsulfonium hexafluophosphate. Suitable commercial photo-initiators include Irgacure184/ PI 184, Irgacure500, Irgacure 907, Irgacure. 369, Irgacure 1700, Irgacure 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur 4265 and Darocur ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO Benzildimethylketal, Benzophenone, 1-Hydroxycyclohexylphenylketone Camphorquinone, 2,4 Diethylthioxanthone, Dimethylhydroxyacetophenone 2- Ethylhexyl-4-dimethylaminobenzoate, Ethyl-4-dimethylaminobenzoate Isopropylthioxanthone, 1-Hydroxycyciohexylphenylketone and Benzophenone Liquid benzophenone, Liquid Photoinitiator blend, Methyl-o-benzoyl-benzoate Methyibenzoylformate, N-Methyldiethanolamine, 4-Phenylbenzophenone 2-Methyl- 1(4-methylthiophenyl)-2~morpholinpropan-1-one, 2,4,6-Trimethylbezoylphenyl- phosphineoxide, Bis{2,4,6-trimethylbenzoyl)-phenylphosphineoxide, Polymeric Aminobenzoate Derivative Polymeric Benzophenone Derivative, Polymeric Thioxanthone Derivative Inhibitors : Suitable polymerization inhibitors include phenol type antioxidants, hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol may also be used. Of these, a phenol compound having a double bond in molecules derived from acrylic acid is particularly preferred due to its having a polymerization-restraining effect even when heated in a closed, oxygen-free environment. Suitable inhibitors are, for example, Sumilizer.TM. GA-80, Sumilizer.TM. GM and Sumilizer.TM. GS produced by Sumitomo Chemical Co., Ltd, and Genorad.TM.16, Genorad.TM.18 available from Rahn of Zurich, Switzerland. Since excessive addition of these polymerization inhibitors will lower the ink sensitivity to curing, it is preferred that the amount capable of preventing polymerization be determined prior to blending. The amount of a polymerization inhibitor is generally between 1-20 % of the total ink weight or the total link composition. Furthermore, the radiation curable ink-jet ink and the radiation curable liquid layer may also contain polymerizable oligomers. Examples of these polymerizable oligomers include epoxy acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, polyester acrylates, and straight-chained acrylic oligomers. Colorants : Colorants may be dyes, but are preferably pigments or a combination thereof. Organic and/or inorganic pigments, pigments dispersion pastes may be used. The pigment particles should be sufficiently small to permit free flow of the ink through the inkjet printing device, especially at the ejecting nozzles which usually have a diameter ranging from 10 .mu.m to 50 .mu.m. The particle size influences also the pigment dispersion stability. It is also desirable to use small particles for maximum colour strength. The particles of the pigment dispersed in the ink-jet ink should have a particle size of less than 10 .mu.m, preferably less than 3 .mu.m, and most preferably less than 1 .mu.m. The average particle size of pigment particles is preferably 0.05 to 0.5 .mu.m. Suitable pigments include as red or magenta pigments: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; as blue or cyan pigments: Pigment Blue 1,15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60; as green pigments: Pigment green 7, 26, 36, and 50; as yellow pigments: Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 177, 180, 185, and 193; as white pigment: Pigment White 6, 18, and 21. Most preferred pigments are Pigment Yellow 1, 3, 128, 109, 93, 17, 14, 10, 12, 13, 83, 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22, 23, 17, 210, 170, 188, 185, 146, 144, 176, 57:1, 184, 202, 206, 207; Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16 and Pigment Violet 19. Carbon black is usually used as the colouring material in black ink. Suitable black pigment materials include carbon blacks such as Pigment Black 71. The pigment is present in the range of 0.1 to 50 wt %, based on the total weight of the radiation curable inkjet ink. Dyes suitable for the radiation curable ink-jet ink include direct dyes, acidic dyes, basic dyes and reactive dyes. Suitable direct dyes for the radiation curable ink-jet ink include: C.I. Direct Yellow 1, 4, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86, 100, 110, 120, 132, 142, and 144 C.I. Direct Red 1,2, 4, 9, 11, 134, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 47, 48, 51, 62, 63, 75, 79, 80, 81, 83, 89, 90, 94, 95, 99, 220, 224, 227 and 343 C.I. Direct Blue 1, 2, 6, 8,1 5, 22, 25, 71, 76, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 236, and 237 C.I. Direct Black 2, 3, 7, 17, 19,22,32,38, 51,56,62,71,74,75,77, 105, 108, 112, 117, and 154 Suitable acidic dyes for the radiation curable ink-jet ink include: C.I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 20, 38, 42, 49, 59, 61, 72, and 99 C.I. Acid Orange 56 and 64 C.I. Acid Red 1,8, 14, 18,26,32,37,42,52,57,72,74,80,87, 115, 119, 131, 133, 134, 143, 154, 186, 249, 254, and 256 C.I. Acid Violet 11, 34, and 75 C.I. Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, and 249 C.I. Acid Green 9, 12, 19, 27, and 41 C.I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 60, 94, 107, 109, 110, 119, 131, and 155. Suitable reactive dyes for the radiation curable ink-jet ink include: C.I. Reactive Yellow 1, 2, 3, 14, 15, 17, 37, 42, 76, 95, 168, and 175 C.I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, and 235 C.I. Reactive Blue 7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, and 235 C.I. Reactive Orange 5, 12, 13, 35, and 95 C.I. Reactive Brown 7, 11, 33, 37, and 46 C.I. Reactive Green 8 and 19 C.I. Reactive Violet 2, 4, 6, 8, 21, 22, and 25 C.I. Reactive Black 5, 8, 31, and 39. Suitable basic dyes for the radiation curable ink-jet ink include: C.I. Basic Yellow 11, 14, 21, and 32 C.I. Basic Red 1, 2, 9, 12, and 13 C.I. Basic Violet 3, 7, and 14 C.I. Basic Blue 3, 9, 24, and 25. Dyes can only manifest the ideal colour in an appropriate range of pH value. Therefore, the radiation curable ink-jet ink preferably further comprises a pH buffer, such as potassium hydroxide (KOH). Resins : The radiation curable ink-jet ink and the radiation curable liquid layer may further contain a resin, also called a pigment stabilizer or dispersant used to obtain a stable dispersion of the pigment(s) in the inkjet ink. The pigments may be added to the radiation curable ink-jet ink as a dispersion comprising a dispersant. Suitable resins: petroleum type resins (e.g., styrene type, acryl type, polyester, polyurethane type, phenol type, butyral type, cellulose type, and rosin); and thermoplastic resins (e.g., vinyl chloride, vinylacetate type). Concrete examples of these resins include acryiate copolymers, styrene-acrylate copolymers, acetalized and incompletely saponified polyvinyl alcohol, and vinylacetate copolymers. Additives : - Surfactants : The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one surfactant. The surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity 0.1-1.0 wt % based on the total ink weight. A fluorinated or silicone compound may be used as a surfactant, however, a potential drawback is extraction by food from inkjet food packaging material because the surfactant does not cross-link. It is therefore preferred to use a copolymerizable monomer having surface-active effects, for example, silicone-modified acrylates, silicone modified methacrylates, fluorinated acrylates, and fluorinated methacrylates. Defoamers : The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one defoamer. The defoamer(s) can be usually added in a total quantity 0.1-1.0 wt % based on the total ink weight. Slip additives : The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one slip additive. The slip additive can be usually added in a total quantity 0.1-1.0 wt % based on the total ink weight. Solvents : The radiation curable ink-jet ink and the radiation curable liquid layer may contain as a solvent, water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents, the solvent preferably being present in a concentration between 10 and 80 wt %, particularly preferably between 20 and 50 wt %, each based on the total weight of the radiation curable inkjet ink, respectively the total weight of the radiation curable liquid layer. However, the radiation curable ink-jet ink preferably does not contain an evaporable component, but sometimes; it can be advantageous to incorporate an extremely small amount of an organic solvent in such inks to improve adhesion to the ink-receiver surface after UV curing. In this case, the added solvent can be any amount in the range which does not cause problems of solvent resistance and VOC, and preferably 0.1-20.0 wt %, and particularly preferably 0.1-10.0 wt %, each based on the total weight of the radiation curable ink-jet ink Suitable organic solvents include alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters. Suitable alcohols include methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol, t.-butanol. Suitable aromatic hydrocarbons include toluene, and xylene. Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2,4-pentanedione and hexafluoroacetone. Also glycol, glycolethers, N-methylpyrrolidone, N,N-dimethylacetamid, N,N-dimethylformamid may be used. Examples: Clear ink base for coloured ink: Compositions based on different combinations of monomers, oligomers, photoinitiators and stabilizers are as follows: Example 1 Take a clean and crater free hopper. To which add 12.5 parts by weight lauryl methacrylate, 31.6 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 9.8 parts by wight ethoxylated phenoxyl acrylate, 4.0 parts by weight ethoxylated trimethylolpropane triacrylate, and 5.4 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 1.2 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 3.0 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 2.5 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed. Example 2 Take a clean and crater free hopper. To which add 3.7 parts by weight lauryl methacrylate, 2.4 parts by weight isobornyl acrylate, 5.0 parts by weight dipropylene glycol diacrylate, 28.8 parts by weight of 1,6-Hexanediol diacrylate, 11.0 parts by weight of triporpylene glycol triacrylate, 31.5 parts by wight ethoxylated phenoxyl acrylate, 10.0 parts by weight ethoxylated trimethylolpropane triacrylate. Stir for 10 -15 minutes. To this solution add 2.8 parts by weight Isopropyl thioxanthone, 2.8 parts by wight 2-Hydroxy-2-methyM-phenyl-propanone, 2.5 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed. Example 3 Take a clean and crater free hopper. To which add 10.6 parts by weight isobornyl acrylate, 33.0 parts by weight dipropylene glycol diacrylate, 33.5 parts by weight of 1,6-Hexanediol diacrylate, 9.6 parts by weight ethoxylated trimethylolpropane triacrylate, 4.8 parts by weight dipentaerythitol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 2.8 parts by weight Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.7 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed. Example 4 Take a clean and crater free hopper. To which add 14.3 parts by weight isobornyl acrylate, 30.4 parts by weight dipropylene glycol diacrylate, 27.4 parts by weight of 1,6-Hexanediol diacrylate, 5.7 parts by weight ethoxylated phenoxyl acrylate, 10.5 parts by weight ethoxylated trimethylolpropane triacrylate, 3.1 parts by weight dipentaerythitol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 2.1 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.2 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 2.3 parts by weight 2,4,6-trimethylbenzoyl diphenyl phosphine oxide under stirring. Stir for 20 min until clear solution is formed. Example 5 Take a clean and crater free hopper. To which add 13.0 parts by weight lauryl methacrylate, 5.6 parts by weight isobornyl acrylate, 5.6 parts by weight dipropylene glycol diacrylate, 4.8 parts by weight of 1,6-Hexanediol diacrylate, 6.7 parts by weight of triporpylene glycol triacrylate, 8.3 parts by weight ethoxylated phenoxyl acrylate, 3.5 parts by weight ethoxylated trimethylolpropane triacrylate, 32.5 parts by weight ethoxylated trimethylolpropane trimethacrylate, 13.0 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 1.0 part by weight bis(2,4,6-trimethy!benzoyl)-phenylphosphineoxide, 1.0 part by weight isopropyl thioxanthone, 1.0 part by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone, 1.0 part by weight 2,4,6- Trimethylbenzoyl diphenyl phospine oxide, 2.0 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed. Example 6 Take a clean and crater free hopper. To which add 12.5 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 32.6 parts by weight of 1,6-Hexanediol diacrylate, 8.2 parts by weight ethoxylated trimethylolpropane trimethacrylate, 7.5 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 3.5 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.7 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone( 1.0 part 2,2-dimethoxy-1,2-diphenylethan-1-one under stirring. Stir for 20 min until clear solution is formed. Example 7 Take a clean and crater free hopper. To which add 10.0 parts by weight lauryl methacrylate, 25.0 parts by weight dipropylene glycol diacrylate, 30.5 parts by weight of 1,6-Hexanediol diacrylate, 6.0 parts by weight of triporpylene glycol triacrylate, 7.3 parts by weight ethoxylated phenoxyl acrylate, 2.1 parts by weight ethoxylated trimethylolpropane triacrylate, 2.1 parts by weight ethoxylated trimethylolpropane trimethacrylate, 2.1 parts by weight dipentaerythritol hexaacrylate, 3.7 parts by weight bisphenol-A epoxy diacrylate, 1 part by weight aliphatic/aromatic epoxy acrylate, 1 part by weight aliphatic urethane diacrylate. Stir for 10 - 15 minutes. To this solution add 2.7 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.5 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone under stirring. Stir for 20 min until clear solution is formed. Example 8 Take a clean and crater free hopper. To which add 10.6 parts by weight lauryl methacrylate, 33.2 parts by weight of isobornyl acrylate, 33.5 parts by weight dipropylene glycol diacrylate, 9.6 parts by weight ethoxylated phenoxyl acrylate, 4.8 parts by weight ethoxylated trimethylolpropane trimethacrylate. Stir for 10 - 15 minutes. To this solution add 2.8 part by weight bis(2t4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.5 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed. Example 9 Take a clean and crater free hopper. To which add 10.0 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 30.0 parts by weight of 1,6-Hexanediol diacrylate, 8.4 parts by weight ethoxylated trimethylolpropane trimethacrylate, 4.0 parts by weight dipentaerythritol hexaacrylate, 9.2 parts by weight bisphenol-A epoxy diacrylate, 1.7 parts by weight aliphatic urethane diacrylate. Stir for 10-15 minutes. To this solution add 1.8 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.9 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed. Example 10 Take a clean and crater free hopper. To which add 3.0 parts by weight lauryl methacrylate, 2.0 parts by weight isobornyl acrylate, 5.0 parts by weight dipropylene glycol diacrylate, 25.0 parts by weight of 1,6-Hexanediol diacrylate, 11.0 parts by weight of triporpylene glycol triacrylate, 31.0 parts by weight ethoxylated phenoxyl acrylate, 4.0 parts by weight ethoxylated trimethylolpropane triacrylate, 1.0 parts by weight ethoxylated trimethylolpropane trimethacrylate, 1.0 parts by weight dipentaerythritol hexaacrylate, 5.7 parts by weight aliphatic/ aromaticepoxy acrylate, 3.8 parts by weight aliphatic urethane diacrylate. Stir for 10 - 15 minutes. To this solution add 0.26 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 0.4 part by weight isopropyl thioxanthone, 5.0 part by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone, 0.84 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinpropan-1-one under stirring. Stir for 20 min until clear solution is formed. Different ink compositions: Different ink compositions are made by different weight percentage of UV curable ink base and different weight percentages of colourants that are dispersed in monomers or oligomers. Colourants used in different proportion are: Suitable pigments include as red or magenta pigments: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177,178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; as blue or cyan pigments: Pigment Blue 1,15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60; as green pigments: Pigment green 7, 26, 36, and 50; as yellow pigments: Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 177, 180, 185, and 193; as white pigment: Pigment White 6, 18, and 21. Most preferred pigments are Pigment Yellow 1, 3,I28, 109, 93,17, 14, 10, 12, 13, 83, 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22,2Z, 17, 210, 170, 188, 185, 146, 144, 176, 57:1, 184, 202, 206,107, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Figment Blue 15:6, Pigment Blue 16 and Pigment Violet 19. Carbon black is usually used as the colouring materiaI in black ink- Suitable black pigment materials include carbon blacks such as Pigment Black 71. Dyes suitable for the radiation curable ink-jet ink include direct dyes, acidic dyes, basic dyes and reactive dyes. Suitable direct dyes for the radiation curable ink-jet ink include: C.I. Direct Yellow 1, 4, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86- 100 11°, 120. I32. I42. and 144 C.I. Direct Red 1, 2, 4, 9, 11, 134, 17, 20, 23, 24- 28, 31, 33, 37, 39, 44, 47, 48, 51, 62, 63, 75, 79, 80, 81, 83, 89, 90, 94, 95, 99, 220- 224, 227 and 343 C.I. Direct Blue 1, 2, 6, 8,1 5, 22, 25, 71, 76, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203,207, 236, and 237 C.I. Direct Black 2, 3,7, 17, 19, 22, 32, 38, 51, 56, 62, 71, 74, 75. 77, 105. 108, 112, 117, and 154 Suitable acidic dyes for the radiation curable ink-jet ink include: C.I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 20, 38, 42, 49, 59, 61, 72, and 99 Cl- Acid Orange 56 and 64 C.I. Acid Red 1, 8, 14, 18, 26, 32, 37, 42, 52, 57, 72, 74, 80- 87. H5, 119, 131, 133, 134, 143, 154, 186, 249, 254, and 256 C.I. Acid Violet 11 34. and 75 c.1 Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, and 249 C.I. Acid Green 9, 12, 19, 27, and 41 C.I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 00, 94. 107, 109, 110, 119, 131, and 155 Suitable reactive dyes for the radiation curable ink-jet ink include: C.I. Reactive Yellow 1, 2, 3, 14, 15, 17, 37, 42, 76, 95, 168, and 175 C.I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, and 235 C.I. Reactive Blue 7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, and 235 C.I. Reactive Orange 5, 12, 13, 35, and 95 C.I. Reactive Brown 7, 11, 33, 37, and 46 C.I. Reactive Green 8 and 19 C.I. Reactive Violet 2, 4, 6, 8, 21, 22, and 25 C.I. Reactive Black 5, 8, 31, and 39 Suitable basic dyes for the radiation curable ink-jet ink include: C.I. Basic Yellow 11, 14, 21, and 32 C.I. Basic Red 1, 2, 9, 12, and 13 C.I. Basic Violet 3, 7, and 14 C.I. Basic Blue 3, 9, 24, and 25 UV curable coloured inks contain following components: 1) UV curable clear ink base (40-100 % by weight), 2) Flow and leveling additives (0.0-1.0% by weight) 3) Substrate wetting additives (0.0-1.0% by weight) 4) Defoamers (0.0-1.0% by weight) 5) Slip additives (0.0-1.0% by weight) 6) Colourant dispersed in monomers or oligomers (1.0- 50.0% by weight) 7) Solvents (0.0-30.0% by weight) Table No .1 Testing and observations: Testing of White ink SR Characteristics Specification example 1 example 2 example 3 example 4 example 5 example 6 example 1 example 8 example 9 example 10 example 11 conventional system 1 System base coat + Ink coat + clear topcoat base coat + ink coat + clear topcoat base coat + ink coat + clear topcoat base coat + ink coat + clear topcoat base coat + ink coat + clear topcoat base coat + ink coat + clear topcoat base coat ■■ ink coat * clear topcoat base coat + ink coat + clear topcoat base coat + ink coat+ clear topcoat base coat + Ink coat + clear topcoat base coat + ink coat+ clear topcoat base coat + decal application* clear coat application 2 Substrate automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied par* automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part automotive base coat applied part 3 Application UV Inkjet printing UV irtkjet printing UV inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing UV Inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing manual sticker application 4 Cost low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional low compare to conventional high compare to UV curing process 5 Skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement very high skill requirement 6 Inventory low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level low inventory level high inventory level 7 Production speed very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional Slow as compared to UV curing process as this is man dependent process 8 Environment friend iy environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process Generates Paper and Plastic waste- Loads environment 9 Curing time very less In terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds very less in terms of few seconds time required for sticking of stickers is high compared to UV ink application 10 Particle size s 1 pm s 1 µm s 1 µm s 1 µm £ 1 µm £1 µm £ 1 µm £ 1 µm £1 µm £ 1 µm £ 1 µm 5 1 µm NA jr Dr/film thickness 10- 15 M 12µ 12µ 12µ 12µ 12 µ 12µ 12µ 12µ 12µ 12M 12M NA 1.2 Gloss @ 60" Min85 92 92 92 92 92 92 92 92 92 92 92 92 13 DOI Min 0.6 07 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 14 Shade of infc White White White White White White White White White White White White NA 15 Hiding {2 coats) Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable 16 Adhesion cross cut Should pass 22/25 Passes Passes Passes Passes Passes Passes Passes . Passes Passes Passes Passes Passes 17 Pencil hardness Should pass H H passes H passes H passes H passes H passes H passes H passes H passes H passes K passes H passes H passes 18 Flexibility (1/4' conical mandrel) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 19 Impact Dupont (direct) (500 gm, '/2', 50 cm) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 20 Petrol resistance (1hr) examine the specimen for peeling, blistering S edge curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 21 Water Resistance ' ■ at room temp, for 48 hrs. examine the specimen for peeling, blistering & edge curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 22 E 10 resistance (1hr) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 23 Xylene rub test Should pass 8 rubs Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 24 ASTM Salt spray Should pass 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168. hrs Passes 168 hrs 25 Water jet test Water et shall have working pressure fo 20-22Kg/sq.cm&a delivery at jet 13.5 LitVmin , 5 min. of exposure. Examine the specimen for peeling, blistering & edge curling off. Similar test to be conducetd by exposing test specimen with a cross cut made by knife anywhere on it to the water jet as above. Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 26 Acid Resistance Test specimen in 0.1N Suphuricacid at room temp, for 12hrs. examine the specimen for peeling, blistering & edge curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 27 Alkali Resistance Test specimen in 0.1N NaOHat room temp, for 6 hrs. examine the specimen for peeling, blistering & edge curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes 28 Humidity (IS 101) Should pass 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs , Passes 168 hrs Passes 168 hrs Passes 168 hrs 29 QUV resistance Should pass 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs 30 Durability Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent if sticking of decal is proper. 31 Chances of failure very less very less very less very less very less very less very less very less very less very less very less very high if unskilled person is used for application 32 consumption of clear coat reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating reduced as compared to conventional coating higher as compared to UV Inkjet application Observations : It has been observed that printing of stickers with UV curable inkjet printing process is useful beneficial with respect to: 1) System of application : Application system on painted automotive part comparatively easy than conventional sticker application system. 2) Cost: Cost effective system as compared to conventional sticker application system. 3) Skill requirement: for application of stickers skilled persons required. But inkjet application process is computerized process. 4) Inventory : In inkjet printing process additional inventory is not required. 5) Production speed : improvement in productivity with inkjet process. 6) Environment friendly and performance: Inkjet printing process is environmentally process. Performance of inkjet ink is better than stickers as there are less chances of application defects and failures. APPLICATION SYSTEM: CONVENTIONAL DECAL UV CURABLE INK FOR INKJET APPLICATION APPLICATION WE CLAIM : 1) Ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or leveling additives, substrate wetting additives, defoamers, slip additives, organic solvents, for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it. Ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or levelling additives, substrate 2) Ultraviolet radiation curable ink composition according to claim 1 wherein UV curable ink blend is one or more more ethylenically unsaturated monomers, oligomers having property to photopolymerized by ultra-violet radiation, photointtiators or mixture of photoinitiators. 3) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein UV curable ink blend is an amino modified polyether acrylate, a cycloaliphatic epoxy compound, an urethane acrylate, a polyester acrylate, a polyether acrylate, and an epoxy acrylate. 4) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein UV curable ink blend is monomers is selected from UV radiation curable one or more ethylenically unsaturated monomers like 2-phenoxy ethyl acrylate, Ethoxylated phenoxyl acrylate, 2-(2-Ehoxyethoxy)ethyl acrylate, Cyclic trimethylol-propane formal acrylate, B-Carboxyethyl acrylate, Lauryl acrylate, Stearyl Acrylate, Isodecyl acrylate C8-C10 acrylate, Lauryl methacrylate, Steryl methacrylate, Isobornyl acrylate, Isobornyl methacrylate, Hydroxypivalyl hydroxypivalate diacrylate, 1,6-hexanediol diacrylate, Ethoxylated 1,6-Hexanediol diacrylate, Dipropylene glycol diacrylate, Tripropylen glycol diacrylate, Polyethylene glycol (200) diacrylate, 1,4-Butanediol diacrylate, Neopentyl glycol diacrylate, Propoxylated Neopentyl glycol diacrylate, Polyethylene glycol (400) diacrylate, Ethoxylated Bisphenol-A diacrylate, Polyethylene glycol (600) diacrylate, 2-methyl-1,3-Propanediol diacrylate, Ethoxylated 2-Methyl-1,3-Propanediol diacrylate, 2-Butyl-2Ethyl-1,3-Propanediol diacrylate, Ethylene glycol dimethacrylate, Polyethylene glycol (200) Dimethacrylate, Polyethylene glycol (400) Dimethacrylate, Ethoxylated Bisphenol-A dimethacrylate, Thriethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, 2-Hydroxyethyl methacrylate phosphate, Tris(2-Hydroxy Ethyl) Isocyanurate Triacrylate, Trimethylolpropane Triacrylate, Pentaerytritol Triacrylate, Ethoxylated trimethylolpropane triacrylate, Propoxylated trimethylolpropane triacrylate, Propoxylated glyceryl triacrylate, Trimethylol propane trimethacrylate, Ethoxylated trimethylolpropane timethacrylate, Pentaerytritol Tetraacrylate, Ethoxylated Pentaerythritol Tetraacrylate, Ditrimethylolpropane Tetraacrylate, Pentaerytritol Tetraacrylate, Dipentaerytritol Hexaacrylate, 2-Phenoxy Ethyl Acrylate, 1,6-Hexanediol Diacrylate, Tripropylene Glycol Diacrylate, Trimethylolpropane Triacrylate, Ethoxylated Trimethylolpropane Triacrylate, Ethylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate Also vinylamide such as N-vinylcaprolactam or N-vinylformamide; or acrylamide or a substituted acrylamide such as acryloylmorpholine; and amino functionalized polyetheracrylates 5) Ultraviolet radiation curable ink composition according to claim any one of the preceding claim wherein UV curable ink blend is oligomer is selected from urethane acrylate oligomers, difunctional, tetrafunctional, Hexa functional, epoxy acrylate oligomers, bisphenol -A Epoxy acrylate, polyester acrylate oligomers , polyester acrylate oligomers, chlorinated polyester, acrylic acrylate oligomers, polyether acrylate oligomers, amine synergists 6 ) Ultraviolet radiation curable ink composition according to claim any one of the preceding claim wherein UV curable ink blend monomer or oligomer is in an amount between 1. 0 to 99.0 %. 7) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein photoinititors is selected from photoinitiator or mixture of photoinitiator are benzophenones, thioxanthones,1,2-diketones and anthraquinones. 8) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein co - inititors are seslected from aliphatic amine, an aromatic amine and a thiol, tertiary amines, Heterocyclic thiols and 4-dialkylamino-benzoic acid. 9) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein photoinititors are selected from benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1 -phenylpropan-1 -one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one or 5,7-diiodo-3-butoxy-6-fluorone, diphenyliodonium fluoride and triphenylsulfonium hexafluophosphate, Irgacure184/ PI 184, Irgacure500, Irgacure 907, Irgacure. 369, Irgacure 1700, Irgacur 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur4265 and Darocur ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO , Benzildimethylketal, Benzophenone, 1-Hydroxycyclohexylphenylketone , Camphorquinone, 2,4 Diethylthioxanthone, Dimethylhydroxyacetophenone, 2-Ethylhexyl-4-dimethylaminobenzoate, Ethyl-4-dimethylaminobenzoate, Isopropylthioxanthone, 1-Hydroxycyclohexylphenylketone Liquid benzophenone, Liquid Photoinitiator blend, Methyl-o-benzoyl-benzoate Methylbenzoylformate, N-Methyldiethanolamine, 4-Phenylbenzophenone 2-Methyl-1(4-methylthiophenyl)-2-morpholinpropan-1-one, 2,4,6-Trimethylbezoylphenyl-phosphineoxide, Bis{2,4,6-trimethylbenzoyr)-phenylphosphineoxide, Polymeric Aminobenzoate Derivative Polymeric Benzophenone Derivative, Polymeric Thioxanthone Derivative 10) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein photoinititors 1. 0 to 20.0 % of the total weight of the total ink composition. 11) Ultraviolet radiation curable ink composition according to claim 1 colorant is dispersed in monomers or oligomers. 12) Ultraviolet radiation curable ink composition according to claim 1 or colorant is 1 to 50 % of the total weight of the total ink composition. 13) Ultraviolet radiation curable ink composition according to claim 1, silicone based flow additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition. 14) Ultraviolet radiation curable ink composition according to claim 1, silicone based substrate wetting additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition. 15) Ultraviolet radiation curable ink composition according to claim 1, silicone based or non silicone defoamers are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition. 16) Ultraviolet radiation curable ink composition according to claim 1, silicone based slip additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition. 17) Ultraviolet radiation curable ink composition according to claim 1, silicone based or non silicone defoamers are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition. 18) Ultraviolet radiation curable ink composition according to claim 1, solvents are selected from alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters. Suitable alcohols include methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol, t.-butanol. Suitable aromatic hydrocarbons include toluene, and xylene. Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2,4-pentanedione and hexafluoroacetone. Also glycol, glycolethers, N-methylpyrrolidone, N,N-dimethylacetamid, N,N-dimethylformamid. 19) Ultraviolet radiation curable ink composition according to claim 1, 17 solvent in an amount between 0.1 to 20.0 % of the total weight of the total ink composition. 20) Ultraviolet radiation curable ink composition according to claim 1 is for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it.

Full Text

FORM 2
THE PATENTS ACT, 1970 COMPLETE SPECIFICATION
(SECTION 10)
TITLE : AN ULTRAVIOLET RADIATION CURABLE INK COMPOSITION FOR INKJET APPLICATION ON THE PAINTED AUTOMOTIVE PARTS OR PAINTED POLYMER AUTOMOTIVE SUBSTRATES FOR DECORATION AND TEXT PRINTING PURPOSE WITH CLEAR TOPCOAT.
APPLICANT : KANSAI NEROLAC PAINTS LTD.,
a Company registered under the Companies Act, 1956 having address at Nerolac House, Ganpatrao Kadam Marg, Lower Parel, Mumbai -400 013, India. Indian National
The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF THE INVENTION
The present invention relates to an UV curable composition which exhibits a relative low viscosity and is curable at a high sensitivity, forming a coating of superior adhesion and hardness, and its use on the base coat painted automotive parts which are lacquered by conventional taping lacquer. The invention concerns coatings curable by ultraviolet radiation, which may be printed on to polymer substrates to provide a thermal drop-on-demand ink-jet receptive layer.
Radiation curable ink compositions that include a curable component having a functionality that is greater than two, is present in the ink composition in an amount greater than 50 percent 6y weight, ana' has a molecular weight in the range of about 400 g/mole to about 10,000 g/mole; a component that has a functionality that is less than or equal to 2; and an initiator component. A solvent component, pigment, a surface tension modifier and other materials also can be included. The radiation curable inks are employed in ink jet printers and are particularly suited for use in printing on large-scale substrates. The printed images described herein have good adhesion to polymeric substrates such as styrene-based, polycarbonates, polyolefins, polyethylene terephthalate glycol ester, acryliC and others.
A composition of an ultraviolet light curable jettable ink which includes a colorant, a photoinitiating system, and monomers and flow additives used for printing onto the painted automotive base coat for decoration purpose and exposing the marking to ultraviolet radiation after at least two second.
BACKGROUND OF THE INVENTION
In general, ink containing a substantial amount of organic liquids would produce undesirable emissions during the printing process. such emissions are substantially avoided, however, with energy curable inks. Energy curable inks use low viscosity

reactive materials to attain the desired viscosity. The reactive materials have reactive groups that are cured after printing with radiation, such as UV radiation or electron beams.
First, faster cure times offer substantial economic benefits. Furthermore, heat sensitive materials can be safely coated and cured with UV light without thermal degradation of heat sensitive substrates. Additionally, UV light is a relatively low cost of energy due to its widespread availability.
Advantages of UV curable inks:
Faster cure time offers substantial economic benefits.
Heat sensitive material can be safely coated and cured with UV light without thermal
degradation of heat sensitive substrates.
Additionally UV light is a low cost of energy due to its widespread availability.
Radiation curable inks are printed onto numerous substrates, both rigid and flexible. These include polymeric substrates, such as various types of PVC as well as polystyrene (usually modified), polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyolefines, polyesters, and others. The appearance of the printed image is affected by "jettable" characteristics of the ink, such as ink viscosity, droplet formation, satellite formation, drying or curing time and other properties that relate to the ejection of the ink from the print head, droplet travel and impact onto substrate.
The low viscosity reactive materials in energy curable inks may include monoethylenically and polyethylenically unsaturated monomers and oligomers. The energy curable inks may also include unreactive oligomers and polymers. Because monofunctional monomers are particularly low in viscosity, ink jet inks to date have included substantial amounts of monofunctional monomers.

Therefore, a need continues to exist for radiation-curable ink compositions that adhere well to multiple substrates, form printed images having good appearance, improved hardness and good flexibility and that are capable of withstanding outdoor weather conditions.
The invention generally relates to radiation-curable ink compositions for inkjet printing, to methods for using them and to printed displays produced by curing the ink compositions on a substrate. In one embodiment, the invention is directed to radiation-curable ink compositions for inkjet printing on multiple substrates.
Prior art:
Ink-jet printing is a technique which puts a number of constraints on the nature of the ink which is used. These constraints include low viscosity (usually less than 50 cP or, for continuous operation, less than 10 cP at 25.degree. C), sufficient surface tension that the jet can produce the necessary large number of small droplets, and (at least for continuous operation) sufficient conductivity that the droplets can be directed as desired onto a substrate to be printed. The ink must be a homogeneous liquid capable of rapid conversion to a dry printed area on the substrate.
Inks for use in piezoelectric drop-on-demand ink-jet printing traditionally comprise a mixture of fatty acids, fatty esters and oil-soluble dyes. Such inks should be slow-drying, to prevent clogging of the nozzles; this constraint results in the process being suitable only for surfaces where the ink may dry through absorption On non-absorbent surfaces, the ink remains wet for an undesirably long period of time. Ink compositions available in market are composed of different monomers, oligomers, pigments, additives and photoinitiators. These compositions tried for printing with inkjet printing machine. These inks found to be inferior in terms of curing, consistency in printing. The printed images have poor water resistant, have poor flexibility characteristics as well as hardness of these images is found to be not up to the mark.

In some cases curing of the inks is not possible even after changing different line conditions of the printing process.
These UV ink compositions are costlier than the described invention. Hence we can get economical advantage with the better performance properties.
Comparable study of performance properties is given in the table no.1
Ink compositions of the invention are compatible with ink jet printing systems, in particular systems designed to produce logos and text art displays. They have favorable dot gain characteristics and result in good quality printed images that exhibit good adherence to many of the substrates being used in outdoor displays. In addition, the printed images are water resistant, have good flexibility characteristics as well as improved hardness,
The invention further provides an ink jet printing method in which an ink jet printer prints the ink jet ink of the invention onto a substrate which is base coat painted metal parts. The use of this UV curable ink is for decoration i.e. printing of company logos and text for decoration purpose.
For example : US patent 6,593,390 describes development of a radiation curable ink jet ink which is essentially free of non-reactive diluent and yet has the desired viscosity, surface tension, volatility, stability and drying rate and produces print of acceptable quality. Inks according to the invention thus can be printed without difficulty from ink jet printers to give good quality print on a variety of substrates including such disparate materials as paper and non-adsorbent materials e.g. metal. They are of particular interest, however, in printing on plastics which are difficult to print on, e.g. polyolefins such as polyethylene and polypropylene

The inks may be employed for printing on to a wide variety of substrates, both absorbent and non-absorbent including paper, glass, plastic and metal, e.g. steel, copper and aluminium, but claimed that suitable for printing on to plastics to provide a strongly bonded print of good definition and optical density, especially if the surface to be printed is pre-treated e.g. by flame, plasma etch or corona treatment to raise the surface energy.
US patent 7365105: The patent describes radiation curable ink compositions and applications thereof. The radiation curable ink gives the printed images described herein have good adhesion to polymeric substrates such as styrene-based, polycarbonates, polyolefins, polyethylene terephthalate glycol ester, acrylic and others.
But these ink compositions are found to be inferior on the base coat painted metal parts. For white ink consistency of printing and curing is found to be inferior. For black ink curing of print is inferior. Over this UV cured printed layer thermosetting acrylic or polyester based topcoat is applied. It is found that inter coat adhesion of base coat, printing layers and acrylic or polyester based topcoat is poor. This ink composition is found to be working well only on plastic parts.
These prior art difficulties are overcome by new novel ink composition which is suitable for base coat (acrylic, alkyd, polyester) painted metal parts as well as on the plastic parts. In addition to good substrate adhesion, the inks adhere to one another when printed in layers.
Over this UV cured printed layer thermosetting acrylic or polyester based topcoat is applied. It is found that inter coat adhesion of base coat, printing layers and acrylic or polyester based topcoat is better.

Present Process of application of stickers on automotive parts:

OBJECTIVE OF THE INVENTION:
It is an object of the present invention to provide new radiation curable composition of radiation curable ink for printing on the base coat painted automotive parts. This radiation curable ink with relatively low viscosity and high curing sensitivity, capable of forming a strong and soft film even under various environments.
It is also an object of the present invention to provide new UV curable ink for inkjet printing on painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it with better hardness as well as flexibility to provide proper adhesion to the base coat painted substrate as well as with the top coat layer.

DETAILED DESCRIPTION OF THE INVENTION:
Conventionally decorative text is applied by application of stickers on the different different substrates including metal, plastic, paper.
The structural composition of the sticker then we can find different layers of the paper and plastic material. When we apply sticker on any substrate only printed part is utilized for application. After application of this remaining plastic coverings of the sticker are thrown away. This will be non value added waste to the environment.
Disadvantages of stickers:
• Costlier.
• Generates Paper and Mastic waste.
• Requirement of skilled person for application.
Advantages of Inkjet printing
• As a system Less costlier than stickers.
• Environment friendly Process as there is no generation of paper and plastic wastes.
• Customized process hence less chances of errors.
By making use of radiation curable ink -jet ink is utilized for ink jet application on the painted automotive parts or painted polymer automotive substrates for Decorative image and text printing purpose with clear topcoat over it.
Composition of Radiation curable ink:
This radiation curable ink is divided in to two parts:
1) UV curable clear ink base :
2) Colourant dispersed in monomers or oligomers:

The radiation curable ink-jet ink and the radiation curable liquid layer contain monomers and/or oligomers, which are polymerized by the curing means of the inkjet printer. Monomers, oligomers or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri- and higher functionality monomers, oligomers and/or prepolymers may be used. These components are curable, typically photo-curable, e.g. UV curable, and should adhere to the ink-receiver surface after printing and serve to bind the colorant. A mixture of two or more monomers of the same functionality is preferred, with particularly preferred a mixture of two di-functional monomers.
The viscosity of the radiation curable ink-jet ink and the radiation curable liquid layer can be adjusted by varying the ratio between the monomers and oligomers.
Any method of conventional radical polymerization, photo-curing system using photo acid or photo base generator, or photo induction alternating copolymerization may be employed. In general, radical polymerization and cationic polymerization are preferred, and photo induction alternating copolymerization needing no initiator may also be employed. Furthermore, a hybrid system of combinations of these systems is also effective.
Description :-
Preparation of a Radiation Curable Ink-Jet Ink blend particularly preferred for use as a radiation-curable compound in the radiation curable ink-jet ink and the radiation curable liquid layer are :
Monomers:
2-phenoxy ethyl acrylate, Ethoxylated phenoxyl acrylate, 2-(2-Ehoxyethoxy)ethyl acrylate, cyclic trimethylol-propane formal acrylate, p-carboxyethyl acrylate, Lauryl acrylate, stearyl acrylate, isodecyl acrylate, C8-C10 acrylate, lauryl methacrylate,

steryl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypivalyl hydroxypivalate diacrylate, 1,6-hexanediol diacrylate, Ethoxylated 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylen glycol diacrylate, polyethylene glycol (200) diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol (400) diacrylate ethoxylated bisphenol-A diacrylate, polyethylene glycol (600) diacrylate, 2-methyl-1,3-propanediol diacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate, 2-butyl-2-ethyI-1,3-propanediol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, ethoxylated bisphenol-A dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate phosphate
Trifunctional monomers:
Tris(2-Hydroxy Ethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerytritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, trimethylol propane trimethacrylate, ethoxylated trimethylolpropane timethacrylate
Multifunctional Monomers:
Pentaerytritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerytritol tetraacrylate, dipentaerytritol hexaacrylate, 2-phenoxy ethyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate.

Also vinylamide such as N-vinylcaprolactam or N-vinylformamide; or acrylamide or a substituted acrylamide such as acryloylmorpholine; and amino functionalized polyetheracrylates
Oligomers:
1) Urethne acrylate oligomers : (Afunctional, tetrafunctional, hexa functional, epoxy acrylate oligomers : bisphenol -A epoxy acrylate, polyester acrylate oligomers : Different functional polyester acrylate oligomers, chlorinated polyester acrylates, acrylic acrylate oligomers, polyether acrylate oligomers, reactive amine synergists, Specific functional oligomers : organic/ inorganic hybrid products.
Ultraviolet radiation curable ink composition wherein UV curable ink blend monomer or oligomer is in an amount between 1. 0 to 99.0 %.
Photo-Initiators :
A catalyst called a photo-initiator typically initiates the polymerization reaction. The photo-initiator requires less energy to activate than the monomers and oligomers to form the polymer. The photo-initiator suitable for use in the radiation curable ink-jet ink and the radiation curable liquid layer may be a Norrish type I initiator, a Norrish type II initiator or a photo-acid generator.
The photo-initiator absorbs light and is responsible for the production of free radicals or cations. Free radicals or cations are high-energy species that induce polymerization of monomers, oligomers and polymers and with polyfunctional monomers and oligomers thereby also inducing cross-linking.
A preferred Norrish type l-initiator is selected from the group consisting of

benzoinethers, benzil ketals, .alpha,..alpha.-dialkoxyacetophenones, .alpha.-
hydroxyalkylphenones, .alpha.-aminoalkylphenones, acylphosphine oxides,
acylphosphine sulphides, .alpha.-haloketones, .alpha.-halosulfones and .alpha.-
halophenylglyoxalates.
A preferred Norrish type ll-initiator is selected from the group consisting of
benzophenones, thioxanthones, 1,2-diketones and anthraquinones. A preferred co-
initiator is selected from the group consisting of an aliphatic amine, an aromatic
amine and a thiol. Tertiary amines, heterocyclic thiols and 4-dialkylamino-benzoic
acid are particularly preferred as co-initiator. Specific examples of photo-initiators
may include, but are not limited to, the following compounds or combinations thereof:
benzophenone and substituted benzophenones, 1-hydroxycyclohexyl phenyl ketone,
thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-
one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil
dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one or 5,7-diiodo-3--butoxy-6-fluorone, diphenyliodonium fluoride and triphenylsulfonium hexafluophosphate.
Suitable commercial photo-initiators include Irgacure184/ PI 184, Irgacure500, Irgacure 907, Irgacure. 369, Irgacure 1700, Irgacure 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur 4265 and Darocur ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO
Benzildimethylketal, Benzophenone, 1-Hydroxycyclohexylphenylketone
Camphorquinone, 2,4 Diethylthioxanthone, Dimethylhydroxyacetophenone 2-
Ethylhexyl-4-dimethylaminobenzoate, Ethyl-4-dimethylaminobenzoate
Isopropylthioxanthone, 1-Hydroxycyciohexylphenylketone and Benzophenone Liquid

benzophenone, Liquid Photoinitiator blend, Methyl-o-benzoyl-benzoate
Methyibenzoylformate, N-Methyldiethanolamine, 4-Phenylbenzophenone 2-Methyl-
1(4-methylthiophenyl)-2~morpholinpropan-1-one, 2,4,6-Trimethylbezoylphenyl-
phosphineoxide, Bis{2,4,6-trimethylbenzoyl)-phenylphosphineoxide, Polymeric Aminobenzoate Derivative Polymeric Benzophenone Derivative, Polymeric Thioxanthone Derivative
Inhibitors :
Suitable polymerization inhibitors include phenol type antioxidants, hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol may also be used. Of these, a phenol compound having a double bond in molecules derived from acrylic acid is particularly preferred due to its having a polymerization-restraining effect even when heated in a closed, oxygen-free environment. Suitable inhibitors are, for example, Sumilizer.TM. GA-80, Sumilizer.TM. GM and Sumilizer.TM. GS produced by Sumitomo Chemical Co., Ltd, and Genorad.TM.16, Genorad.TM.18 available from Rahn of Zurich, Switzerland.
Since excessive addition of these polymerization inhibitors will lower the ink sensitivity to curing, it is preferred that the amount capable of preventing polymerization be determined prior to blending. The amount of a polymerization inhibitor is generally between 1-20 % of the total ink weight or the total link composition.
Furthermore, the radiation curable ink-jet ink and the radiation curable liquid layer may also contain polymerizable oligomers. Examples of these polymerizable oligomers include epoxy acrylates, aliphatic urethane acrylates, aromatic urethane acrylates, polyester acrylates, and straight-chained acrylic oligomers.

Colorants :
Colorants may be dyes, but are preferably pigments or a combination thereof. Organic and/or inorganic pigments, pigments dispersion pastes may be used.
The pigment particles should be sufficiently small to permit free flow of the ink through the inkjet printing device, especially at the ejecting nozzles which usually have a diameter ranging from 10 .mu.m to 50 .mu.m. The particle size influences also the pigment dispersion stability. It is also desirable to use small particles for maximum colour strength. The particles of the pigment dispersed in the ink-jet ink should have a particle size of less than 10 .mu.m, preferably less than 3 .mu.m, and most preferably less than 1 .mu.m. The average particle size of pigment particles is preferably 0.05 to 0.5 .mu.m.
Suitable pigments include as red or magenta pigments: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; as blue or cyan pigments: Pigment Blue 1,15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60; as green pigments: Pigment green 7, 26, 36, and 50; as yellow pigments: Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 177, 180, 185, and 193; as white pigment: Pigment White 6, 18, and 21.
Most preferred pigments are Pigment Yellow 1, 3, 128, 109, 93, 17, 14, 10, 12, 13, 83, 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22, 23, 17, 210, 170, 188, 185, 146, 144, 176, 57:1, 184, 202, 206, 207; Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16 and Pigment Violet 19.

Carbon black is usually used as the colouring material in black ink. Suitable black pigment materials include carbon blacks such as Pigment Black 71.
The pigment is present in the range of 0.1 to 50 wt %, based on the total weight of the radiation curable inkjet ink.
Dyes suitable for the radiation curable ink-jet ink include direct dyes, acidic dyes, basic dyes and reactive dyes.
Suitable direct dyes for the radiation curable ink-jet ink include: C.I. Direct Yellow 1, 4, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86, 100, 110, 120, 132, 142, and 144 C.I. Direct Red 1,2, 4, 9, 11, 134, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 47, 48, 51, 62, 63, 75, 79, 80, 81, 83, 89, 90, 94, 95, 99, 220, 224, 227 and 343 C.I. Direct Blue 1, 2, 6, 8,1 5, 22, 25, 71, 76, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 236, and 237 C.I. Direct Black 2, 3, 7, 17, 19,22,32,38, 51,56,62,71,74,75,77, 105, 108, 112, 117, and 154
Suitable acidic dyes for the radiation curable ink-jet ink include: C.I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 20, 38, 42, 49, 59, 61, 72, and 99 C.I. Acid Orange 56 and 64 C.I. Acid Red 1,8, 14, 18,26,32,37,42,52,57,72,74,80,87, 115, 119, 131, 133, 134, 143, 154, 186, 249, 254, and 256 C.I. Acid Violet 11, 34, and 75 C.I. Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, and 249 C.I. Acid Green 9, 12, 19, 27, and 41 C.I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 60, 94, 107, 109, 110, 119, 131, and 155.
Suitable reactive dyes for the radiation curable ink-jet ink include: C.I. Reactive Yellow 1, 2, 3, 14, 15, 17, 37, 42, 76, 95, 168, and 175 C.I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, and 235 C.I. Reactive Blue

7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, and 235 C.I. Reactive Orange 5, 12, 13, 35, and 95 C.I. Reactive Brown 7, 11, 33, 37, and 46 C.I. Reactive Green 8 and 19 C.I. Reactive Violet 2, 4, 6, 8, 21, 22, and 25 C.I. Reactive Black 5,
8, 31, and 39.
Suitable basic dyes for the radiation curable ink-jet ink include: C.I. Basic Yellow 11, 14, 21, and 32 C.I. Basic Red 1, 2, 9, 12, and 13 C.I. Basic Violet 3, 7, and 14 C.I. Basic Blue 3, 9, 24, and 25.
Dyes can only manifest the ideal colour in an appropriate range of pH value. Therefore, the radiation curable ink-jet ink preferably further comprises a pH buffer, such as potassium hydroxide (KOH).
Resins :
The radiation curable ink-jet ink and the radiation curable liquid layer may further contain a resin, also called a pigment stabilizer or dispersant used to obtain a stable dispersion of the pigment(s) in the inkjet ink.
The pigments may be added to the radiation curable ink-jet ink as a dispersion comprising a dispersant.
Suitable resins: petroleum type resins (e.g., styrene type, acryl type, polyester, polyurethane type, phenol type, butyral type, cellulose type, and rosin); and thermoplastic resins (e.g., vinyl chloride, vinylacetate type). Concrete examples of these resins include acryiate copolymers, styrene-acrylate copolymers, acetalized and incompletely saponified polyvinyl alcohol, and vinylacetate copolymers.

Additives : -
Surfactants :
The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one surfactant. The surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity 0.1-1.0 wt % based on the total ink weight.
A fluorinated or silicone compound may be used as a surfactant, however, a potential drawback is extraction by food from inkjet food packaging material because the surfactant does not cross-link. It is therefore preferred to use a copolymerizable monomer having surface-active effects, for example, silicone-modified acrylates, silicone modified methacrylates, fluorinated acrylates, and fluorinated methacrylates.
Defoamers :
The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one defoamer. The defoamer(s) can be usually added in a total quantity 0.1-1.0 wt % based on the total ink weight.
Slip additives :
The radiation curable ink-jet ink and the radiation curable liquid layer may contain at least one slip additive. The slip additive can be usually added in a total quantity 0.1-1.0 wt % based on the total ink weight.

Solvents :
The radiation curable ink-jet ink and the radiation curable liquid layer may contain as a solvent, water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents, the solvent preferably being present in a concentration between 10 and 80 wt %, particularly preferably between 20 and 50 wt %, each based on the total weight of the radiation curable inkjet ink, respectively the total weight of the radiation curable liquid layer.
However, the radiation curable ink-jet ink preferably does not contain an evaporable component, but sometimes; it can be advantageous to incorporate an extremely small amount of an organic solvent in such inks to improve adhesion to the ink-receiver surface after UV curing. In this case, the added solvent can be any amount in the range which does not cause problems of solvent resistance and VOC, and preferably 0.1-20.0 wt %, and particularly preferably 0.1-10.0 wt %, each based on the total weight of the radiation curable ink-jet ink
Suitable organic solvents include alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters. Suitable alcohols include methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol, t.-butanol. Suitable aromatic hydrocarbons include toluene, and xylene. Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2,4-pentanedione and hexafluoroacetone. Also glycol, glycolethers, N-methylpyrrolidone, N,N-dimethylacetamid, N,N-dimethylformamid may be used.
Examples:
Clear ink base for coloured ink:

Compositions based on different combinations of monomers, oligomers, photoinitiators and stabilizers are as follows:
Example 1
Take a clean and crater free hopper. To which add 12.5 parts by weight lauryl methacrylate, 31.6 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 9.8 parts by wight ethoxylated phenoxyl acrylate, 4.0 parts by weight ethoxylated trimethylolpropane triacrylate, and 5.4 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 1.2 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 3.0 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 2.5 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed.
Example 2
Take a clean and crater free hopper. To which add 3.7 parts by weight lauryl methacrylate, 2.4 parts by weight isobornyl acrylate, 5.0 parts by weight dipropylene glycol diacrylate, 28.8 parts by weight of 1,6-Hexanediol diacrylate, 11.0 parts by weight of triporpylene glycol triacrylate, 31.5 parts by wight ethoxylated phenoxyl acrylate, 10.0 parts by weight ethoxylated trimethylolpropane triacrylate. Stir for 10 -15 minutes. To this solution add 2.8 parts by weight Isopropyl thioxanthone, 2.8 parts by wight 2-Hydroxy-2-methyM-phenyl-propanone, 2.5 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed.
Example 3
Take a clean and crater free hopper. To which add 10.6 parts by weight isobornyl acrylate, 33.0 parts by weight dipropylene glycol diacrylate, 33.5 parts by weight of

1,6-Hexanediol diacrylate, 9.6 parts by weight ethoxylated trimethylolpropane triacrylate, 4.8 parts by weight dipentaerythitol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 2.8 parts by weight Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.7 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed.
Example 4
Take a clean and crater free hopper. To which add 14.3 parts by weight isobornyl acrylate, 30.4 parts by weight dipropylene glycol diacrylate, 27.4 parts by weight of 1,6-Hexanediol diacrylate, 5.7 parts by weight ethoxylated phenoxyl acrylate, 10.5 parts by weight ethoxylated trimethylolpropane triacrylate, 3.1 parts by weight dipentaerythitol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 2.1 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.2 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 2.3 parts by weight 2,4,6-trimethylbenzoyl diphenyl phosphine oxide under stirring. Stir for 20 min until clear solution is formed.
Example 5
Take a clean and crater free hopper. To which add 13.0 parts by weight lauryl methacrylate, 5.6 parts by weight isobornyl acrylate, 5.6 parts by weight dipropylene glycol diacrylate, 4.8 parts by weight of 1,6-Hexanediol diacrylate, 6.7 parts by weight of triporpylene glycol triacrylate, 8.3 parts by weight ethoxylated phenoxyl acrylate, 3.5 parts by weight ethoxylated trimethylolpropane triacrylate, 32.5 parts by weight ethoxylated trimethylolpropane trimethacrylate, 13.0 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 1.0 part by weight bis(2,4,6-trimethy!benzoyl)-phenylphosphineoxide, 1.0 part by weight isopropyl thioxanthone, 1.0 part by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone, 1.0 part by weight 2,4,6-

Trimethylbenzoyl diphenyl phospine oxide, 2.0 parts by weight of isopropylthioxanthone under stirring. Stir for 20 min until clear solution is formed.
Example 6
Take a clean and crater free hopper. To which add 12.5 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 32.6 parts by weight of 1,6-Hexanediol diacrylate, 8.2 parts by weight ethoxylated trimethylolpropane trimethacrylate, 7.5 parts by weight dipentaerythritol hexaacrylate. Stir for 10 - 15 minutes. To this solution add 3.5 parts by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.7 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone( 1.0 part 2,2-dimethoxy-1,2-diphenylethan-1-one under stirring. Stir for 20 min until clear solution is formed.
Example 7
Take a clean and crater free hopper. To which add 10.0 parts by weight lauryl methacrylate, 25.0 parts by weight dipropylene glycol diacrylate, 30.5 parts by weight of 1,6-Hexanediol diacrylate, 6.0 parts by weight of triporpylene glycol triacrylate, 7.3 parts by weight ethoxylated phenoxyl acrylate, 2.1 parts by weight ethoxylated trimethylolpropane triacrylate, 2.1 parts by weight ethoxylated trimethylolpropane trimethacrylate, 2.1 parts by weight dipentaerythritol hexaacrylate, 3.7 parts by weight bisphenol-A epoxy diacrylate, 1 part by weight aliphatic/aromatic epoxy acrylate, 1 part by weight aliphatic urethane diacrylate. Stir for 10 - 15 minutes. To this solution add 2.7 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.5 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone under stirring. Stir for 20 min until clear solution is formed.

Example 8
Take a clean and crater free hopper. To which add 10.6 parts by weight lauryl methacrylate, 33.2 parts by weight of isobornyl acrylate, 33.5 parts by weight dipropylene glycol diacrylate, 9.6 parts by weight ethoxylated phenoxyl acrylate, 4.8 parts by weight ethoxylated trimethylolpropane trimethacrylate. Stir for 10 - 15 minutes. To this solution add 2.8 part by weight bis(2t4,6-trimethylbenzoyl)-phenylphosphineoxide, 5.5 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed.
Example 9
Take a clean and crater free hopper. To which add 10.0 parts by weight isobornyl acrylate, 30.0 parts by weight dipropylene glycol diacrylate, 30.0 parts by weight of 1,6-Hexanediol diacrylate, 8.4 parts by weight ethoxylated trimethylolpropane trimethacrylate, 4.0 parts by weight dipentaerythritol hexaacrylate, 9.2 parts by weight bisphenol-A epoxy diacrylate, 1.7 parts by weight aliphatic urethane diacrylate. Stir for 10-15 minutes. To this solution add 1.8 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 4.9 parts by weight 1-Hydroxy-cyclohexylphenyl-ketone under stirring. Stir for 20 min until clear solution is formed.
Example 10
Take a clean and crater free hopper. To which add 3.0 parts by weight lauryl methacrylate, 2.0 parts by weight isobornyl acrylate, 5.0 parts by weight dipropylene

glycol diacrylate, 25.0 parts by weight of 1,6-Hexanediol diacrylate, 11.0 parts by weight of triporpylene glycol triacrylate, 31.0 parts by weight ethoxylated phenoxyl acrylate, 4.0 parts by weight ethoxylated trimethylolpropane triacrylate, 1.0 parts by weight ethoxylated trimethylolpropane trimethacrylate, 1.0 parts by weight dipentaerythritol hexaacrylate, 5.7 parts by weight aliphatic/ aromaticepoxy acrylate, 3.8 parts by weight aliphatic urethane diacrylate. Stir for 10 - 15 minutes. To this solution add 0.26 part by weight bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 0.4 part by weight isopropyl thioxanthone, 5.0 part by weight 1-Hydroxy-cyclohexylphenyl-ketone, 1.0 part by weight 2-Hydroxy-2-methyl-1-phenyl-propanone, 0.84 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinpropan-1-one under stirring. Stir for 20 min until clear solution is formed.
Different ink compositions:
Different ink compositions are made by different weight percentage of UV curable ink base and different weight percentages of colourants that are dispersed in monomers or oligomers.
Colourants used in different proportion are:
Suitable pigments include as red or magenta pigments: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177,178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; as blue or cyan pigments: Pigment Blue 1,15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60; as green pigments: Pigment green 7, 26, 36, and 50; as yellow pigments: Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 177, 180, 185, and 193; as white pigment: Pigment White 6, 18, and 21.

Most preferred pigments are Pigment Yellow 1, 3,I28, 109, 93,17, 14, 10, 12, 13, 83, 65, 75, 74, 73, 138, 139, 154, 151, 180, 185; Pigment Red 122, 22,2Z, 17, 210, 170, 188, 185, 146, 144, 176, 57:1, 184, 202, 206,107, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Figment Blue 15:6, Pigment Blue 16 and Pigment Violet 19.
Carbon black is usually used as the colouring materiaI in black ink- Suitable black pigment materials include carbon blacks such as Pigment Black 71.
Dyes suitable for the radiation curable ink-jet ink include direct dyes, acidic dyes, basic dyes and reactive dyes.
Suitable direct dyes for the radiation curable ink-jet ink include: C.I. Direct Yellow 1, 4, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86- 100 11°, 120. I32. I42. and 144 C.I. Direct Red 1, 2, 4, 9, 11, 134, 17, 20, 23, 24- 28, 31, 33, 37, 39, 44, 47, 48, 51, 62, 63, 75, 79, 80, 81, 83, 89, 90, 94, 95, 99, 220- 224, 227 and 343 C.I. Direct Blue 1, 2, 6, 8,1 5, 22, 25, 71, 76, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203,207, 236, and 237 C.I. Direct Black 2, 3,7, 17, 19, 22, 32, 38, 51, 56, 62, 71, 74, 75. 77, 105. 108, 112, 117, and 154
Suitable acidic dyes for the radiation curable ink-jet ink include: C.I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 20, 38, 42, 49, 59, 61, 72, and 99 Cl- Acid Orange 56 and 64 C.I. Acid Red 1, 8, 14, 18, 26, 32, 37, 42, 52, 57, 72, 74, 80- 87. H5, 119, 131, 133, 134, 143, 154, 186, 249, 254, and 256 C.I. Acid Violet 11 34. and 75 c.1 Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, and 249 C.I. Acid Green 9, 12, 19, 27, and 41 C.I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 00, 94. 107, 109, 110, 119, 131, and 155

Suitable reactive dyes for the radiation curable ink-jet ink include: C.I. Reactive Yellow 1, 2, 3, 14, 15, 17, 37, 42, 76, 95, 168, and 175 C.I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, and 235 C.I. Reactive Blue
7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, and 235 C.I. Reactive Orange 5, 12, 13, 35, and 95 C.I. Reactive Brown 7, 11, 33, 37, and 46 C.I. Reactive Green 8 and 19 C.I. Reactive Violet 2, 4, 6, 8, 21, 22, and 25 C.I. Reactive Black 5,
8, 31, and 39
Suitable basic dyes for the radiation curable ink-jet ink include: C.I. Basic Yellow 11, 14, 21, and 32 C.I. Basic Red 1, 2, 9, 12, and 13 C.I. Basic Violet 3, 7, and 14 C.I. Basic Blue 3, 9, 24, and 25
UV curable coloured inks contain following components:
1) UV curable clear ink base (40-100 % by weight),
2) Flow and leveling additives (0.0-1.0% by weight)
3) Substrate wetting additives (0.0-1.0% by weight)
4) Defoamers (0.0-1.0% by weight)
5) Slip additives (0.0-1.0% by weight)
6) Colourant dispersed in monomers or oligomers (1.0- 50.0% by weight)
7) Solvents (0.0-30.0% by weight)

Table No .1
Testing and observations:
Testing of White ink

SR Characteristics Specification example 1 example 2 example 3 example 4 example 5 example 6 example 1 example 8 example 9 example 10 example 11 conventional system
1 System base coat +
Ink coat +
clear topcoat base coat +
ink coat +
clear topcoat base coat +
ink coat +
clear topcoat base coat +
ink coat +
clear topcoat base coat +
ink coat +
clear topcoat base coat +
ink coat +
clear topcoat base coat ■■
ink coat *
clear topcoat base coat +
ink coat +
clear topcoat base coat +
ink coat+
clear topcoat base coat +
Ink coat +
clear topcoat base coat +
ink coat+
clear topcoat base coat + decal
application*
clear coat
application
2 Substrate automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied par* automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive
base coat
applied part automotive base coat applied part
3 Application UV Inkjet printing UV irtkjet
printing UV inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing UV Inkjet printing UV inkjet printing UV inkjet printing UV inkjet printing manual sticker application
4 Cost low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional low compare
to conventional high compare to UV curing process
5 Skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement Less skill requirement very high skill requirement
6 Inventory low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level low
inventory
level high inventory level
7 Production speed very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional very fast as compared to conventional Slow as
compared to UV
curing process
as this is man
dependent
process
8 Environment friend iy environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process environment friendly process Generates Paper
and Plastic
waste- Loads
environment
9 Curing time very less In
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds very less in
terms of few
seconds time required for sticking of
stickers is high compared to UV
ink application
10 Particle size s 1 pm s 1 µm s 1 µm s 1 µm £ 1 µm £1 µm £ 1 µm £ 1 µm £1 µm £ 1 µm £ 1 µm 5 1 µm NA

jr Dr/film thickness 10- 15 M 12µ 12µ 12µ 12µ 12 µ 12µ 12µ 12µ 12µ 12M 12M NA
1.2 Gloss @ 60" Min85 92 92 92 92 92 92 92 92 92 92 92 92
13 DOI Min 0.6 07 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
14 Shade of infc White White White White White White White White White White White White NA
15 Hiding {2 coats) Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable Acceptable
16 Adhesion cross cut Should pass 22/25 Passes Passes Passes Passes Passes Passes Passes . Passes Passes Passes Passes Passes
17 Pencil hardness Should pass H H passes H passes H passes H passes H passes H passes H passes H passes H passes K passes H passes H passes
18 Flexibility (1/4' conical mandrel) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
19 Impact Dupont
(direct) (500 gm, '/2',
50 cm) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
20 Petrol resistance (1hr) examine the
specimen for
peeling,
blistering S edge
curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
21 Water Resistance ' ■ at room temp, for 48 hrs. examine the
specimen for
peeling,
blistering & edge
curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
22 E 10 resistance (1hr) Should pass Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
23 Xylene rub test Should pass 8 rubs Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
24 ASTM Salt spray Should pass 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168
hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168. hrs Passes 168 hrs

25
Water jet test Water
et shall have
working pressure fo
20-22Kg/sq.cm&a
delivery at jet 13.5
LitVmin , 5 min. of
exposure. Examine the
specimen for
peeling,
blistering & edge
curling off.
Similar test to be
conducetd by
exposing test
specimen with a
cross cut made
by knife
anywhere on it to
the water jet as
above. Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
26 Acid Resistance
Test specimen in
0.1N Suphuricacid
at room temp, for
12hrs. examine the
specimen for
peeling,
blistering & edge
curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
27 Alkali Resistance
Test specimen in
0.1N NaOHat
room temp, for 6
hrs. examine the
specimen for
peeling,
blistering & edge
curling off Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes Passes
28 Humidity (IS 101) Should pass 168 hrs Passes 168 hrs Passes 168
hrs Passes 168
hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs Passes 168 hrs , Passes 168
hrs Passes 168
hrs Passes 168 hrs
29 QUV resistance Should pass 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs Passes 800 hrs
30 Durability Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent if sticking of decal is proper.
31 Chances of failure very less very less very less very less very less very less very less very less very less very less very less very high if
unskilled person is
used for
application
32 consumption of clear coat reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating reduced as
compared to
conventional
coating higher as compared to UV Inkjet application

Observations :
It has been observed that printing of stickers with UV curable inkjet printing process is useful beneficial with respect to:
1) System of application : Application system on painted automotive part comparatively easy than conventional sticker application system.
2) Cost: Cost effective system as compared to conventional sticker application system.
3) Skill requirement: for application of stickers skilled persons required. But inkjet application process is computerized process.
4) Inventory : In inkjet printing process additional inventory is not required.
5) Production speed : improvement in productivity with inkjet process.
6) Environment friendly and performance: Inkjet printing process is environmentally process. Performance of inkjet ink is better than stickers as there are less chances of application defects and failures.

APPLICATION SYSTEM:
CONVENTIONAL DECAL UV CURABLE INK FOR INKJET
APPLICATION APPLICATION

WE CLAIM :
1) Ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or leveling additives, substrate wetting additives, defoamers, slip additives, organic solvents, for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it. Ultraviolet radiation curable ink composition comprising UV curable ink blend, colourant, flow or levelling additives, substrate
2) Ultraviolet radiation curable ink composition according to claim 1 wherein UV curable ink blend is one or more more ethylenically unsaturated monomers, oligomers having property to photopolymerized by ultra-violet radiation, photointtiators or mixture of photoinitiators.
3) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein UV curable ink blend is an amino modified polyether acrylate, a cycloaliphatic epoxy compound, an urethane acrylate, a polyester acrylate, a polyether acrylate, and an epoxy acrylate.
4) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein UV curable ink blend is monomers is selected from UV radiation curable one or more ethylenically unsaturated monomers like 2-phenoxy ethyl acrylate, Ethoxylated phenoxyl acrylate, 2-(2-Ehoxyethoxy)ethyl acrylate, Cyclic trimethylol-propane formal acrylate, B-Carboxyethyl acrylate, Lauryl acrylate, Stearyl Acrylate, Isodecyl acrylate C8-C10 acrylate, Lauryl methacrylate, Steryl methacrylate, Isobornyl acrylate, Isobornyl methacrylate, Hydroxypivalyl hydroxypivalate diacrylate, 1,6-hexanediol diacrylate, Ethoxylated 1,6-Hexanediol diacrylate, Dipropylene glycol diacrylate, Tripropylen glycol diacrylate, Polyethylene glycol (200) diacrylate, 1,4-Butanediol diacrylate, Neopentyl glycol diacrylate, Propoxylated Neopentyl glycol diacrylate, Polyethylene glycol (400) diacrylate,

Ethoxylated Bisphenol-A diacrylate, Polyethylene glycol (600) diacrylate, 2-methyl-1,3-Propanediol diacrylate, Ethoxylated 2-Methyl-1,3-Propanediol diacrylate, 2-Butyl-2Ethyl-1,3-Propanediol diacrylate, Ethylene glycol dimethacrylate, Polyethylene glycol (200) Dimethacrylate, Polyethylene glycol (400) Dimethacrylate, Ethoxylated Bisphenol-A dimethacrylate, Thriethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, 2-Hydroxyethyl methacrylate phosphate, Tris(2-Hydroxy Ethyl) Isocyanurate Triacrylate, Trimethylolpropane Triacrylate, Pentaerytritol Triacrylate, Ethoxylated trimethylolpropane triacrylate, Propoxylated trimethylolpropane triacrylate, Propoxylated glyceryl triacrylate, Trimethylol propane trimethacrylate, Ethoxylated trimethylolpropane timethacrylate, Pentaerytritol Tetraacrylate, Ethoxylated Pentaerythritol Tetraacrylate, Ditrimethylolpropane Tetraacrylate, Pentaerytritol Tetraacrylate, Dipentaerytritol Hexaacrylate, 2-Phenoxy Ethyl Acrylate, 1,6-Hexanediol Diacrylate, Tripropylene Glycol Diacrylate, Trimethylolpropane Triacrylate, Ethoxylated Trimethylolpropane Triacrylate, Ethylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate Also vinylamide such as N-vinylcaprolactam or N-vinylformamide; or acrylamide or a substituted acrylamide such as acryloylmorpholine; and amino functionalized polyetheracrylates
5) Ultraviolet radiation curable ink composition according to claim any one of the preceding claim wherein UV curable ink blend is oligomer is selected from urethane acrylate oligomers, difunctional, tetrafunctional, Hexa functional, epoxy acrylate oligomers, bisphenol -A Epoxy acrylate, polyester acrylate oligomers , polyester acrylate oligomers, chlorinated polyester, acrylic acrylate oligomers, polyether acrylate oligomers, amine synergists
6 ) Ultraviolet radiation curable ink composition according to claim any one of the preceding claim wherein UV curable ink blend monomer or oligomer is in an amount between 1. 0 to 99.0 %.

7) Ultraviolet radiation curable ink composition according to claim 1 or 2 wherein photoinititors is selected from photoinitiator or mixture of photoinitiator are benzophenones, thioxanthones,1,2-diketones and anthraquinones.
8) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein co - inititors are seslected from aliphatic amine, an aromatic amine and a thiol, tertiary amines, Heterocyclic thiols and 4-dialkylamino-benzoic acid.
9) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein photoinititors are selected from benzophenones, 1-hydroxycyclohexyl phenyl ketone, thioxanthones such as isopropylthioxanthone, 2-hydroxy-2-methyl-1 -phenylpropan-1 -one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, benzil dimethylketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one or 5,7-diiodo-3-butoxy-6-fluorone, diphenyliodonium fluoride and triphenylsulfonium hexafluophosphate, Irgacure184/ PI 184, Irgacure500, Irgacure 907, Irgacure. 369, Irgacure 1700, Irgacur 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur4265 and Darocur ITX available from CIBA SPECIALTY CHEMICALS, Lucerin TPO , Benzildimethylketal, Benzophenone, 1-Hydroxycyclohexylphenylketone , Camphorquinone, 2,4 Diethylthioxanthone, Dimethylhydroxyacetophenone, 2-Ethylhexyl-4-dimethylaminobenzoate, Ethyl-4-dimethylaminobenzoate, Isopropylthioxanthone, 1-Hydroxycyclohexylphenylketone Liquid benzophenone, Liquid Photoinitiator blend, Methyl-o-benzoyl-benzoate Methylbenzoylformate, N-Methyldiethanolamine, 4-Phenylbenzophenone 2-Methyl-1(4-methylthiophenyl)-2-morpholinpropan-1-one, 2,4,6-Trimethylbezoylphenyl-phosphineoxide, Bis{2,4,6-trimethylbenzoyr)-phenylphosphineoxide, Polymeric Aminobenzoate Derivative Polymeric Benzophenone Derivative, Polymeric Thioxanthone Derivative

10) Ultraviolet radiation curable ink composition according to claim 1 or 2 or 7 wherein photoinititors 1. 0 to 20.0 % of the total weight of the total ink composition.
11) Ultraviolet radiation curable ink composition according to claim 1 colorant is dispersed in monomers or oligomers.
12) Ultraviolet radiation curable ink composition according to claim 1 or colorant is 1 to 50 % of the total weight of the total ink composition.
13) Ultraviolet radiation curable ink composition according to claim 1, silicone based flow additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition.

14) Ultraviolet radiation curable ink composition according to claim 1, silicone based substrate wetting additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition.
15) Ultraviolet radiation curable ink composition according to claim 1, silicone based or non silicone defoamers are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition.
16) Ultraviolet radiation curable ink composition according to claim 1, silicone based slip additives are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition.
17) Ultraviolet radiation curable ink composition according to claim 1, silicone based or non silicone defoamers are present in an amount between 0.0 to 1.0 % of the total weight of the total ink composition.

18) Ultraviolet radiation curable ink composition according to claim 1, solvents are selected from alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters. Suitable alcohols include methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol, t.-butanol. Suitable aromatic hydrocarbons include toluene, and xylene. Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2,4-pentanedione and hexafluoroacetone. Also glycol, glycolethers, N-methylpyrrolidone, N,N-dimethylacetamid, N,N-dimethylformamid.
19) Ultraviolet radiation curable ink composition according to claim 1, 17 solvent in an amount between 0.1 to 20.0 % of the total weight of the total ink composition.
20) Ultraviolet radiation curable ink composition according to claim 1 is for inkjet application on the painted automotive parts or painted polymer automotive substrates for decoration and text printing purpose with clear topcoat over it.

Documents:

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Patent Number

270327

Indian Patent Application Number

869/MUM/2011

PG Journal Number

51/2015

Publication Date

18-Dec-2015

Grant Date

11-Dec-2015

Date of Filing

24-Mar-2011

Name of Patentee

KANSAI NEROLAC PAINTS LTD

Applicant Address

NEROLAC HOUSE, GANPATRAO KADAM MARG, LOWER PAREL, MUMBAI - 400 013, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	VAIDYA MRUNAL MILIND	21/203, TULSIDHAM AMRAPALI CO-OP. HOUSING SOCIETY, GHODBUNDER ROAD, NEAR TATVADYAN VIDYAPEETH, THANE - 400 607, MAHARASHTRA, INDIA.
2	MEHROTRA MAHESH GOVIND	B-904 SAVOY, RAHEJA GARDENS, OPP: TIP TOP PLAZA, OFF: L.B.S. MARG, THANE, MAHARASHTRA, INDIA
3	KHISMATRAO PRADEEP KRISHNAJI	SHREE SADGURU SADAN, PLOT NO. D-18, SECTOR - 12, KHARGHAR, NAVI MUMBAI 410 210, MAHARASHTRA, INDIA

PCT International Classification Number

C09D11/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA